BOUGHT WITH THE INCO FROM THE SAGE ENDOWMENT THE GIFT OF ficnrg W. Sag* 1891 ME FUND A'/i3l2,F CORNELL UNIVERSITY LIBRARY 3 1924 087 125 617 Cornell University Library The original of this book is in the Cornell University Library. There are no known copyright restrictions in the United States on the use of the text. http://www.archive.org/details/cu31924087125617 THE VOLATILE OILS BY E. GILDEMEI5TER and FR. HOFFMANN. LEIPZIG ■ BERLIN Written under the auspices of the firm of SCHIMMEL & CO., LEIPZIG. Authorized translation by EDWABD KREMERS MADISON, WIS. With four maps and numerous illustrations. MILWAUKEE. PHARMACEUTICAL REVIEW PUBL. CO. 1900. A -^- ■- \ Copyrighted by Edward Kremers, Madison, Wis. Germania Publishing Co., Milwaullace of traffic and commerce for westward bound Chinese and Indian merchandise. To the northward the cai-avan roads led out of Babylon thi-ough Assyi'ia and Armenia to the Black sea- (Pontu.s Euxinus) and westward through Syria to the Mediteri-anean sea (Mare Iitteriium), thence through Palestine to Egypt. In spite of their highly developed industry the Egyptians, as is well known, closed theii- doors to foreign peoples as did the Chinese. As a result commen.'ial centres were wanting in Egypt that were open to foi-eign rnei-chants and to ti-ausitory commerce. During the prime of the Babylonian empire, about 2000 to 1000 B. C, a lively caravan trade was developed which extended from China, India and Arabia to Egypt, Palestine, Syria and the Black sea. During this period, Arn.bia acquired a special importance by means of the sea traffic of hei- southern coast, which was favored by the Persian gulf and the Eed sea. At an early date, the Arabian population conducted a lively intermediate trade with Indian and Egyptian goods which were brought to the .Arabian ports. By means of caravans these were carried northward to Babylonia, Syria and othei- countries. The principal route from southwestern Arabia to Babylon, Damascus and Egypt led from Cane on the Arabian gulf (Erythraean sea) via Saba, Macoraba, Hippos and Oinie to Elath (the present Akabah) at the north-eastern end of the Ked sea. From this point the eastern route crossed the Jordan via Petra-, Kir Moab, Anmionitis and Dan to Damascus; the western route to Egypt via Azab. Axomis and MeroB. About 1.5 centuries before the Christian era, the world's commerce was gradually and, in the course of time, very greatly expanded by the Phoenicians, who lived on the narrow Syrian coast district. In the industrial and commercial held they acquired a prominent position ; as mariners,' however, a dominathig position annnig the nations of their time. Besides having practical control of sea navigation, the Phoeni- cians were the first extensive and successful colonizing nation of 6 Historical Introdncti6n . antiquity. They establislied or extended eomnieree witli tlie peoples living along the coast of the Mediterranean, they ventured through the "Pillars of Hercules" (Gibraltar) into the ocean and made accessible the products of the Madeira and Canary islands, the western coasts of Bpain and France, the British islands, and the northland as far as the amber coasts of the Baltic sea. For almost a thousand years, dui'ing whic-h time they held their prominent position in marine traffic, the Phoenicinns were the principal commercial agents between the nations of the orient and the Occident. Sidon and, since the ninth century B. C, Tyre became prominent centres of the world's commei-ce of that time, i) The Phoenicians also extended their navigation to the Ked sea and the Arabian gulf and from these to the Persian gulf. In the latter thej^ established the colonies on Arados and Tylos, islands belonging to the present Bahi-ein group. From the twelfth century up to their decline in the fifth century B. ('., these cities carried on a large transit-trade with goods from India and Ceylon to Bab,ylon, Damascus, Tyre and Sidon, and to Egypt. A caravan I'oute led from Geri-a via Salma, Thaema and Madiana, to Elath. Fi-om Elath the older i-outes to the north, to Damascus, Tyi-e and Sidon were followed, also westward to Egypt. To Babylon, on the other liand, the water route up the Euphrates or Tigris was taken from Arados and Tylos. Carthage, a Phoenician colony established in 840 B. C, soon flourished and developed su(;h powei- that it became the greatest I'ival of the motlier (.-ountry in the following century. Owing to the rise of the Pei'sian empii'e, the inland commerce of western Asia was soiriewhat shifted during the period from the sixth to the fourth century B. C. The ohl routes of traffic passing through countries controlled fiy the Pei-sians were not only kept in good condition but extensions were also made. These old highways of traiis- continental commerce underwent further changes at the time of the, Greek conquests undei- Alexander the Great at the close of the fourth century B, C. Still greater,, however, were the changes brought about by the migration of nations during the fourth and fifth centuries of the Christian era. Wars and other disturbances of the commei-cial inter- course alcHag the old caravan routes frequently restricted traffic to the ' 1) ■ Aa iS' "(veil known, the Phoenicians supplied Kinft- Solomon with the material ft)r the bnilding of the temple at .Teinisalem about loeo H, c ^^\^ Kinft-s .5 ■ 9 10" also 2. Chron., li : :i, 9; Ezel;iel, 27.) THE HIGHWAYS OF COMMERCE IN AJ^CIENT TTMF _ ^Spicerrand Grocery- TVaflpc-i-n A-nr.,-o^+ T^ — „ „_:,.,. .n. V;.T^\-^ -I IMi^ , 3eiy Trades In. Ancient Times arLdintTxe Middle A^es ) The Spice-Trnde in Antiquity and During the Middle Ages. 7 rivers arid seas. Upon the reestablishment of peace, however, commerce always seems to have found its way back to the ti'aditional caravan routes. In the course of time, however, and especiahy during the sixth and seventh centuries stiU other changes were made. Tlius, e. g. the products of the Chinese and Indian coast districts and of the Indian islands were hrouglit in part by sliip over tlie Bay of Bengal and by way of Ceylon t(.) tlie commercial centres of the Persian gulf and the Red sea. From these they were distributed by coast- wise tra.de, by river navigation up the Tigris and Euphi-ates, or by caravan to the north and west. From tlie more northern Chinese and, Indian districts the caravans passed through the present East-Turkestan following the older routes mentioned on p. fS through the countries of the Oxus to the Ai-axes. The goods, instead of being carried by river to Phasis and the Black sea, were taken as far as Artaxata and then by caravan through Persia to the ports of Asia Minor. The old route from Kandahar along the northern bordei- of the Iranian plateau, which likcAvise led through Persian territory, was also followed by caravans. During the reign of the East Eoman emjjeror Justinian, in the sixth century, when the woild empire of the Romans was broken up by the migration of nations, Persia experienced a new i-ise to power under the Sassanichv. The Persians ruled the entire territory from the Caspian to the Arabian seas and from Afghanistan of to-day to Syria and Armenia. They improved the old high-ways and caravansaries, kept them in repair and promoted commerce and traffic;, directing both over routes leading through their own territory. Owing to the wealth and luxury of the Roman empire, the commerce in oriental spices, aromatics etc. had risen to an unusual height. The East Roman empire which at that time was the principal western state with its capital at Constantinople, was forced by the Persians to procure such oriental goods as were not shipped by water, from and through Persia and to pa,y a heavy duty on them. The principal places of storage and for the collection of revenue at that time were Artaxata on tlie Araxes, Nisibis, south of the Tigris, and Callinicum (Rakkaj on the Eu])lifates. To Artaxata were brought tlie goods from the countries of the Oxus over the Caspian sea. Those that were conveyed along the caravan routes south of the Caspian sea, and those that came from the coastlands of the Persian bay up the Tigris or Euphrates centered at Nisibis. For nearly five i-enturies, the aromatics of China and India, of the Malayan an-hipelago which came via Ceylon, and in part those of Arabia were transported over 8 Historical Introduction. the two last mentioned routes to the western countries. About this time also, the levant commerce, which became so important in a future period, had its beginning. During the life of the Persian empire (up to the middle of the seventh century A. D.) all attempts, made by Justinian and his successors, to divert the transmarine commerce from its (iour.se through Persian territory remained unsuccessful. They did not even succeed in opening up marine traffic between India and Ethiopia, liec'ause Persian merchants visited the Indian markets and persuaded the Indians and Chinese not to sell their goods to new customers. In the course of time, however, the Greeks succeeded in obtaining larger consignments by water from the ports of India and Ceylon and more particularly from the coast- lands of the Arabian sea, which were rich in spices. These were delivered directly to their own ports, Kolsum, and Akabah and Berenice near the entrance to the Eed sea. About this time there existed three great caravan routes from China westward. They began in the territory of the Hoang Ho and the Yangtsekiang and passed through the Gobi desert. The northern route then took its course through the oasis of Chami, then northward along the Thian-Shan mountains through the present Dsungarai, past the Balkash sea, and via Talas. It tlien followed the Syr-Darya river to the Aral sea and the Caspian sea. The middle route passed to the south of the Thian-Shan mountains through the northern part of East Turkestan via Chami, Turfan, Karaschar, Kutscha, and Aksu to Kashgar; thence over the Terek pass to Ferghana via Samarkand, Buchara and Merw to Persia. From the Gobi desert, the southern route passed through the southern part of East Turkestan via Chotan and Yarkand, then over the Pamir plateau and through Afghanistan to the Pandschab (India) crossing the Bamian and Gazna passes to Multan. Goods intended for the west, coming via this i-onte, were taken down the Indus river to Daybal. From this port they were shipped by sea with other goods from India and Ceylon. During the seveirth and eightli centuries A. I), the Arabs carried on an extensive marine commerce with Indiii and China, especially in spices and aromatics. These were supplied in large quantities to the luxurious courts of the caliphs and the Byzantine emperors. The principal centres between China and Arabia were at that time on the Malay peninsula, to which were also Virought the products of Java and other Sunda islands. Later commerce concentrated itself in Kalah, a citv on the The Spice-Trade in Antiquity and During the Middle Agei^. 9 east «iiore of the Malay peninsula. In the tenth century there existed between Kalah and Siraf, a city on the east coast of the Persian gulf, reo-ular commercial intercourse between the Arabians and Chinese. From the northern point of Sumatra the Chinese crossed the bay of Bengal to Ceylon. Arabian merchants also settled along the Malabar coast, in Ceylon and in the Indian sea ports. From the eighth to the tenth century, Daylial at the mouth of the Indus was the most important commercial centre and seaport of India. It was the principal emporium for the" products of the iTidus valley and the Pandschab on the one side and of Mesopotamia, Persia and Arabia, on the other. For the products of northern India, Multan on the Dschelam river in the Pandschab, was the first larger rallying point. It was also a place of pilgrimage that was much revered and visited by the Hindoos. From the eighth century on, Suhar and Mus. -at, near the entrance of the Persian bay, developed as rival ports for Indian and Chinese commerce with occidental countries. At the same time Aden, at the entrance to the Red sea, bei-ame the principal port and commercial centre for the products from Yemen, Hedsjaz, Ethiopia and Egypt. In addition there were caravan routes : one from India to Persia through Seistan ; the other via Gazna. and Kabul to Afghanistan. Seti I. and Rameses II., Egyptian pharaohs, had during the first quarter of the fourteenth century B. ('. connected the Red sea. with the Mediterranean sea. In order to reestablish this sea-route, Pharaoh Necho toward the end of the seventh century B. C. tried to have a new canal constructed from Bubastis on the Nile to Patumos on the Bed sea. This was not completed, however, until 500 B. C. by Darius Hystaspes and was widened and improved by the Ptolemies. Before the beginning of the Christian era it was again choked up with sand. Under the caliph Omar in the seventh century A. D. the canal from Cairo to the Red sea was again restrjred, but did not exist longer than a c-entury. From the seventh to the twelfth century there also existed several land routes across the Suez isthmus. One of these followed the course of the old canal (clioked up with sand) from the Red sea to Cairo, whence the o-oods were shipped down the Nile and then by sea. If the passage of the goods through Alexandria, was not necessary, the shorter route over the isthmus from Kolsum to Pelusium (Faramiah) was preferred. At this time Damascus and Jerusalem were also important commercial centres. Here also oriental goods were exchanged by the luerchants of Mecca on the one hand and those of Tripoli, Beirut, Tyre and Acre on the other. 10 Historical Introduction. From the seveiitli t(.) the twelfth centurj' there existed an active coast- wise trade along- the north African coast, having its centres in Sjria and Egypt and extending as far as Morrocco and Spaiii. This commerce ac-quired a special importance for spices and aromatics although for a time it was limited by Mohammedan laws against intercourse with Christians. Commerce also soon flourished among the Greeks, who obtained spices and aromatics, possibly also i-ose water and aromatized fatty oils from Antioch, Alexandria and Trapezunt and brought them to Constantinople, Thessalionica and Cherson. Already in the tenth century Trapezunt was an important emporium for the spices and aromatics of India and Arabia and for Persian pei'fumes. The Greeks, however, purchased these luxuries only for home consumption, which was large, without distriljuting them farther to other nations. From the tenth to the fifteenth centuries, the commerce of the Mediterranean was c-onducted principally by Italian cities. In the tenth anrtaiit article of commerce of the Persians during his and the pi-evious century. Xonus Theophanes*) who in the tentii century was plivsician of Emperor Michael A''III in Constantinople, I'ecommended ro.se water as a medica- 1) Conringiu.s, Ue lu'riii. Acp;yi)t.. lib. J) Aetius, Libri me(lienl,nk'.s, fol. lo. ir, cap. 4; Bergmann, Hi.>it. cluMU., vol.4; 5) De ilestiUaticme. Schmieder's Gcsch. d. Alch., p. .S.j. 6) Antldotaruun, fol. SO. 2) S.vnesii Tract, chlmlcus. 7) Historiae chemiae etc., p. 7. 3) See Bibliosraphy; also Hoefer, Hist. ») Notices et e.Ktraits, 19, p. 364. de la ctiim., I, pp. 261—270, 9) Synesius de febribus, cap. 28, p. 112. History of Vohitile Oils. 19 ment. The Syrian physician Serapion (Janus Damascenus) wlio hved in the ninth century; also Avenzoari) who hved about a century later and who was physician to the Caliph Ebn Attafln of Morocco, used rose water as an eye-remedy and rose oil sugar as an internal remedy. In the medical writings of Abn Dsehafar Achmed, an Arabian physician of the eleventh century, which were translated into Greek by Synesius of Constantinople, rose water, rose oil and camphor are mentioned among the current remedies. 2) While Geber was the first, and also the most important Arabian writer who was acquainted with distillation, the writings of Albucasis who lived three centuries later, reveal such an exact knowledge of the subject, that the thought seems justified that distillation was largely practiced by the Arabians. The "Liber servitoris" 3) of Albucasis con- tains a very clear description of the process of distillation, also specific directions for the distillation e. g. of water, acetic acid and alcohol. Torbert Bergmann,*) the Swedish chemical historian, regards this description as one of the first and best. During the period from the eighth to the twelfth centuries, many Araliian scientists were especiallj^ active in furthering the s(.4ences of medicine and materia medica. Distillation was frequently resorted to as a means of securing the active constituents of drugs. In spite of the crude methods often emplo,yed, it seems probable, tlierefore, that the volatile oils which, no doubt, separated at times must have attracted the attention of the curious experimenter. Owing to the complete lack of knowledge regarding the nature of the oils as well as on account of the idea that the distilled waters contained the subtle active ingredients of the drugs, the oils whicli separated may have received but little consideration, being regarded as crude separations. They were, therefore, not valued highly and, as the literature of that period shows, only a few of them found application. The desire to transmute the baser metals into gold, which began to predominate in the eleventh century, brought about the decay of Arabian science. From the conquest of Bagdad by the Mongols in 1258 dates the political downfall of the Arabs. In Spain and also in Italy, through their school at Salerno, Arabian science still held sway 1) Liber Theizier etc., Liber 7, fol. 1; Lib. .'., cap. 9, fol. 44. 2) Synesius fie febribus, pp. 58 & 240. 3) .See .4rabian -ivriter under Bibliography. *) Bergmann, Historlae chiniiae. Comp. also Liber Servitoris, fol. 339b, 341b & 342. 20 Historical Introdin-tion. for some time. In these coimti-ies also, through tlie crnsades, Europeans became acquainted with Ai-abian scientifi(; ideas, as well as with their methods, among others with the process of distillation and the utensils used in this ijrocess. In the Eui-opean countries alohemistic speculations were welcomed ill the monasteries where mysticism and faith in miracles were at home. Though distillation did not become a lost art by any means, it was employed principally hi the search for the philosopher's stone and the panacea for all human woes. The distillation of alcohol also was given much attention during this period. Thus the Cardinal Vita lis de Furno at the beginning of the fourteenth century declared it a true j)anacea.. Albertus Magnus (1193—1280), Bishop of Regensburg, carefully described the distillation of alcohol in his works. Arnoldus Villanovus (123.') — 1312) seems first to have introduced the Arabian term alcohol into German literature, and on account of its properties, designated it aqua vitae. i) The latter was also acquainted with the distillation of the oils of turpentine, 2) rose- mai-y,'') and sage. His oleum mivabile c-onsisted principall.y of an alcoholic solution of two of these oils. This mixture was used as an external remedy and later, with the omission of the turpentine oil, as an aromatic perfume. For centuries it remained a much praised specialty under the name of Hungarian water. Alcohol was also used for the extraction of spices and other plant proilucts. In this manner alcoholic solutions of volatile oils, of aromatic resins and balsams were obtained. *) From the thirteenth centurj' on distilled aromatic waters were nn.ire extensivelj^ used as medicaments. The separation of oils both at the surface and beneath the aqueous distillate wag observed, but apparently received but little attention. Owing to the practice of using alcohol in the preparation of many of these aromatic waters, the oil must frequently have rema,ined in solution wholly or in part. Thus, e. g. the plants or plant products to be distilled were moistened with wine or aqua vitae before distillation; or steeped in water they were first allowed to undergo fermentation. Both alcohol and volatile oil were lost, in part at least, by submitting the plant products to a ]irocess known as circulation, a prehniiiiary operation consisting of more or less prolonged digestion. In this manner inferior ilistilled aromatic waters were (jbtaiued. 1) Opera omnia, I,ib. de Yinie, p. 55.S. 3| Opera omnia, T,ib. de viiiis, p. 389. 2) Kerviarum practieac, p. 1055. i) Ph. Ulstadii, Coelum pliilosoplioriim. History of Volatile Oils. 31 Nevertheless, several of the more important experimenters and writers of that period knew and described volatile oils. In addition to the oils of turpentine and rosemary alreadj' mentioned. Arnoldus VillanoTUsi) and Eaymundus LuUus^) describe the distillation of oil of sage; Sancto AmandoS) that of bitter almond oil, oil of rue and oil of cinnamon ; Saladinus of Aesculo*) that of oil of rose and oil of sandal- wood. The writings of their contemporaries also reveal a knowledge of these and othei- distilled oils without, however, making mentioti of their use in medicine or the arts. The epoch-making inventions and discoveries of the fourteenth and fifteenth centui-ies wr(inght great changes in the natui-al sciences and their application. The discovery of the new world and the circum- navigation of •Africa to the East Indies widened the horizon of the people. The period of the Kenaissance and the Keformation assisted in doing away with the blind faith in authority, not only in theology but in the natural sciences, as well. The founding of universities and the invention of printing assisted largely in the spreading of knowledge. Thus information and skill, previously the secret of the few, now soon became common property of many. With the rise of Paraiielsus, who taught that the object of chemistry was to make remedies and not gold, and the establishment of the iatrochemical school, the art of distillation was once more directed into its more proper course. More particularly, with the separation of pharmacy from medicine and the establishment of apothecary shops, the distillation of aromatic waters was carried on in the laboratories of these pharmacies and was here developed until the distillation of volatile oils became an independent industry. As was largely the case with the Arabians, the progress of the art of distillation again finds expression in medical literature. Though medical books became much more numerous with the invention of printing, they cease largely to be a source of inff)rmation with regard to methods of preparation of volatile oils and their introduction. Nevertheless, they give information about the introduction of aromatic drugs and aromatic waters. The numerous works that come under consideration may be classed in three groups of equal importance: the antidotaries and later dispensatories; the treatises on distillation, which were prominent from tlie close of the fifteenth to the close of the 1) Opera omnia, Lib. tie vinis, foi. .589. 3) ExpOHitio supra Antidot., toi .32S. 2) Experimenta nova, vol. 5, fol. 829. *) Compencliiini aroHiatariorum, fol. .'i49b. 22 Hintorieal Introduction. sixteenth centuries ; and the price ordinances for spices and drugs of various cities, whicli came into use about the same time. Before discussing these works, attention should once more be called to the fact that the term "distilled'' as used in ancient and mediaeval writings is not always employed in the same sense as to-day. In fact, up to and including the middle ages it was a collective term implying the preparation of vegetable and animal extracts according to the rules of the art, or rectificiition and separation : it involved such processes ars maceration, digestion, expression, straining, filtering and even processes of fermentation and decay. Aside from turpentine or cedar oil, the term (iistilled oil, as it is used in older literature, applies as a. rule to fatty oils whic'li had been aromatised with the respective plants or parts of plants. That many seeds and fruits often yielded aromatic oils upon hot or cold expression, or when boiled with water was also known in early antiquity. These aromatic and aromatised fats and fatty oils were used medic-inally as ointments and for cosmetic purposes. Whether the oils of rose, andropogon, and calamus, mentioned in the Ayur-Veda as distilled oils, wei'e such in the modern seiise of the term, cannot be decided. The same is true of the oils of spike, ro.semary and sage, as well as of other oils of later writers. Altlicjugli the Indians, the Babylonians, and especially the Egyptians were aequainted with the art of distillation, and also with volatile oils, a sharp distinction between true distilled oils and ai'omatised fatty oils does not seem to have existed at the beginning of the Christian era. Inasmuch as the aromatised oils were used principally in religious rites and for purposes of toilet, it seems natural that tliey were given preference over the distilled volatile oils. Indeed, the pi-ocess of ]>reparation of "distilled" oils described by DioscoridesM and copied by Pliny 2) is one of aromatization. It may well be doubted that volatile oils esi'aped observation by Arabian naturalists and others who distilled aromatic waters, although, as has alreadj- been pciinted out, the presence of alcohol in the distillate may frequently have kept the oil in solution. Tliough a number of distilled oils are mentioned in various treatises and were evidently known, yet one of the oldest known lists of current drugs and spices, that of the city of Frankfort-on-the-Main of the 1) Matthioli Opera quae et., lib. 1, cap. 53: Germ. traiiKlation of DioBCoi-ide.«' worke in TromniMdoi-ff's .Jour. d. Pharni.. 11, pp. 112. 2) Naturalis lilstoriae, lib. i:!, cap. 2. Sibcr&catrcoiltill9ndi,9esim(Mia'bu0, ^0 buclj x>a recl?ten hmk 0t)iftilierent>ie emt^igetMtig von^^ictcnymo Pmnrc^wy^f/Pittti^vriwimtmrQet^erfnfetlK^e (rye (TrtttfTrAgPnixr, un gctrucht Ourcb Oen wobLgeacbte Jobannem gcucntngcr 3u Straesbucg in Oen acbtc tag C»e6 mc^cn als man 3e(t von &er geburt Cbristi tunfscbnbunOert. Xob 015 got. Hnno 1500. Fis. 1. 24 Historical Introduction. year 1450, does not mention any dintilled oils. However, a similar list of the same city for 1582 mentions forty-two, and another of the year 15S7 enumerates fifty-nine such oils, i) To return, however, to the literary documents of the sixteenth century. Among- the most interesting, if not the most valuable, are the treatises on distillation, the "Destillirbiicher". The first larger work of this class was written hj the Strassburg ]3hysicia.n, Hieronymus Brunschwig (1450—15.34), the two volumes being published in 1500 and 1507 respectively. 2) The work describes principally the preparation and use of the mui4i lauded distilled waters (gebmnnte Wasser), dis- tilled wines {gebrannte Weine). life elixirs, simple and mixed oils and balsams. How little attention was given to distilled oils is shown by the fact that but four distilled oils are mentioned and described, viz., the oils of spike, 3) turpentine,*) juniper woods) q^^iA rosemary. 8) Directions for the rectification of turpentine oil are also given, viz., by shacking first with water, then with rose water or wine, and by final distillation. Ax\ oleum benedictum coniposituni'') consiatii of a distillate of rosemary, turpentine, olibanum, mastic, ammoniac, galbanum, opopanax, cloves and cinnamon. Directions are further given for the prepai-ation of a number of aromatic balsams, mixtures of volatile oils, bj^ the distillation of nuxtures of oleo resius and spices with the addition of turpentine oil. ^ ) How little the nature of the distillates was uudei'stood becomes apparent from Brunschwig's definition of the process of distillation. He states that it consists merely of the separation of the subtle from the crude, to make that which is fragile and destructible indestructible, to render immaterial that which is material, spiritual that which is corporeal, handsome that which is not handsome. Nevertheless he dis- plays a considerable knowledge of the technique of distillatiou. For this verj' reason, however, it seems strange that no mention is nuide of the observation of oils when such aromatic plant products as the umbelliferous fruits, the labiate leaves, juniper berries, cloves, cinnamon and other spices were subjected to distillation with water. This is all the more remarkable since the volatile and even empyreumatic oils and other products of distillation such as a,cetic acid were regarded, like alcohol, as the quintessences of the ci-ude materials from which they were obtained. 1) See the price ordinances fur tlie 4) ibiilem, Voi. 1, toi. 88. corresponding year.'i under Biijliogvaptiy. a) do Vol. 2. fol. 280. 2) See fig. 1 and 2, pp. 23 and 25. r,) iici Vol. 1, fol. 52. 3) Hieron. Brimscliwlg, Lilier de arte 7| ,1,, vui i f,-,) ^y distillandi, Vol. 1, tol. 72, S) (],, \q\ o. fol. 271 History of Volatile Oils. 25 Xibei?t>€ai?te^ifril landi X>c dompofiti^* CompejiM w fimplicw/ionb b? 336{§ t^efattrae pttt^ tCwpcnma votnirJ^ttommobmfc^widvfF gcclitbtvftgcoffeiibrtrt 5ttttO|t bctte{»iee6b^K» gctrucftt un gcnOigt in Oic hcisserlicbc fr^e statt Straesburg uff sanct ^atbis abent in 5em jar 1507. Fis. 2. 26 Historical Introdnetion. Brunschwig's "Destillirbuch" was followed by a number of similar treatises, all of which reveal the important position which the distilled waters held in the materia medica of the sixteenth century. To some extent they contribute to the history of the volatile oils themselves. About twenty-flve years after the publication of Brunschwi{i"s treatise, the smaller work of Philipp Ulstad, physician and professor of medicine in Niirnberg, appeared 1 1 and became widely known. Ulstad held notions similar to those of Brunschwif;- with regard to the nature of distillates, and sini-e his quintessences contained more or less alcohol, no mention is made of the oils themselves. The principal value which these w(3rks have at the present time as far as the hist(n-y of volatile oils is concerned, lies in the thorough Jind careful description and figurative reproduction of the methods of distillation and utensils employed at that time. About 5(5 years after the appearance of Bruns(.-hwig's "Destillir- buch" and 28 years after that of the first edition of Ulstad's "Coelum Philoso])horuni," Walther Hermann Eeiff (Gualtherus H. Eyff), who was sni-geon in Strassburg during the first half of the sixteenth century, jmblished a third tivatise^) of tliis kind Avliieh for a long time was held in high repute. His definition of distillation does not differ materially from that of Brunsi-hwig. In the last part of the book he also describes ''the correct methoil of preparing by means of artificial distillation several precious oils." They are distilled, some of them with wine, from m3rrrh, liquid storax, sagapenum, opopa.nax, ainmouiac, storax calami ja, sacocolla, benzoin, labdanum, galbanum, turpentine, mastic, sandarac, guaiac wood, rosemary, spike, anise, cloves, cinnamon, mace, safron, and from various mixtures of spices (balsams). Under spike and lavender oil (fol. ISO) he mentions that the.se oils are (commonly imported from France in small bottles and sold at a high price. In liis "Reformirte Apotliek" which was published in 1563 he states (fol. 101) that "when lavender flowers are distilled a fragrant oil usually floats on tlie surface of the distillate. In Franre. in the province about Nai-bonne, where the plant grows abundantly it is especially distilled; likewise oils from other useful and frn;;rant herbs flowers, fruits and roots." This statement is of si)ei-ial interest inas- much as it seems to be the earliest reference in German literature to the French volatile oil industry which evidently (kites back as far as the early part of the sixteentli i;entui'v. 1) See Bibljosraphy. 2) (Jlialth. Ryff, Neii gro.sN Dftstillirbucli. See Bililiosraphy. History of Volatilf Oils. 27 How little KyH knew ab<3ut the nature of volatile oils becomes apparent from fol. 187 and 188 where he describes "how from several strong- and good spices precious oils can be distilled." To prepare specially good oils from cloves, nutmeg, mace and safron these spices are to be comminuted and distilled with rectified spirit. When the "spirits" have been distilled off and oil begins to come over, the mass is to be taken out and pressed between warm plates. The oil thus obtained is to be rectified by "circulation" until it is clear. Brunsch wig's "Destillirbuch" seems to have stimulated the distilla- tion of aromatic waters and of spirituous aromatic distillates, and their introduction into medicine, as well as the art of distillation itself. It would appear that his and other treatises of a like nature, in a measure at least, displaced the older antidotaries. However, in the course of the sixteenth centurj^ the latter wei-e also reprinted and revised in various European cities. Among the principal treatises in this group are those of Valerius Cordus and Conrad Gesner, whose writings acquired great i-eputation and served as the standard for others. Valerius Cordus was born in 1.51.5 in Simshausen. His father was professor of medicine in Marburg. Here he studied medicine, receiving the bachelor's degree in 1531. In the same year he went to Wittenberg to attend the lectures of Melanchthon, and soon received permission to deliver a course of lectures on the materia medica of Dioscorides. He died 1511 in Eome. His commentaries^) on Dioscorides and other scientific writings were published after his death by Conrad Gesner (1516—1565) of Ziirich, a talented medical writer, who probably made additions of his own to the text of Cordus. These "An7iotationes" of C(jrdus are of special importan(?e in the history of volatile oils, partly on account of the reputation of the author, partly because of his knowledge of the subject and also because they appeared in a century that was so productive of literature. Whereas Brunschwig's book reveals a retrogression in the technique of dis- tillation as compared with the Arabian period, Ulstad, Eyff, Matthiolus, Loiiicer and others made many improvements themselves and also made known many of the older pieces of apparatus that had been forgotten. Cordus and Gesner utilized their discoveries and went even farther. In the chapter on the distiUation of oils,*) Cordus discussed the nature of the "extrticts" of plants obtained by expression and dis- tillation. Concerning the oily plant extracts, Cordus distinguished 1) See Bibliography. *l Liber de lirtiflclora's extractlonibua, lol. 22G iit the Annotationes. 28 Historical Introduction. between the viscid, fatty oils (oleum erasnum, viscosum, terrestre) ohitained by expression, e, g-. of seeds, and those of a spirituous nature {aerea) which can be separated from the "terrestrial" substances by distillation. As illustrations of the first class, he mentions a number of the common fatty oils, as illustrations of the second class the oils of carpol)alsam,i) cnrdaniom. culjeb, pepper, cloves, cinnamon, mace, nutmeii', hgnaloes and those of some of the common umbelliferous fruits, such as anise, fennel, caraway, cumin, angelica, Ligiistruw, Lil/anotns, Pa^tinaca, Apium, Petroselinuw. Pinipinella and Anethnm. In his description of the properties of volatile oils, f'ordus makes mention of the remarkable propei-ty of the oils of anise and fennel to congeal to a Ijutyraceous or spermaceti-like mass; also of the property of the oils of cimiamon and cloves to sink under water. The method of distillation of volatile oils has Ijeen carefully described by Cordus, the description being accompanieil by a cut of a primitive glass still constructed by himself. -) Of still greater value than the "Annotationes" of Cordus is the "Thesaurus Euonymi Philiatri" of Conrad Gesner. The Latin edition was pf)ssibly published as early as 1550 ; a German edition in 1555 uniler the title of "Ein ko.stlicher theurer Schatz des Euonymus Philiatrus." Compared with Brunsdiwig's treatise it not only reveals a decided a.dvani'e in the technique of distillation, but the first German edition of 1555 also contains several chapters on di.stilled oils (pp. 212 — 240) and on "balsams"' and other mixed oils (pp. 249 — 273). The distillation of a number of oils, viz.: of the oils of lavender, ro.se- mary, r>ie, cinnamon, cloves, nutmeg and others, is described, and the description accompanied with cuts of the apparatus to lie used ; also the distillation of juniper berries and juniper wood by clestillatio per ascensum and destillatio per descensuni. The oils of galbanum, lab- danum. myrrh, opojianax, liquid storax and styrax calamita. mastic and turpentine an ilescribed. The oils from guaiac wood and sandal wood and from several other woods and barks are mentioned (pp. 244 — 247) and their distillation described. Gesner's notion about the nature of the volatile oils does not differ much from the traditional one mentioned in connection with Brunschwi'i'. His practical conception of a volatile oil is also rather confused, for in describing the several methods according to which one and the same 1} The fruits of Bjtisnrnen lueccanensis (IkMUtsfh { BalsniuorJenrlron opolialfiamiin Kunth) were formerly known an carpohalsanium and used medicinally. 2) De artifieioHis extractionibus, vol. 2, fol. 226. History of Volatile Oils. 2& '"distillpd"' oil can be obtained, he not oidy enumerates distillation proper, but also the di|j;estion with fatty oils, e. ' l)urnt. Possibly it was found that in some instances a larger yield of oil was obtained. Glauber also made similar use of muriatic acid. These presumptive improvements, however, did not raise the art of distillation in general above the basis of empirical experimentation, and t]iP seventeenth century closes without having made any material con- ti-ibution to the history of volatile oils. Neither did the eighteenth centui-y have much to add. The phlogistic, theory conceived by J. J. Becher (1635—1681) and logicaly worked out by G. E. Stahl (1660— 1734) failed altogether in throwing new hght on the organic world and thus could not assist in a better understanding of the composition of volatile oils. 3 34 HistorialJ In troduetion. ' Renewed progress, however, in tlie manufacture arid use of volatile oils is to be recorded during the eiohteenth century. The technique i^f rlistilla- tion was improved in the laboratories of the apothecary shops wliere the oils were lai'gely distilled and a better product was prepared. The oils found ap[)lication not only in medicine, but also in the art.s and in the household. The number of oils irientioned in municipal price ordinances and other literature up to l.jOO had l)een only thirteen; in 1540 the number had increased to thirty^'our and in 1589 to one hundred and eight oils. The "Dispensatorium Noricuiu" of Cordus mentions only three oils in 1543; the edition of 1552 mentions tive ; that of 1563 six; ami tliat of 1589 fifty-six oils. In 17(18 one hundred and twenty oils are mentioned in the price ordinances of that time. The distillation of pure volatile oils and the skill to mix them so as to produce agreeably fragrant mixtures, not only stimulated the improvement of methods of preparation, but also their use for pui'poses of comfort and luxury. As has already been indicated') a volatile oil industry seems to have developed from small beginnings in soutliern France during the fifteenth and sixteenth centuries with the distillation of lavender and rosemary oils. In like manner, tlie perfume industrv seems to have had its origin. The preparation of "Hungarian water" in the sixteenth century by making an alcoholic distillate from fresh rosemary has already been referred to.^) During the .seventeenth <;eutury, a "Ka.rmeliter Geist," an alcoholic- distillate from balm and lavender, ■') was intrfxluced. In 1725 .Toha.nn Ma.ria Farina of Cologne introduced his famous Eaii rle Cologne. The successful nuxture of several odors and the prime quality of the oils used ]>roved an importa,nt stimulus to the manufacture of these oils.J^) From these small beginnings the perfume industrv gradually developed into the important position it has held since the miildle of this century. With the increased importance of the volatile oils, inore attention was bestoweil upon their nature ami composition. Boerha.ave, who at the begimung of the eighteenth century was professor of medicine, liotany a.nd chemistry at the University of Leyden, in his treatise on chemistry states that volatile oils consist of two elements: the one cruder and resinous, insoluble in water {ni;iter)\ the other more subtle, ethereal, which can sc-arcely be weighed and which by itself is possiblv gaseous (spiritus rector). The first part he considered to be connnon to all oils and a unit by itself. The chara.cteristic odor a,nd taste. 1) See p. 2(j. 3) See Oil ol Banu. 2) See p. 211. 4) See Oil of Spike. History of YoJatile Oils. SsR however, of the various oils were clue to the spiritu.s rector which was peculiar to each oil. It was water soluble and therefore gave to the distilled waters their odor, taste and medicinal virtue. The changes produced in volatile oils upon exposure to air and light \vere attributed, in harmony with this theorj-, to the escape of the spiritm rector.^) This conception was perfectly in harmony with the belief in the subtle properties and medicinal virtues of aromatic plant substances and their aqueous distillates. With the assumption of the water solubility of the spiritu.s rector the distilled waters were naturally regarded as being charged in the highest degree with the medicinal properties of the crude drugs Boerhaave's dnalistic theory was therefore received as the most rational explanation of the firmly estab- lished belief in the efficac.y of distilled waters, and was also accepted as a further argument for their retention in medicine. Even after the anti- phlogistic nomenclature came into vogue after 1787, the spiritus rector was not discarded, being rebaptized as arome. The first chemists who discarded the dualistic theory of the volatile oils in their writings, and claimed that odor and taste are due to the oil as such, are T. A. C. Gren,^) Professor of Medicine in Halle, and the French chemist Ant. Franc;ois de Fourcroy^) of Paris. The former ■exposed the untenability of Boerhaave's theory in 1796, the latter in 1798. Indeed Fr. Hoffmann (16G0 — 1742), a contemporary of Boerhaave and professor at Halle, had not accepted the latter's theory without reserve. A many-sided investigator and writer, he had prepared and studied the volatile oils with great care.*) Yet he had no clearer conception concerning the preparation, yield and properties of the oils than his contemporaries. He distinguished between oils obtained by expression, by de.stillatio per Hscensuw and per desceimum.") He regarded sulphur as a fundamental principle of all oils, the liituminous and empyreumatic oils containing a relatively large amount of sulphur, s) He also believed that the color and odor of oils was influenced by their larger or lesser sulphur content. 1) Boerhaave; Elementa chemiae, vol 2, p. 124. 2) Grundri.ss d. Chemie, vol. 2, p. 217. 3) Ann. de chiniie, 25, p. 232; also Systeme des connaisKanees cliimique. *) Opera omnia. See Bibliography. 5) The desf/IUitio per ascoTtviiin corresponds to the method now generall.y used, allowing the vapors to pass upwards in the still and removing them from above. In the destillatlo per descensiim the vaijors were forced downward through the material and collected in a receptacle underneath the still. An incomplete e.^ctraction was thus effected. (Comp. chapter .3.) H) Opera omnia, tom 4, liber 1, p. 4i9— i.'jl. 36 . Historical Introduction. It h'hould be of interest to note that camphor which liad been regarded as a volatile organic salt, was pronounced liy Hoffmann to be a congealed volatile oil.i) He also made the (jbservation that most of the commercial oils of his time were adulterated with turpentine oil. oleum vini, alcohol and fatty oils. 2) Further he determined the yields) and specific gravity*) of many oils. Glauber's suggestion that oils which had become colored by age be rectified with dilute liydro- chlorici acid") was opposed b.y Hoffmann. He de(/lared the employment of spiritus salis,'^) dilute sulphuric aeid,'^) potash; tartar and alum*) in the distillation of volatile oils as useless, but consented to the use of common salt. He argued that the addition of salt facilitated the separation of the oil particles and prevented decay; that it made the water "heavier" and thus prevented the settling and Ijurning of the plant material; that it also purified the distillate.^) In some instances recourse was again taken to the process of fermentation before distillation which was in vogue during the fifteenth and sixteenth centuries. This was done e. g. with juniper' berries, wormwood, sage and other herbs, honey and yeast i^') occasionally being- added. The old practice of previously moistening the plant nuiterial with alcoholic) was also resorted to. In this manner a larger yield of oil was obtained but it would seem that the dilution of the oil with alcohol was not recognized. Downward distillaticin (dostillutio per descensuw) was applied by Hoffmann 12) in tJie preparation of oils with high specific gravity such as the oils of cinnamon and cloves. This method was evidently regarded as being better because the dark colored oils thus obtained were supposed to contain more sulphur. With the increased use of volatile oils during tlie first half of the eighteenth century it became more and more desirable not only to prepare oils of good quality but to obtain the largest possible yield as well. As guides there a-ppeared new treatises on distihation which had 1) Opera omnia. Liber 72. Observatio IS, p. 44—50. 2) Ibidem. Liber (57. Obsorvatio 2, p. 9—11. 3) •' " fi:". " 1, p. 1— 1, vol. 4, p. ,->0. s) Olanberli, Fnrni novi philosophioi, pars 1, p. 38: et pars 8,' p. 31. 0| Hoffmann, Opera omnia. Supplemen'tum secnndnm. Pars 1, p. 730. ID) Berl. .Jahrb. f. Pharm., 1804, p. 380. 11) Demachy, I.,aborant im Grossen,' ]j. 238. 12) Hoffmann, Opera omnia, torn. 4, lib. 1, p. 44.)-L-, 1 . - Snpplementum secundum pars 1, p. 730. ' Histnrv of Volatile Oils. . 37 little more than the title in common with the older Destillirbiicher. Of these the works of Bnrghart,^) Dejean and Demachj'-i) may here be mentioned. Following the lead of Winther,-') Boerhaave and Hoffmann, a number of investigators of the eighteenth century ascertained the yield of oil obtainable from the more common aromatic plant products. Of these the following deserve special mention: Joh. Fr. CartheuserS) (17()4_ 17(50), Professor of Medicine, Botany and Chemi.stry at the University of Frankfurt-on-the-Oder ; Caspar Neumann^) (1083—1737), a Berlin apothecarj- Claude Joseph Geoffrey,'') a Parisian apothecarj^; and Francois EouelleS) (170.H— 1770). Their experiments were conducted on a small scale and with simple apparatus. Their results, however, published in their works and in journals, 8) were regarded as standard and were quite generally introduced into the literature on the subje(/t. Through the dispensatory of the English physician and chemist, William Lewis, ■^) the results of the above mentioned investigators and of others found their way into English literature. Aside from the publications already mentioned, the intei-est shown in the study of volatile oils toward the <;lose of the seventeenth and during the course of the eighteenth century is possibly best shown by the number of dissertations on the subject which were written at German universities under the stimulus of a number of univei-sity teachers. The more important ones are herewith enumei'nted : 1670. 'De oleorurn destillationim iiatura et u.sn in g-enere." Dinsertatio ab David Kelhier. Helriistadii. 1690. "De oleis destillatis.'' Dissertatio ab Henrico Rosenberg. -Jenae. 1741. "De oleis destillatis empyreumaticis.'' Dissertatio ab Cliristian LiiKhier. Fraiicofurti ad YiadT'Uin. 1 ) See Biblioflraph.v. 2) See p. yi. 3) See works enumerated under Bibliography. *) In tlie second volume of his Chymia medica, etc. 5) M^moires de I'Academle Itoyale des Sciences de Paris, 1730— 17G0. 6; In 17811, Remler of Erfurt collected and tabulated the oh.servations relative to the yield and ijroperties of volatile oils published up to that year. A similar tabular compilation taking into consideration also the origin of the oils was published in the ".Journal de pharmacie" for August 1K34 by Raybaud of Paris in connection Avith the industrial exposition of the previous year. A German translation appeared in Buchner's "Repert. d. Pharm." for 183.5, vol. .51, ji. 54. Two further treatises on this subject appeared by CJ. H. Zeller In 1850 and 1S55 respectively in the ".Jahrbuch fiir iiralitisehe Pharmacie und vern-andte Fiicher." The former appeared also as a sefjarate u)ider the title of ■'Studien iiber iitherische Oele," I.andau, 1850; the latter under the title '-Ausbeute und Darstellung der iitherisclien dele." Stuttgart. 1855. 7) See Bibliograph.v. 174-t. 1745. 1746. 1747. 1748. ] 752. 1759. 1765. 1765. 1765. 177H. 38 Historical IntTorhiction. "De sale volatili oleoso solido in oleis aetbereis noiinunquaiii Teperto." Dissertatio ab Fr. Gtiiitlier. Francofiii-fi ad Viadruiii. "Ue oleis vegetabilium esseLitialibus.'' Dis.sertatio ab A. Fr. Waltlier. Lipsiae. "De spiritu rectore in regno animali, vegetabili et fossili, atraosiiliaei-ico." Dissertatio ab Gottfried de Xhora. Leydae. "De oleoriiin destillatoruni usu niultiplice principue in ea.stris." Dis- sertatio ab Job. Paul Ziegler. Altorfii. "Dissertatio cbemiea inauguralis si-stens Dosioiasiani concretionum in nonnuUis oleis aetbereis observatuni" ab F. Hagen. Regiomontaiiae. "De oleis essentialibus aetbereis eornmque modo operandi et nsu." Dis- sertatio ab Jobann Friedr. Vangerow. Hallae. "De oleis destillatis aetbereis." Dissertatio ab Fr. W. Eiken. Helnistadii. "De partibus oleoruni aetbereoruni constitutivis." Dissertatio ab Jobannes Cbrist. Scbniidtins. .Tenae. "De partibus oleoruni aetbereoruni constitutivis." Dissertatio ab J. Vr. Faselius. .lenae. "De oleis vegetabilium essentialibus, eorunique jiartibus constitutivis." Dissertatio ab W. B. Troiniusdorff. Erfurti. "De adulterationibus oleum aethereorum. Dissertatio ab K. W. (Jhr. Miiller. Goettingen. The investigations reported in these dissertations, however, rest on false premises and, therefore, produced no valuable results. Research based on the phlogistic theory and the doctrines of Boerhaave and Hoffmann concerning the constitution of volatile oils, could hardly be expected to yield i-e.sults of any importance. How crude the notions concerning the chemical natni-e of volatile oils were even at the time of Scheele, is shown in a dissertation i) of the year ITGo accepted by the University of Jena. From it the following propositions or conclusions are (juoted : : "Tbe essential constituents of volatile oils are of two kinds, solid and liquid. To the first class belong sulpbur, |)blogiston, eartli and salts; to tbe second class air, tire and water. Tbe presence of tbe first is revealed by the inflaniniabibty of tbe oils, for every object tbat burns witb a flame contains niucb sulpbur or phlogiston. Tbe color as well as tbe coloration of tbe oil likewise argue in favor of tbeir presence. Some oils are .yellow, otbers green or blue; with age, tbe colors become darker. .\s is known, all coloration is due to particles of sulpbur or pblogiston. Such oils bave a penetrating odor, which is caused by tbeir content of volatile saline sulphur particles. Tliey, therefore, contain sulpbur or pblogiston in sufflcientl.v large quantities. "In tbe course of time these oils are converted into a resinous mass, a cbange tbat is not conceivable witbout pblogiston. 1) "He jiartibuH oleornni ai'tlicreiiriiin cnnstitutivis." Dissertatio inaujiui-alis .ToiianTH's CliriHtianus Sclimidtitis. .lenae rl. 30. Maerz tTG.j. History of Volatih Oils. 89 "Volatile oils always burn with a smoking flame. All soot, lio\\ever, consists of earth, salt, water and phlogiston. When the oils ai-e treated with nitric acid, a residue of earth and earbon remains. "Some volatile oils have a higher specific gravit3' than water. This is due to their larger content of earthy constituents and salts." The crystallivie deposits formed in .some oils upon standing, also the congealing of certain oils at lower temperatures. whi(-h had l)een observed by A'alerius Cordus m l.'riO, by Kunkel in KiH.""), by J. H. Lhdc in 1717, by Friedr. Hoffmann in 17t»l, hy Caspar Neumann in 1710 and by others, \vere .studied. The crystalline parts were regarded' as a volatile salt, later as a camphor peculiar to each oil, at times also as benzoic acid.i) Hoffmann explained the congealing of oils of rose, anise and fennel by assuming the formation of a curdled modification of the oil. NeuTTiann in 1719 and Geoffroy in 1726 regarded the crystals formed upon standing as camphor. ^) The formation of such crystals was observed in the oils of thyme, cardamom and ma.rjoram bj' Neumann ; 3) in peppermint oil by Gaubius*) of Leyden in 1770; in oil of mace by Wieglel)5) in 1771; in the oils of lavender, rosemary, sage and marjoram by Arezula") in 1785. They regarded these separations as varieties of camphor, only Wiegleb thought them to be peculiar combustible salts. '^) In 1793 and 1791 Margueran studied the action of frost on volatile oils and observed the formation of crystals and congealing in i-omiection with a number of the more common oils.'*) The study of the action of various reagents on vi^latile oils, which was begun aliout the middle of the seventeenth century, yielded but a superficial insight into their nature. Tlie repeated distillation of oils over rlialk or burnt lime,") conducted l)y the excellent (/hemist Homberg about the year 1700, produ(;ed no results whatever. The action of .strong acids had been observed by Glauber lo) as early as l(i(53. The 1) Hagen, "DiHsertatio (.'hemica inaiisuralis sistens dci.siiiiasiam, concretionnm in nonnulliH oleiB aethereis observatoruiii." Eesiomontanae 1748. P. .]. Macquer'H "Dictionnaire de Chyniie." Germ, transl. by .J. (i. Leonhardi. Vol. ■4-, i». -l:fi.5, loot note 0. 2) Mem. de I'Acad., 172*;, p. 95. . 3) Ue HalibuH alcalino Axis et camphora. Bernlini 1727, p. 10.5. ■1) Adversariornm varii argumenti liber unus. Leidae 1771. Sectio 7. ji. '.)'.) — 112 = ) Vogel's Lehrsiitze der C'heniie, § 34.2. 6) Kesultato de las e.\periencas hachas sobre alfanfor de Mnrcia con licencia. En Segovia 1789. 7) Comp. Vogel's Lehvsatze der Chemie, edited by Wiegleb. 8) .lour, de chim. et de phy.s., 2, p. 17K; Crelts Cheni. .inn., 2, pp. 19.^. SI and 4H0. 9) .\I^m. de I'Aead., 1700, |i. 29S ; and 1701, \i. 129: also ('hem. u. hotan. Ahhandl., vol. H. p. l.oo — li^7. 1") Pro«perita.s rjermaniae. _ . ; I 40 Historical Introduction. effect of stronji- uitric' acid on a iiumljer of distilled oils was studied by Borrichiugi) in 1G71, by Tourneforts) in 1698, by HasseS) in lim; that of sulphuric acid by Kunkel*) in 1700 and byHombergS) in 1701. A more detailed study of the action of strong acids on volatile oils was made by Hoffmann") and by Geoffroy'^) in 1726 and by EouelleS) in 1717. Upon distillation of oils with strong hydrochloric acid, especially if the acid was generated in an almost anhydrous condition in the experiment, it was supposed that compounds of the oil with the acid were obtained. Such a supposed compound was known tf) HombergM) as early as 1709. The preparation, however, of such a compound of definite chemical composition was first accomplished by Kind.i") an apothecary in Eutin, in IHOH bj^ the action of hydrogen chloride gas on turpentine oil. The solubility and color of distilled oils also re<-eived attention during the eighteenth eenturj'. Thus Macquer") in 174.j published his investigations on the solubility of distilled oils in alcohol, whidi wei-e the most extensive on this subject. The color of oils and the changes in color were studied by Hombergis) in 1707 and by Bindheimi^) of Moscow in 17H8. The latter arrived at the conclusion that the color depends on a larger or lesser amount of resin carried over in the process of distillation, hence the darker (/olored oils are apt to contain considerable resin. As has alreadj' been pohited out. the phlogistic theory afforded no satisfactory basis for the study of organic substances and consequently of volatile oils. ' With the discovery of oxygen by Scheele and Priestley during the years 17711*) t,-, 1774 and the ingenious interpretation of this and other discovei'ies by Lavoisier with the aid of the balance, a reaction against the phlogistic theory set in whidi resulted in the inauguration of the present i/hemi(?al period. The study cif the chemii-al constitution f)f substances was placed on a rational scientific basis. Inorganic chemistry, liMving to deal with the sinqiler substances. 11 ,\cta med. et iihil. HiiFfn.. 1<;T1. i"l Ticuiinisdin-ffs .luiini. d. Phnriii. II- i!)a. n, 1.. laii. 2) Hist. res. scii'Tit. acad., p. 4',>.".. ii) Mum. de r,\caha"'m' 8| Iliidem. 1747. p. 4.->. Itiuidscdian, 11, pp. 2s and 4s. "t Cheni. bot. Abb., 8. p. l.".-,. History of Volatile Oik. 41 profited first by the new theories of the opponents of the phlogistic school. Organic chemistry, and with it the stndy of the volatile oils, were benefited somewhat later. Though of little consequence, the experiments of the Dutch chemists Deimann, Troostwyck, Bond and Lanwerenburgi) should here be mentioned. They passed the vapors of volatile oils through red hot iron tubes and examined the resulting gases. At the same time they made the bold attempt to synthesize oils by the action of gaseous hydrogen chloride on oleflant gas. The first investigation suggested by the new theories that was of positive value, was the elementary analysis of turpentine oil made by Houtton-Labilliadipre.2) He found the ratio of carbon to hydrogen to be five to eight, the same that was later established for all hemiterpenes, terpenes, sesquiterpenes and polyterpenes. Attention has already been called to the crystalline deposits that had been observed in the course of several centuries. These were mostly considered as identical with ordinary camphor because like it they were volatile, soluble in alcohol and fatty oils, and burned with a smoky flame. Only in a few instances, however, had the.se deposits been proven to be identical with camphor. Berzelius,-^) therefore, argued against the indiscriminate generic use of the term camphor. In its place he suggested the u.se of the term stearoptene (from a-riap, tallow, and TTTi^vov, volatile). He pointed out the analogy existing between volatile and fatty oils in so far as they can lie a mixture of several oils having different congealing points. Thus oils may, under favoraljle circum- stances, be separated into an oil which is solid at ordinary temperature, the stearoptene, and one which is liquid at low temperatures, the elaoptene (from iXaiov, oil, and tvttivov, volatile). The result of this was that the solid deposits from volatile oils were thereafter designated alternately stearoptene as well as camphor. Up to this day the older abuse of the term camphor has not ceased as becomes apparent from such words as cedar camphor, cubeb camphor, juniper camphor, etc. Soubeiran and Capitaine*) even made things worse by ajjplying tlie term '•liquid camphor" to t\w lifjuid hydrogen-cliloi-idc addition products of the terpenes. After it had lieen shown that true camphor contained rjxygen, the term camphor in its generic sense was also applied to other oxvgenated constituputs of volatile oils thougli tliey were li(|uid. 1) .Journ. de ehiiii. et de ph.v-^ , -. !>■ - • -fonrn. i\v pharin.. +, ]i. ;'. 178: Ci-ell's Chem. Ann., 2. |ip. 1(>"', 'iT' ■' • Lehrl), d. Cheuiip [;-l I, vol. li, ]). ,~iSO. and 480. -I Lieltig's Annnlen, 84-, ]>. >m . 42 Historical Introdnction. In 183:5 Dumas pulilished an article entitled "Ueber die vegetabili- srhen Suhstaiizen, welclie ,sich dem Gampher nJihern und iiber einige atheriHche Oele."i) Although a number of important observations of rather striking- properties of individual oils had l)een made, the systematic study of the volatile oils may be said to have begun with the analysis of a number of stearoptenes by Dumas. He suggested the following classification of volatile oils ; 1.) ThoKe that consist of carbon anrl hydrog-eii only, like turpentine oil and oil of lemon ; 2.) Those that contain oxygen, like camphor and anise oil; 3.) Those that contain sulpliur,^) like mustard oil, or nitrogen, like oil of bitter almonds. The elementary analysis of sohd peppermint oil, eainphor and solid anise oil revealed the composition CsHmJ^O, C'sHs^O and Vr,Yia%(). By doubling these formulas of Dumas the modern formulas for the respective substances are obtained. Of the oxygen free oils, he analyzed turpentine oil and tlie hydrocarbons of lemon oil, verifying the earlier results of Houtton Labilliardiere. During the years liS;{:{ — l.s;i.">, Dumas published further contributions on the subject of volatile oils, several jointly with Pelouze and Peligot. They pertain to artificial c-amphor (pinene hydrochloride), mustard oil, cinnamon oil, terpin liydrate, orris oil, pepper oil, oil of juniper berries and others. Almost simultaneousljr .with the first publications by Dumas, Bla.nchet and Sell^) pul)lished the results of their investigation whiidi hfl,d been carried out in Liebig's laboratory and which involve in large part the same substances studied by Dumas. The most notewortliv result of these investigations is the recognition of tlie identity of the stenroptene froTu fennel oil and that from anise oil. Several years later, in 1H87, the highly important and very inter- esting results of Liebig and Woehler's work on bitter almond oil were published. ■*) As early as 1802 Schrader and Vanquelin ha.d discovered hydrocyanic acid in the di.stillate of bitter almonds. In 1822 Robiquet showed that no volatile oil preexisted in the almonds, and with Boutron- Charlard he had prepared amygdalin in 183(1. They had init succeeded, 1) IJebig'H Aniialeii, G, i). 24.^). -1 The f«ct that mn-stard oil contains wnlpiinr was recog:nizefl liy Tliibiei-ffu in lsl<> i.Iourn. (le pliarni., n, pp. 20, 439 and 446; Troninisilorff k Xeucs .loiirn. rt. riiarm. 4 II. p. 250.) Ttiat sulphnretted liydrogen i.s given off dnrinK tlie distillation of several umtM'lliferous fruits, snch as caraway, dill, fennel, etc.. was iiointed ont by L. ,\. Planche of Paris in 1S20. (Trominsdorff's .N'enes .Journ. d. Pliarni., 7i, ji. H.TG. i :^ I Liebig:'s Annalen, 7, f). 1.04. i) Ibidem, 22. p. 1. History- of VohitUe Oils. 43 however, in preparhig- bitter almond oil from amygdaliii. That this is decomposed by emulsin into benzaldehyde, hydrocyanic acid and sugar was demonstrated byLiehig- avid AYoehler. They also point out that the manner of formation of mustard oil must be closely related to that of liitter almond oil. for the mustard seeds deprived of their fatty oil possess no odor, this being produced only when water is present. The investigation of mustard oil by AVillM in 1844 substantiated this supposition. ('hemists now became especially interested in the action of liydrogen chloride on various terpenes and in the resulting hydrochlorides, some of which were solid, others liquid ; also in the study of terpin hydrate and its decomposition pi-oducts. The study of the literature pertaining to these subjects is rendered difficult liy the error of regarding mixtures of several substances as chemical individuals and describing them as sui.-h ; further by the fact that almost every author, irrespective of the work of others, coined a nomenclature of his own. This confusion continued until veiy recently when Wallach and his disciples created order. 2) (Jry.stalline pinene monohydrochloride had been discovered by Kindt, 3) an apothecary, in 1802. He regarded it as artificial camphor, a view shared by Trommsdorff.-*) The true composition of this compound was ascertained by Dumas in 1888. Crystalline dipentene dihydrochloride was discovered l)y Thenard in 1807. It is the "salzsaures Citroneuol." muriate of lemon oil, of Blanchet and Sell, the artificial lemon camphor of Dumas. These and similar substani;es were investigated by Soubeiran and Capitaine (turpentine oil), Deville (turpentine oil and elemi oil), Schweizer (carvene) and Berthelot (turpentine oil).-'') The formation of terpin hydrate and the action of acids on this sul)stance was studied principally by Wiggers, List, Deville and Berthelot.") 1) Liebiff's Annalen, .52, p. 1. A more otiiiiplete insight into the mechanism of the reaction by which mn.starrt oil is produced was supplied by the later inyestiKations of Will and Koerner in 1S6.3. (Liebig's Annalen, 125, p. 257.) See Oil of Mustard. 2) The historical deyelopment of this chapter of the chemistry of the terpenes Is described in "Terpene und Terpenderiyate, ein Beitrag zur Geschichte der atherischen Oele" by E. Kremers (Pharnl. Rundschau, '.). pp. ."i.'j, 110, 1.59. 217. 287; and 10, pp. 10, 31, fiO; also I'roc. Wise. Acad. .Sc Arts and Letters, 8, pp. B12— 362. 3) Trommsdorff's .Tourn. d. Pharm., 11 n, p. 132. *) Ibidem, p. 135. 3| Of later inyestlgators of this subject Oppenheim (1S64), Hell and Ritter (1884)," Bouchardat and Lafont (188fil, and finally Wallach (1884—1887) may be mentioned. 6) The same subject \yas later inyestigated by Oppenheim (1884). Fla\yitzky (187'J), Tilden (1878 — 79), Bouchardat and Voiry (1887). Here also Wallach'a exact inyesti- gations revealed the fact that different acids, as well as the same ,acid in different degrees of concentration, pi'oduce different res\ilts. 44 Historical Introduction. A paper published about this time (1841) by Gerliardt and Calioursi) is of special interest in so far as it contains a definition of a volatile oil which in a g-eneral way holds good to-day. It also makes known new methods of investio-ation. About oils in general the authors state: "Tliere are, indeed, but very few oils whieli can be crystallized; most oils are liquid and consist of a mixture of two and even three peculiar substances, which rarely are obtained by tliemselves when distilled at different temperatures." The separation of the individual substances is effected by first allowing any solid constituent to crystallize out, then the lower boiling hydrocarbon is isolated by distillation at a temperature 20—30° below the boiling point of the crude oil. 2) Inasmuch, however, as the hydro- carbon cannot be completely freed from oxygenated constituents in this manner it is treated with fused alkali. The oxygenated constituents also are subjected to like treatment with fused alkali, and cumin oil is thus made to yield cuminic acid, oil of valerian valerianic acid. .Strong reagents are also employed by Rochleder, Persoz, Laurent and Gerliardt in order to obtain an insight into the nature of volatile oils. They oxidized either the entire oil or fractions thereof with chromic acid or nitric acid. Their investigations included the oils of valerian, sage, anise, staranise, fennel, cumin, cinnamon, tansy and estragon. The conclusions drawn from these oxidation experiments were in part correct, in part wrong. Thus e. g. CT?rlia,rdt pointed out the identity of (li'agonic ai-id, obtained from estragon oil, with anisic acid, and clafmed that estragon oil and anise oil were absolutely identical. This conclusion was wrong, for the anethol of anise oil is paramethoxypropenyl- benzene, whereas the formation of anisic ai-id from estragon oil is due to the presence of pafamethoxyallylljenzene.'') Tliis method, however, rendered it impossible to decide whether a substance obtained after the oxidation ])reexiste(l in the oil or not. Tims i-amphoi' was fomid in several oxidized oils ami was regarded as an original constituent although, as was tlie case in the oils of valerian and sage, it had resulted from b:)niei)l. Persoz, however, seems to have 1) Liebig's Aniuileii. /is, ji. (17. ^) Fractional diKtlllation, ht.wever, way previDtisly employed in the exauiiiiati(tn of volatile oils. A.'^ early as 1888 Walter had sulije(.-ted pepi)eriniiit oil to interrupted di.stillatioii, "p^ebrochene Destination" Mfiui'lin. Handbuch d. Cheni. [4], vol. 7a, p. 4(14). In isto Volckel ( Lielilg's .\nna|pn, :■!,". ji. :',il;i) spealis of "fractional distillation." Already Hlanchet and -Sell in ls:t:l hail apiilied fractionation with water vapor as a means of separation and had found that, the first fraction of lemon oil boiled at 1(>7'-, the last fraction at 178^^. ^1 This difference was first ascertained in the laboratory of Schimniel ,.^c Co. ( Berieht S. A; Co.. April 1S02, p. 17) and \erlfied by Orimaus in ls;»3 tl^'onipt. rend.. 117. p. USUI. History of Voliitile Oils. i~> liad doubts as to the reliability of tliese conclusions, for he leaves it undecided whether the camphor obtained from oil of tansj'- was contained in the oil or not. As a matter of fact, tansy oil contains camphor as an original constituent,!) this being less readily attacked by the oxidizing agents than the other constituents of the oil. Of considerable importance in the farther development of the chemistrj' of volatile oils are the investigations of Berthelot from 18.")2 to 1.S63, which involve principally the hydrocarbons contained in these oils. He studied first of all the hydrocarbon of turpentine oil 2) and its isomers and polymers obtained from its hydrochloride. By heating pinene hydrochloride with barium stearate or sodium benzoate he obtained a new hydrocarbon which he regarded as "camphene proper" s) and which is identical with the camphene of to-day. This new camphene was either dextrogyrate, laevogyrate or optically inactive according to the turpentine oil employed. Berthelot, therefore, distinguished between the following hydrocarbons : 1.) Terebentene (1-pinene) from French turpentine oil, laevogyrate*) b. p. 161°. It yields a laevogyrate monhydroehloride, also under proijer cfniditions an inactive dihydrochloride (dipentene diliydrocliloride). 2. ) Terecainpliene (l-r-amphene) from terebeiitene liydrocliloride, laevogyrate, in. p. 45°, b. p. 100°. With hydrogen chloride it forms a dextrogyrate hydrochloride. 3.) AustrnJene (d-pineue) from .\niericau turpentine oil, b. p. 161°, dextro- gyrate like its hydrochloride. Its beliavior to hydrogen chloride is analogous to that of terebentene. 1.) Austraciinipherje (d-camphene) from austi-alene hydrochloride. It corresponds to terecamphene. ij.) Ina.i-tivp. cnrnphene (i-campliene) can be obtained b.y proper treatment from the hydrochloride of terebentene as well as that of auRtralene. 6. TfTfhene,^) b. p. 160°. 1) Berii-ht von S. & Co , Oct. 1893, p. .-U. -') Compt. rend. 5.5, pp. 4fli3 and .o-t-l ; also rjebig's AnnaJeii, Sn|>)>l. 11. p. 226. 3) .Soubeli-an and fajjltaine in 1840 had applied the term eamjihene to all h.vdro- carVionK CsHg (Liebis's Annalen. 34, p. 8111. 4) The rotatcarbons. Almost simultaneous! v Barbier^^) (1872) and Oppenlieim-'l (1872) obtained cymene by heating the dibromide of terpin either by itself oi- with aniline. By the action 1) Berthelot in 18.18 changed the name borneol to camphol. Liehig's Annalen 110, p. 368; from Cornpt. rent!., 47, p. 266. 2) ,Jonr. Chen;. Soc. 17, p. 1. .\ second contribution appeared eight vearK later Ibidem. 25, j), 1. ' ' ' 3) Lehrbnch der organiHChen Chemie (1866), voi. 2, p. 437 : " on the other hand the oil of turpentine and numerous isomeric hydrooarlions. which may be designated by the generic term teri)enes." *) Oompt. rend., 74, p. l'.)4. .-•) Berichte, 5, p. 94. History of Volatile Oik. 4) The liquid.s included in each group are allotropic modifications of the same hydrocarbon distinguished one from another b.v their various rotatory action on thf polarized ray. It will, however, be found I believe that the terpenes from several ditferen(3 plants will on further examination be conclusively proved to be really identical and not simply isomeric. This, I believe, to be the case with the terpenes from French turpentine and sage, also with the terpenes from orange peel, bergamot and lemcjn." Tilden's prediction, that the number of terpenes would tie shown to be much smaller than assumed in his days, has proven itself true. His clas.sifieation, however, was insufficient, for it included only a small number of terpenes. Indeed the material at liand was not sufficiently sifted for an attempt of that kind. It consisted of a large number of dLsconuected observations, the study of which was rendered difficult by an arbitrary nomenclature. Only by a systematic; e.xploration of this disorderly realm could a <-leai' insight intf) tlie subject be gained. 1) Berichte, 6, p. 437. 2) Kekuld's tornuila (or camphor was liased on the .same consideration. 3) Compt. rend., so. p. 14-46. *) Jour. Chem. Soc, i!S, p. .514; Ibidem, 31, p. .'334; Pharm. Journ.. 1S77, p. I'.H. 5) This statement is incorrect (or dipentene and limonene lilvewise produce terpin hydrate. Comp. Fliicltiger, Arch. d. I'harm., 222, p. 362; also Kremers, Am. Chem. Journ., 17, p. 69.5. 48 Historical Introduction. That we are able to-day to distinguish sharply between so many terpenes and their derivatives is due primarily to the excellent experi- mental researches of Otto Wallach, the founder of modern terpene chemistry. Inasmuch as it was impossible to isolate the numerous terpenes boilinR- between l.j.j and 185° by fractional distillation, methods had to be sought which enabled the characterization of these hydrocarbons, even in mixtures, by means of r/rystalline derivatives. Only after the characterization of the numerous isomers was accomplished was it possible to study su(;cessfully the relation of one terpene to another, the relation of the terpenes to their oxygenated derivatives, and the problem of their constitution. These problems have been solved in so far that it is now possible to identify many if n, 2,-.2, 253, 2.58, 2.59, 268, 264 268 26'.l, 270, 271, 272, 27.5, 276, 277, 278, 27',l, 281, 284, 2S6, 2S7, 289, 29l', 296, SOid' 302, 305, 306, 309. Several paper.s from his ])en also appeared in the Proceedino-'s of the German (■hemical Society since 1890. Of the latter, his lecture before this sirciety in 1S91 in which he prehented a general survey of his work up to that date should receive special mention (Bei-ichte, 24, p. 1525). History of Volatile Oils. 49 investigate(i primarily the ej^elic compounds, Semmler paid special attention to cliain oompomids. He showed that the alcohols geraniol and linalool and the aldeliydes citral and citronellal, which occur fre- quently in volatile oils, are chain compounds ; also that they, like the more or less closely related cj^clic compounds, can be converted into cymene.i) Other chapters of the chemistry of volatile oils were included in his researches, 2) some of which were conducted jointly with Tiemann.^) The investif^ations bj^ the latter and Kriiger of orris oil and irone, led to the discovery of ionone, the artificial perfume of violets. In addition to these, numerous other chemists have investigated the composition of volatile oils and the constitution of their constituents. In so far as their results pertain to the composition of volatile oils, their results are included in the special part of this treatise. The constitutional problems involved in the stud^- of the terpenes and their derivatives are among the most difficult of organic chemistry because of the readiness with whicli rearrangements within the molecule take place under the influence of ordinary physical and chemical reagents. A ty])ical example of some of the difficulties involved may be had in ordinarj' (-aniphor. Although investigators had an almost unlimited supply at their disposal and in spite of the fact that many chemists have been incessantly investig;iting this compound for several decades in order to obtain an insight into its constitution, the views held with regard to its structure^) are still divided. This brief history of volatile oils would not be complete witliout some reference to the literature on the subject since the beginning of this century. So long as the volatile oils were principally prepared in the laboratories of apothecary shops, the description of tlie oils and of the methods of their preparation was found in pharmaceutical refei-ence works and pharmacopoeial commentaries. The I'esults of scientific and technical studies were also published in pharmaceutical rather than in purely chemical journals, ^^'ith the early forties the preparation of volatile oils was taken out of the pharmaceutical laboratories and a separate literature was created. 1) The reverse prooe^hi, the conver.sion of the cyclic menthone into chain compouncl.s of the citronellal serie.s was accomplished by Wallach in 18'.»7. (Liebig'.s Annalen, 296). 2) The oils of Allium ursiniim. asafetida, garlic, onion; also tanacetone (thujone), menthone, pnlegone, terpineol, etc. 3) Bergamot oil, lavender oil, citral, pinene, methyl-heptenone, tanacetone, etc. i) Not less than two dozen structural formulas have been proposed for camphor In the course of these investigations. 4 50 Historical hitrodnciion. Zeller's*) publicatii)iis (lH.-)()— 185.-)), already mentioned on p. ;-!7, contain a compilation of the yield, also a very meagre description of the physical properties of the oils and their behavior toward reagents. Maier's*) treatise (1H()7) also takes into consideration the scientific inves- tigations. The methods of preparation and the suliject of distillation are described in detail by Mierzinski*j (1872). X similar work was written by Askinson*) in 187(i. "Die Toiletten-chemie" of Hirzel*) which pa8.sed through four editions, also "The art of perfumery" by Piesse,*) which was translated into several languages, may here be mentioned. The results of the earlier papers by Wallach are contained in the excellent work of Bornemann*) (1891), whereas the "Odorographia" of Sawer*) emphasizes the botanical side of the subjeirt. Finally the monogi-aph by Heusler*) on the terpenes should be mentioned for it has proven itself well nigh indispensable for the scientific investigation of terpenes and their derivati^'es. Altlnjugh remarkable progress has been made in the chemistry of the volatile oils during the past fifteen years, the investigations of this branch of science are fai' from being completed. On the contrary, the newly acquired knowledge has caused an ever in(.-reasing number of problems to present themselves for solution. It is quite remarkable, however, that the interest bestowed upon purely theorpti(_-al questions has c-a,used a falling off in the systematic analytical study of volatile oils. There are still n, considerable number of oils that are much used and readily accessible, the composition of whicli is liut imperfectly known. Even many oils that hnve been repeatedly examined will be made to yield still othei' constituents when cai'efully reexamined. Pbuit physiological prol:)lems also have scai'cel.y been touched upon, and the assay of volatile oils is just beginning to assume a modern scientific aspect in harmony with recent theoretical results. Hence there still remains a large field for ]irofitable work. It may well be said, therefore, that in spite of thi' unprecedented progress in recent years, the chemistry of volatile oils is but in its initial stages. Following the paths of Wailach and of other reformers, chemi(.'al investigators (if a,ll civilized countries are busily at work opening up new fields for investigation. iSciem-e and industrv are working hand in hand and it nmy reasonably be expec'ted that both will profit greatly by the results of the incessant labor thus fostered and stimulated. *) See I'ibliDA'raiiliy. HISTORY OF THE METHODS OF DISTILLATION AND OF DISTILLING APPARATUS. The literary documents considered in the previous chapter, reveal the slow process of evolution leading up to a better understanding of the subject of volatile oils. In like manner, a short historical retrospect of the methods of distillation and distilling apparatus may result in an insight into the gradual development of the art of distillation and the methods of preparation of distilled oils. The history of the evolution from the primitive Cucurbita, the Alembic and the Berchile to the steam and vacuum appa- ratus of our own time reveals a long and varieii course which had to be followed by this apparently modi^rn branch of industry in order to bring it to its present technical and scientific perfe(_'tion. The first definite statement found in ancient writings whicli indicates a kind of primitive distillation, although probably not pictured until the middle ages, is the mention of the method ff)r olitaining oil of cedar {■maa-iXaiov) in the writings of Hero- dotus. i) Dioscorides") and Pliny.3) This oil is said to have been obtained from the oleoresin by boiling with water in an open earthen kettle. The oil either collected at the surface of the liquid and was removed, or its vapors were condensed in layers of wool spread over sticks of wood laid crosswise Fig. .s. 1) Historiae, lib. 2, p. S'j. 2) De mat. med., lib. I, 34. .'!!i, SO. 3; Hi.^t. nat., lib. 1.''., cap. 6—7; lib. 16, cap. 22. 52 Historical Introduction. on the kettle as in figure 3. The wool was replaced from time to time bj fresh portions and the saturated wool expressed with the hands. Authentic representations of the distillhig vessels used by the Egyptians do not exist. Some of their forms of apparatus were undoubtedly adopted by the Arabians and improved by them. To the oldest known writings which give information on methods of dis- tillation and distilling apparatus belong those of the Greek physician Dios- coridesi) and of the Greek philosopher Zosimow.i) FiS. -i- Fie. : In a manuscript Arabian translation of Dioscorides" Materia Mediea in the librarj' at Leyden distilling ranges and apparatus are mentioned and described. These descriptions probably occur in the original Greek text. Among them are found the cururbita and the aleinbicfi) Fiff. ( FiK Just as jjictures of animals have served as symbols in the oldest mythology and as characters in writing of the earliest peoples, the forms of animals were used by the ancients as prototypes in the making of jewelry, and of all kinds of useful artirles and apparatus. The same 1) Compare BibliogTjiphy. 2) Extracts from thin hh well as the umcli later Arabic writingK of Rhases and an unimportant llliistratioii of an Arabic dlsUllinK apparatus were published in 1878 by I'rof. Wiedemann in the Ztsch. d. deutsch. niorgenland. Gesell., ;!2, )), 57,5. History of the Methods of Distillation and of DistilUng Apparatus. 53 seems to have oecured iu the preparation of primitive digestion and distilling vessels. Such pictorial representations liave been carried over from the writings of Zosimos and probably also of others into the writings of the Arabians and from these into other alchemical works of the middle ages.i) As prototype of a common flask the figure of an ostrich is given (fig. 4) ; as that of a retort a goose (flg. 5) or a pelican (flg. 6). The shape of a bear served for a still (cucurbita) and head (alembicus) (fig. 7). An improved form of this simple distilling apparatus is found in the writings of Geber^) and Albucasis.3) The latter not only described glass distilling vessels but ^^^^^ Fiff. 8. Fig. y. also those prepared of glazed earthenware (flg, 8) and a kind of fractional distillation for the purpose of a better condensation and separation of subtle spirits by placing several alembices*) on top of one another (fig. 9). From the writings of Geber and Albucasis, also from those of the excellent physician and writer Kha.ses (El Razi), it becomes apparent that the Arabians distinguished as early as the eighth century between distillation over open Are and from a water bath and ash bath, s) Geber described both methods iu rletail") For the purpf)se of better condensation, Costaeus of Lodi,^) a physician and alchemist of Bologna, recommended that the beak of the 1) ,Joanni.'< Rhenani. See Bibliography. 2) Summa perfectionis magisterii. 3) See Bibliography. 4) Albucasis, Liber servitoris, lib. 27, ]•. 247. f') Ithases, Das Biich der Geheimnisse. 6) Suinma perfectionis mag., cap. .50. 7) See Mesuij, Simplleia et couiijosita. (fiff. l;^) Am one: 54 Historical Introducrion. alembic be oooled bv water (flft-s. 10 and 11), also that the distillate be improved by the use of the water bath (balneum Marme) (fi}r. 12) and the sand bath (balneum arenae) the writings left by the Arabians, the work of Albucasis previously mentioned probably contains one of the first and most striking- descrip- tions of the manner of distillation and distilling apparatus. From the fourteenth century on the practice of making distilled liquors increased very considerably. As a result the methods of distillation and the Fig. 10. FiK. 11. distilling apparatus, especially those parts em]il(.)yed for the con- densation of the vapors, were greatly improved. The method of con- Fiff. 12. densation of the vapors, already well known to the Arabians, of ]>assing the straight or bent tube of the alembic, or an elongation of the same wound into a spiral (wormtube, serpentina) through c-old water was History of the Mptbods of Distillation and of Distilling Apparatus. 55 alreadjr in general Uise at that time for the distillation of wine and fermented plant juices. As examples of such distilling apparatus and methods, "die mancherley Khhlungen der Teutschen und Welsche Wein- brenner" are described and illustrated in treatises on distillation of the first half of the sixteenth century, namely in those of Brunsclnvig, Ulstad, Eyff and Lonicer. In these a distilling apparatus constructed with considerable skill is described. The helm of the still and the outer condenser jacket were made of sheet copper. The form of the headlike expansion of the helm with the outer jacket, the lower open rim of which was tightly luted to the still, gave rise to the name of "Mohren- kojif."' The condensation was effected by a continuous flow of cold water through the outer jacket (flg. 14). Fis. li. The method of condensation ilerived from the Arabians was con- sidered as the most perfect for the distillation of spirit of wiue (;i(jua, vitae). The illustration of this apparatus was selected for the title page of tlie second volume of Brunschwig's Destillirbuch published in tlip year ]507 and is reproduced on page 25. AMiere the two upright serpentine coiine(/ting tubes (serpentinae) Ijetweeii the i-etorts (cucurbitap) and the receivers (receptacula) cross 56 Historical Introduction. each other they pass through a condensing tube filled with cold water. The cooling effect thus produced is not sufficient tor the condensation of all the vapor. The worm acts therefore, as a dephlegmator and increases the alcoholic strength of the distillate. This is emphasized con-ectly hj Brunschwig.^) The perfection of the apparatus for the preparation of distilled lirpiors, also distilled oils, which up to that time had received but little attention, seems to have progressed much more slowly and with greater difficulty. In comparison with the ready volatility of the alcohol, water was considered as that product of distillation most closely related to it, whereas the oil was regarded as the ''obese and fatty substance that had to be driven over with a stronger and more violent heat." This had led to the firmly established belief that in the process of purification, tlie \'olatile and subtle part must penetrate and exhaust the material as much as possible. As a result all sorts of queer apparatus and souri-es of heat were invented. They all resulted in a prolonged digestion and an unintentional loss of the alcohol ofttimes formed by fermentation, and of the aroma. Circulation was therefore considered not only as the essence of distillation but also as an important preparatory part of it. It was believed that the plant a,nd animal material finally to be distilled was thereliy prepared for the refinement and purification of the ''geistige Wesen" contained in them and for their better and easier separation and ]iuriflcation. A large variety of vessels, usually i^instrueted after some syml)olic prototype was used for this purpose. The simple Circulntonn were ordinary glass flasks, retorts with the tubes bent in a varietv of ways, also so-called urine glasses used by physicians for diagnosis. 11 De arte iHstillaiuli, vol. '2, lib. 1. History of the Methods of DistUhitwn and of Distilling Apparatus. 57 The operation performed in the pelican (fig-. 1.")) and double or twin circulatoria (fig. 16) provided with reflux tubes were considered as the most perfect kinds of circulation, especially for refining- the "spirits." FiK Fig. 18. Still more peculiar than the form of the circulatoria was the source of heat used for the purpose of circulation, usuallj^ a,ceompanied by fermentation, and even decomposition processes. Not only was the water bath (balneum Mariae) (fig. per cinerem) (fig. 18) employed, l)ut also the sun bath {destillatio soli.-,) (fig. 19). The circulation vessels were also immersed in fermenting dough, and heated with this in an oven (rlestillatio panis) ; or they were inibedde;! in decomposing well 17) and the ash liath (balneum pi I jMJBaMaM^ pp -^ rT ^^= \^ 7 ffi ml Lpfili n '■ — S j| ^H — — ^^= -=^^z:l \ w^ SSl\K^ ^^ ^ f^ ~^ '■ V^^^£|iis4uikttbUi\SttM**> ^ J.^L '■fc- ^ — ^ J 1 ^m l^:^==:^^yr J^ ^^^^70 M '-^SlfBk • 1 \^^ ^HM s W^M i^^^^^^m^^ ^^S BmmiBil ■^ '''^-^^^^"\.. ■™ ^^^~^ ^ IMwiiUliMHilil n '^^ ^ - '^/■'-^^'im\ Fig. 19. Fig. 2(1. wetted horse manure which was placed in a layer above unslaked lime in pits (destillatio per ventrem equinum) (fig. 20). With the introduction of aromatic waters as one of the principal forms of medication, the condensation of the vapors gave rise to difficulties, because a greater degree of heat was necessary for their 58 Historical TntroiJuction. (iiistillatioii. Plant material lying on the bottom of the still was also easilj- burnt, and the distillate receiA'ed therefrom an empyreumatic odor and taste. With a strong- heat a serious overheating of the helm and tube, which were usually constructed of lead or tin, took place, while with the employment of a moderate heat the yield of the distillate remained unsatisfactory. In order to overcome these disadvantages and to prevent the flowing back of the distillate condensed in the helm, as well as to increase the cooling effect of the air, the helm known as the "BoseTdmt" (fig. 1, p. 23) and (tig. 21) was constructed as early FiR. 21. as the fifteenth century. Near the barse, at about the height of the outlet tube, this had a groove extending around the inside of the helm, and through which the water condensing on the upper wall of the helm and running down was conducted uito the outlet tube and from there into the receiver. The "Rosenhut" was therefore in itself an inefficient air i.'ondenser, which served its purpose with much less efficiency than did the "Mohi-enkopf" in the alccihol distillation (fig. 14)- The first step toward a better condensation witli cold water, in the preparation of the distilled waters, consisted in surrounding the liead History of the Methods of Distillation and of Distilling Apparntns. 59 of the helm (ulembic) with an oxbladder. It was securely fasteued and provided with a wooden stop-cock. The hood-like basin thus formed (fig. 22) was kept cold by means of flowing water. In a similar manner the helm was also surrounded by a basin-like metallic addition which was either fastened by luting or soldering. Thus the hehn could be well cooled by running water (fig. 23). By means of an inner horizontal groove like that in the "Eosenhuf (fig, 21) the distiUate which condensed on the walls of the helm was conducted into the receiver. Walter Eyff in his treatise on distillation describes and illustrates distilling apparatus with condens- ing tubes which are passed through vessels of cold water. The first apparatus has two tubes connected with the helm (fig. 24) which are passed through a barrel of water. Fig. Fis. 2.3. However, Ryff declares this method of condensation as insufficient and recommends a worm tube for the shape of which he gives two forms (figs. 25 and 26) and concerning the use of which he gives a detailed account. A peculiarly constructed apparatus for the distillation of aromatic waters and oils was recommended bj^ Adam Lonicer in his "Krauter- und Destillirlmch'' published in I.ITS. The construction of the apparatus becomes readily apparent from the accompanying cut (fig. 27). Finally, the Aratiians and probably others before them practiced "downward distillation" which corresponds on the whole to our modern 60 Historical latroduction. dry distillation for obtaining empyreumatie and tar oils. At the time ot the revival of the distilling art this method was also used in the preparation of the oils of certain woods, barks and spices. Juniper Fig. wood especially had been sulmiitted to this destillatio per de.sren.sum since antiquity, later also guaia(,' wood, (/inuamon, cloves, mace and other spices were distilled in this manner. The furnai'e contained a History of the Methods of Distillation and of Distilling Apparatus. 61 division in tlie middle, with a ('entral opening into whicli a pot provided with a beak-lilve opening at the bottom was eitlier linng, or plastered in. On top of the opening extending into the upper part of the furnace Fig. 26. was placed a wire gnuze and a second pot tilled with the drj' substance to be distilled was luted with it.s opening on the top of the lower pot. The heatin"- was then effected by building a fire around the upper pot 62 Historical Introduction. (fig. 28). Sometimes the lower pot wa.s buried in the earth and a fire built about the upper pot fastened on top of this one in the same manner. For the destillatio per descensum on a small scale glass vessels heated from the side (fig. 29) were also employed and even for some easilj' distilled substances the heat of the sun {destillatio .solis) (fig. 80) was used. At present the preparation of empyreumatic oils as well as of the finer tars is effected in cast iron or earthenware cylinders. The treatises on distillation published during the sixteenth century reveal by both text and illustration that about that time more attention was again given to the construction of furnaces and implements used for the purpose of distillation. Besides the distilling apparatus most generally used at that time and repro- duced ill figs. 10, n, li, 17, 21, 2:^, 24 and 2.j, the socalled "faule Heinz" or Atlnuioi (from d^'^ai/aros, imperishable) called by Ulstad farnus Acediae (fig. ;■!!) was mm-li in favor and was used to a great extent for the distillation of waters and oils. Alxive a common Fig. 29. FiR, :!(). fireplace were placed tliree or more distilling retorts with 'Rosenhut- helm" (p. 104, fig. 21). The fireplace ended in a, central iron, copper or earthenware pipe the opening of which could be closed by a cover. By means of slides at the sides of tlie fireplace the heat could be conducted under any one of tile stills or retorts as desired and the distillation was thus regulated. History of the Methods of Distillation unci of Distilling Apjjaratns. 63 For the distillation of large quantities in a large number of .single retorts or stills, larger i-upil furnaces after the manner of the so-called "galley furnaces" appear also to have been in use. Tlie illustrations and descriptions of these in the treatises on distihation of the sixteenth century represent no doubt more the possibility than the realization of perfection. The illustrations of these furnaces were transferred from one distilling book to another, but probably have not been generallj^ used in practice. Among others they are thoroughly described in the text and reproduced in illustration in the works of Matthiolus and of Lonicer previously mentioned. They are built either in the shape of a terrace (fig. 32) or of a bee hive (fig. 88). Although the compilers of the distilling books of the sixteenth century have in succession followed the pioneer work of Brunschwig, especially in regard to illus- trations, their writings nevertheless quite often show considerable differences in views, practiral skiU, and experience, and also in the origuialitv of their knowledge and abilitv. With but little public intercourse these secluded workers and writers toiled mostly far from one another, each in his own sphere and manner, often with but a slight knowledge of the older writiTigs and of the CA Historical Introduction. work of hip contemporaries. With i-egard to the manner of distillation of the aromatic waters and oils this is shown in an unmistakable manner in works compiled in tlie course of the first half of the sixteenth century by Philipp Ulstad, Walter Eyff, Adam Lonicer, Valerius Cordus Fis. m. and Conrad Gesner. All of these were mainly based on the writings of Hieronymus Brunschwig-. Their views, however, as to the nature of distillation itself and of the distilling- methods and apparatus are neither in accord with those of Brunschwig, nor with tliose of their contemporaries. History <>l the Mftliods of Distilhition ;iuil of DistiU'uii^ A/ijinnitiis. (;5 Hi)\v little personal skill, practic-al experience and faniiliaritj- with the liteT-ature on the subject may be fdund iu the writings and niethiids of workino' of the most prominent experimenters of that time becomes apparent e. ft', from the eonstrni-tion of and preference for the distilling vessels employed. Thus for instani'e, Valei'ius Cordus, profound in theoretical sc-ience. but ignoring the rationally constructed distilling apY)aratus then well kTiown. used and recommended "ein Kolb mit einem anges(.-hinelztem Helm'' (fig. 34) as an etficient apparatus meeting all the requirements of the art. At the same time Conrad Gesner, his con- temporaiy, u.sed for tlie same jiurpose a distilling furnace (tig. .'!."i), wliich had been used for some time. As has already been mentioned, the seventeenth centnrv, ci'ippled as it was ly the destru(.-tive stoi-ms of the Thirty Years war, adiled but little to the further development of the art of distillation a,nd other technical si-ientiflc industries. The few active experimenters, however, favored with a better undei-standing, endeavored to perfect not only the aiijiaratus used but the processes as well. ^r;-?^^— ^•^-^"c-- IMS-. 34. As the "Destillii-buch" of Hrunscliwig ami similai- treatises of his successors leflect the practi(.-al and theoretical knowledge of the sixteenth century with its mistakes and imperfections, so Glaul)er's treatise on distillation reflects the condition of the art and science of distillation durine- the second half of the seventeenth century. Although (ilauber's laboratory work and the character of his writings was of a wider scope than that covered by the older "Destillirbiicher," yet he also paid spec-i;il attention to the distillation of aromatic plants and spices. In this, he and his contempoi-aries seem to have paid special attention to the improvement of the methods of di.stillation for the purpose of relatively increasing the products of di.stillation. For this purpose as has already been mentioned on page :i:!, a very rational expedient of inca-easing the .specific gravity and thus raising the boiling point of the wa,ter used 06 Hixtoiiinl [ntrofhiffinn. for tlif distillation, was resorted to. Tliis was effected liy tlie addition (if sfdts. The use of innriati(; ai-id {siiiiitus .sa/i.s) reeoniniended liy Grlanliei- for tlie distillation of oil of cinnamon and other expensive oils has also been allnded tci (p. :'.;!). His idea was that tlie ai-id peiietrateil the material and thus drove out the oil. A small amount of muriatic aciil was .supposed to take tlie jilace of a lar^-e quantity of water thereby avoiding' loss of oil. He also recommend.s that dark colored and resinified oils be rectified with iiritu,s sull.s. Glauber's authority was recognized until the middle of the eighteenth century, and the methods rif distillation re<'ommendeil by him in his several writings were employed liy his contemporaries and their successoi-s. Boerhaave, therefore, and Hoffnumn, their contemporaries, and later investigat(U'S prepared the volatile oils liy using i-ommon and other salts or hydrochloric acid. It is perhaps due to the observation that metal was pre.scnt in an oil or a distilled water, especially if an acid had been used in its preparation, that in the cour.se of the eighteenth century more attention was again bestowed upon the material from which the still was i;-oustru(/ted. In consequence glass and glazed earthenwari' were substituted for metal. As a matter of fact it seems that as early as the sixteenth century the presence of metals in the distillates olitained from metallic stills did not escape the notice of some of the experimenters. Among others Joh. Krafft ^ ) (l.'ilO — l-'iH.")) cautions against the use of i:-(i]ippr distilling vessels. The famous Parisian jihysici.iu Andu-oise Pare-) (I.'ilO — ].")!)()) warns against the use of lead helms and con- denser tubes "which ofttimes cause the distilled water to lie milkv." The Bologna physician and professor Benedetto A'ettori of F.-ienz,i ( 14-Sl— l"i(il) declan.'d about the year l."i."."i. that waler oil beini:- conducted tlirough lead jiipes ilissolves leail and thus becomes poisonous.-^) Howevei-. these observations like so many others nmde in the art of distillation ajipear eithi^' to have been known to but a few or else wi're unheeded and ag:iin forgotten, for even dm-ing the si'venteenth and eigliteentli c-enturies wlien oils were distilleil with acids, lead ,-nid tin heads and condeTisers were in general use in c(uini'ction with copper stills or glass and earthenware retorts. i| Concilionim et epist., 1, fol. Itiii. 2) Lea oeuvres, p. 740. y| Practk'iU' iiiaaiuif, 1. cjip. 21. fel. 144. History of tl]f Met/iods of Distill.-ition and of Distilling AjipaniUis. CiT As ah-eady mentioned in the ]ireeedinj;- chapter, tlie distillation of the volatile oils and the construction of the distilling apparatus received more attention and underwent a nuDre rapid development Avitli their general introdui'tion into the laboratories of apothecaries. In these the volatile oils used in medicine and the arts were prepared up to the tirst decades of tlie nineteenth i-entury. Only a few oils, such as the oils of lavender, rosenniTV and ro.se which could lie readily proilucf^d in some countries and which were largely used in the perfume and soap industries, have hpen obtained since the sixteenth century in laruer quantities liy nu'ans of [iriniitive ]iortable distilling apparatus.') viK. ai The distillino- vessels used in the a])otliecarv laboi'atories and the itinerant stills (Wanderdestillirgvnitlw), or nhimhics royageants used in France, Spain, Italy and Bidgaria, consisted of copper stills with a copper or tin head and tin condensing tubes of various shapes. One of the better distilling ajjparatus used for the distillation of volatile oils in the eighteenth century consisted of a. tin or coyiper body 1) Comp. p. 2(i; alHO mider Oil of LiiTender, Oil ol' Kose and Oil of Koseniary. OS Historjca 1 liitroiluction. siis]ifiiile(l in a water liatli, and provided witli a "Molnvnkojif" (iiy-. 14, p. "I'l). a "KDsenlmt" (flg. 21, p. oS) and a spiral tube for condensation. An illustration (flji: '.\(\) and description of this distilling a])paratus was ])iil)lislied in 171^4 liy Franruis Demacliy.i ) direct(n- of tlie ajiotlieeary laboratories of the civil hospitals of Paris. The copper kettle i- serves as a waterbatli wliicb can lie tm-ni^d liy the liaiidles .s .s' and refilled with a fresh supply of water through the side tube rn. Tlie tin still tl rests with the upper i-iug ;; on the rim h of tht^ ];ettli'. The lower UHck (/ of the liead of tlip still // rests at ;/ on the upjier i-iui of the still. Around tlie lownr edge of the head runs llie trougli r in which llie distillate that has been condensed in the cone collects and jiassi's with uneondcnsHd vapors thi'ough the tube c—n into tlie s]iiral condenser. The "Mohrenkopf" a serving as a cooler for the "Roseiihut" /< is soldfied to the neck A- of the condensing aow. The water in the cooler warmed during the ]iroc;ess (jf distillation, runs off through th(.' upper tube e as fast as cold water is added. Kig. H7 Shice the beginning of the nineteenth centnry attem]its have bp^n made to simplify and to improve The construction of the distilling apparatus, more es]iecially of the cooler, also to pre\ent tlu' Imrning of the plants on the bottom of the still with the use of direct heat. 8ueh imiirovements were made especially by .F(di. Gottfr. l)in>;ler, the apothecary, in Augsbiu-g-') during the years l.Sl . ",—182(1, by Smithson Tennant'M in ISl.", and by Henry Tiltton + I in INIS, both of Kimland. 1) I.'art (111 aestlllateiir. Oerra. traiisl. liy Hatineinanii, vol. 1 . |>. ]'.I2, iuid ])latf2 tl"- 1 21 rTOiam-sidorffs .Toiirn. d. Pharni., lli, p. 241; al.sc, i^ucliiiei'-s Mnn-rt ^^ 'n \W nnil IJ, |i. 3 42. ■. -. i . •- , :<) I'lill. TraiiH. islr.; Ufpei-tory (if .\rts, Sept. ISl.'i. ■i| .\iiTialH of I'hil., .June ISIS: I!iichnei-V Rcpei-t.. C. p, '.is. History (if the Metliods of Distillntion luiil oi Distilling Appnnitus. 69 The liitter attenn.ited to carry on the distillation at a- lower temperature by putting- the apparatus in connection with an air pump. The distilling apparatus more commonly in use at that time for the distillation of volatile oils was the one shown in the accom])anyinii' cut (fig. 37). Steam distiUation was recommended in 182() by H. Zeisei) and especially for volatile oils liy van Dyk in Utrecht, 2) wlio thereby materially aided in its introdm-tion. He demonstrated that the volatile oils which were obtained by steam alone from the vegetable material, distina-uished themselves from those obtained by distillation over open fire, bv a lighter color and purer odor. Clove oil distilled with steam is nearly colorless, cinnamon oil light straw yellow and orange peel oil completely <-olorless.3) The first steam di.stillation on a larger scale in a pharmaceutical laboratory appears to have been that in the old Apotliecary's Hall in London.*) 1) BfitiJiffp ziir Xutzainvenduns 'lei' Wassf nliimpfe ; .\it1i. iI. Phai-iii., IC, p. ll'.l. 2) Biichner's I'.epert., 2'J, p. 'H- 3) Ibiilein, 2!i, p. lie. 4) do., 29, pp. 112 & KS:!. 71.) Histork-.-i I IntKxJurtion. Ill Gt^rmaiiy steam distillation for the preparation of volatile oils in apothecary laboratories was also made possible by the introdnction of a. stearin distilKiiy apparatus/) constructed about the year l.s2(i by Johaiin Beindorff, mechaiiii/ and tin founder in Fi-ankfurt a. M. (fi.ii'. •!>*). AVith this apparatus, soon perfected in many ways, the distillation of volatile oils with steam under pressure was possible. The condensing- arrangement also had the advantage over tlie spiral tulie of being made up of separable parts, and thus iillowing it to be reiidily clpaned even on the inside. For the preparation of volatile oils on a small scale, tlip arrange- ments liased on the original steam distilling apparatus of Bniiiclorff remained, until the industry conducted on a large scale became dominant also in this field aiid prepared products of a (|Uiility and at prices with which tlie preparation on a small scale could not comjiete. Of tlie arrangements userl for a. long time for the separation and removal of the oils from the water the Florentine flask in Viirions forms anil sizes lias shown its utihty and has been in continual use It probably came into use in the middle ages. A method of sc])ar;itii.)ii of oil and water wlu(.-h in its principles corresponds to tlmsc ni the Florentine flask has, it a];)]iears been describeil for the ttrst time by Porta-) in the latter half of the sixteenth centm-y. The Fliu'entine flask like many other facts and impro\-ciiipnl s ]ier- taining to the art of distillation which were not geiierall.\- known, was soon forgotten. As a, ];esult it wsis redisi'overed several times from the beginning of the seventeenth century to the year 1S2:!. Thus the flask was agnin described and introduced by HonibHroa) at the end of the seventeenth century about one hundred ve,-irs after Porta's description — only, however, to be again forgotten for a con- siderable period <.)f time. A century kiter, in the year IHO;!, the Fh.irentine flask wa.s again rer'ommcndeil for the distillation of vohitilc oils li\- the Augsburg a]iothecary .loliann (iottfried I)ingler-t) and later in 1S23 once more introduc-ed as something new by the apothecary Sanniel I'eetz in I'esth.-") Tlie Flin-cntine flask of oliler construction as desciilied b\- Porta, has Ijeeii in u.se foi- a lon^' time. The oil was si]ihone(l off liv ineans of 11. porous si]ihon consistine- ()t' m laminvii'k into small bottles (tiu-. .•!<)). 1) (ieiRer'H .Magazin f. I'liann.. 11, |i|). 17+ & L",il ; HiiL-hiici-'s Urpei-i., :\:\, ],. 4:;(;. -) Magiae natiiralie, lib, (li'ciinns, p. ;l(^7. ■il PlilUppc iinil Ludwig, OeKi'hicli tc (lev .Vpulhoker, |>. .".l:?. ■i) Tri.iininRilurff' s ,]i»iirn. d. Pliarm., ll'i, p. 242. ■'I Biic'hner'K Itepert., 1+i", ]j. +S1. Hisfon- of the Metlioils of DmUhitioii nwl of l»stiirn,y means of steam admitted under jiressure tln-ciugh the holes of a, ring at the bdttiaii or 1)3' allowing the steam to escajie directly into the lower double walled jacket B. The advantage possessed by the receiving flask E over the ordinary Florentine flask consists in the flowing back of the distillation water saturated with oil, through the tube 7''. into the still. In the distillation with dry steam (ttg. 4;!) the still is filled with the plant material without the addition of water and distilled with steani passing through the material from the liottom upwards. These or siTuilarly i-onstructed steam distilling apparatus are employed even at the present time for tlie distillation of some of the oils, onlv in iil;i(>e of the spiral a t>d)e condenser is used. History nf the Metlinds of Di.stJII:ition nnil of Distilling Ajiimnitus. Ta With tlip iuti-odnctiou of these api>aratns during' the middle of this century tlie volatile oil industry had taken its position as a. branch of the rapidly developing chemical industry at large with southern France and central Germany as the principal centers of production. Sini-e then this branch of chemical industry has witnessed great technical improvements which have reacted favorably on its growth and permanent development. Owing to the remarkable development of the entire perfume industry during the second half of this c-entury. the consumption and commerce of the volatile oils a.ssumed entirely unanticipated jiroportions and importance. Scientific and technical attainment, (•ommercial iiitf^rests and l)Usine.ss competitioTi brought about numerous i-hanges in 7-apid .succession. Moiv rational methods of distillation were devi.sed, large apparatus for the distillation of enormous quantities were 74 HistDvkn I liitrndnction. constructed, the quiility of the proihict was iin]ii-oveil wliile the piire of its production w;is diniinislied. Some of the hii-jj.est stills used in the manufacture of volatile oils have a capacity of .•!().(»(»(» to (lii.OOO liters (= 7,92(5 to 15,S.'')2 ■;allons). Connnensuriite with their size is their construction and operation, the arranjiement for (■har;iiii^' and discharging, for the condensation of the vapors in as (]uiek and efficient a, manner as possible, and above all their produc'tiveness. Considerable historical interest is attached not only to the theory and ]iractice of the present art of distillation in its application to the pre]inration of the volntile oils but to the gradual development of the distilling vessels as well, which iire employed for this purpose. >.;:;oii.^. >..-,*;, ,. -...w/y/Z^ On tlie following ])agi'S will be found a number of illustrations of some of the modern stills used in (ierman and French factories. Looking back- ward it might seem as though no relation existed betwi'cn the modern giant stills and theii- prototyjies. Yet every one i_)f them is but a link in the long chain of develo]>ment of tlie art of distillation. Thnt the ]ii-ocess of evolution has licen exi;-eediii;il\- i-ajiid during the pnst ten yeais di .e.^ uot affect the truth of this st.iteinent. Almost evej-y one of These pieces of apparatus has been newly i-reated out of the ruins of its immediate predecessor. in modern chemical iiidnsti-y (xermany unquestionablv ranks first. Of the vai'ious branches of this industry that of tlu' manufacrnri' of vohitile f)ils and synthetic aromatics has acqnireil an importance ]ireviously unsuspected ami witli it a coi-respondingly influential position. Hintorv 1)1' tlie ilethoils of t)istiIlatioii and of DiatiUhig Ajiparatus. 70 Fig. 44. Modern Di.slilling niid Kpetifyiug Aii|>ni-atiif^ 76 ffistoriml Tntro'luctjon. (•■is. •i-'i. Distilling and Ueetifying Apparatus History or the Methoih of nistilhtion .■tin! of Distilliiif;- Aiiiianiti I'iff. it>. Apparatus for Uistillation witli Water. 78 Historic:! 1 In troilnctioi). Fig-. 47. Distilling- Aiiparatus of 30,000 Liter Ciipncity Hititory of tlw Mfthofh of Distillnlinn ;ui(l of Distilling Apjitinitus. 70 V\K. 4.S. Distilling Apparatus foi- Spices. 80 Historicnl hitroiJuctioii. Fig. 4;i. Great Still of G0,000 Liter t'aiiacit.v. History a/' Hip Methixls iil' Distillntioiranil of Disiilluif^- Aiij);ii-:itun. ^il Histoi-ii-;il Introductio/i. GENERAL PART. THEORETICAL BASIS FOR OBTAINING VOLATILE OILS BY STEAM DISTILLATION. From the t'(irp;:()iiij^- rlmpters it liec-cjines ai)])arpiit tliat tlie miiiiii- t'iii-ture of volatile oils was fonuerly coiulucted on a. small scale, larjiely after the style of the small mer-haiiic. But a siiif;'le iii-ocess for obtaiiiinfi' the (lils was nsed. even thouji'h here and there it was condncteil in a scientifli- manner, i. e.. i-ori-es])ondiii^- to the status of science at the time. All crude material.s and all oils were distilled in the same manner from a distilling; ajiparatus i-onsistiuc- of still, head, and condenser. When the still was heated directly by tire, only one kind of distilla.tion took place, namely water ilistillation. in which ea.se the material to he (listille' numlier of small factories and laboratories where (jils were distilled on a small .scale, a few have i-isen dnriuf;- the last few decades, and have develo])ed to such an e.xtent as to im])art to the entire industry a different aspect. It is. however, not merely the matter of size whicli sejiarates the ])a.st from the present. Tlie rapid development of chemical science is even nnn-e resjionsible for this difference. Throuji'h it the ]u-e](aration of essential oils has developed into a real industry, a liranch of cliendcal ti'chnolo^y. The .successful iuve.stifiatious of W'allach have 7)Ot only led the way in chemical science, but they have also done ]iioneer seT'vice in pi-actice. N<; Gen^nil Fart. Tills ilpvpl())imeiit of the volatile oil induwti-y has tjikeii plaiv in a ivniarkaljly short period of time, liideeil the nuusually rapid i;To\vth of cheniical knowledg-e tiiade it ditticiilt for ]irogTessive factories to keej) abreast with the theoi-etieal advancement, as did a,lso the fact that tlie simple a)i])aratus and methods no longer sntflced for the new requi)-e- ments. Some apparatus could be borrowed from other technical bi-an<-lies bat nuich had to be specially designed arul made. In addition to the simple stills formerly used, new rather com])licated a])paratns were con- structed. Although these reipiired greater ability and unjre iittention on the part of the ojierator. 1liey ga\'c in evei-y res])ect more satisfactory results. The evohiticm from (he simiile to the more highly ]ierfected technique i-an best l)e i-ompared to that of the alcohol manufacture from the whisky distillation on a small scale. The simjile stills of a. ]}ast time, which a,]-e now only used here and thei-e foi- the ])i-e])ai-ation of whisk\- on a snuill scale, will scarcely l)e recognizt'd as the i)rotrjty])es of the cohmni apparatus with continuous sup])ly of wort aTid i-ontinuous or pi.'i-iodic i-emoval of the wash, as tlii^y may now lie seen in their most perfect construi-tion and operation in modern alcohol (hstilleries. \Vhereas tlie former wliisky (hstiller first distilled off an intermediate ]iroduct, and from this by rectification obtained a whisky of only ;i() to -l-()"(i alcohol, the present column a])paratus yields with less attention, time and fuel. .1 s])irit of over '.H)"-'„ :dcohol in a single o]ieratic)n. In tlie alcohol distillation the coiKUtions are. liowe\ei-. much sin]]>ler than in the ])re])aration of the volatile oils. Thei-e a few raw materials : ]iotatot's. coi-ii oi- maize, and only one iMiil ])roiluct: alcohol. The knoAvleilge of the ajijiar.'itus is conniion pi-o])erty. it can be constructed by ;iuy i-elial)li^ co])]ii'rsmith : and its manijiulation is shown by the builder. Hei-e on the other hand, there are numerous i-rnde materials as well as numerous different ])roducts, which according to the use to which they are to be put i-eipiire different methods for ]a-odnction and purification. The a])])aratus necessary for these various o]iei-ations must be constructed and jierfected by the manufacturer him.si'lf. if he does not wish to remain liehind in the i-iaii])etition lironght .-ibout bv changes in the methoils of ]iro(biction. The adva,ntages of the ])resen1 ovei- the Former inilustr\- are a saving in time, laljor ji.nd steam, an increa.se in the yield ,and especiallv a,n ini]irovement in the quality of the oils. ('ou]iled with these are. liowever, a considerable increase in the cost of the wliole ]il;int. and resulting From this, the necessity' for ]irodnction on a larLi'e scale. Theoreticiil JSnsis for OliUiiuuig Volatile Oilfi, ftc. 87 Briefly desrribed, tlie uiaiiufHi-ture takes pla^ce in tlie following- manlier. The pivpared raw material is tilled into the distilling apparatus, wliirli is heated by steam. The vapors saturated with oil particles are eoiidensed in the cooler. The distillHte. consisting of water and oil, collects and separates in the receiver, and the crude oil thus obtained is ])uritied when necessary, in order to yield the tinished ])r(.)duct. The manufacture consists therefore of the following oi)erati nun. TndeT- this jiressure the water, if heated alone wonld boil at 100° ('. and the oil of turiientine. for the ji'reater jiart, would not boil until about l."i,S°. If. how^■ver. a mixture of water and oil of tui-]ientine is heated, the va]ior ]iressnri' of the water anil ,ilso that of the oil of turjientine. take pai-t in overcominj;' the outer ]iressure of TbO mm. The mixture of water and oil of tur]ientine will, therefore, boil when the sum of the two va]ior ]iressui-es is eipial to 7°, Ac(-or(lini: to this the aniouut (if service obtainable from the steam is the same with tlie (lire(-t as with the in(li7-e(-t heating proi-ess. In ]ii-actii-e, liowever, the two Wiivs of heating ai-e not ef|ually eftii-ieiit. With tlie indii-ect heating i| (.lue caliiry, abbreviated 1 cal., i" the unit iiiiantlt.v ef beat. II i.s the if heat reipiired to raiHe 1 k. of water ef about 1 .T^ one decree <\\ procpss nil lit' rlip liPiit (■(iiitiuiipd ill tlii' stPiiiii riiiiiiot liiMitilizpil. ;is loss of lient riiiniot bi' ]ii-pvriiteil. On tlip ntlier liiiiiil in the ilirert lieatiug- ]iMirpss. if tlip stPMiii is riiiiilnitpil into tlip oil-roiitniiiiiifi' Tiuiterial sns]ipiiilpil ill Wiitpi-. Ill- into tlip volntilp oil itsplf. in rasp of i-prtitiration or frai-tioiiiition a loss of lipat is only jjossiblp tlirmi^li carplpss ronilnction of tlip stpaiii. If tlip oil-contaiiiinji- niatprial is ili-y in tlip still, tlip loss of lipat ill iliivrt lipatiiifi' will hp nsuallv lai-i;p. ami with i-arplpss iiianiii\ilation may lipronip so lai-pp. tliat only a small ]iai-t of the ilii-pi-t stpam is iitilizt'il. wliilp tlip lar.iipr ])art iiops nnuspil into tlip ronili'iispi-. Tlip tlipovptiral lipatiiij:' pffpft of tlip stp;im may also lip otitaiiipil whpu tlip oil-i-ontaiiiinii- matpvial is ilry, hut this can lip iloiip only nndpi- cpitaiii sn]ii)i)sitioiis. Ill ovilpr to cali-nlatp from tlip aliovp lipat vahips of tlip stpam tlip i-ost of tlip stpam for a ilisrillation. tlu' proilurt of tlip ilistillatioii. i. p., tlip ilistillatp. must fii-st Iip morp rlospl,\' pxamiiipil. Tlip ilistillatp ronsists of wati'i- anil vulatilp oil. Tlip i|npstiiin tliprpfoiv arisps, how mni-li wati'r anil how mni-li volatilp oil is a i-prtain amount of stpam rajialilp of ilistillin^'? pj\'iilpntl\' tlip answer to this qupstioii ilpppiiils tirst of all on tlip ri'lativp wpifilits of tlipwatpr ami tin- oil in tlip ilistillatp. Thisrplation. of i-oiirsp. iliffpi's with tlip iharaitpi- of tlip volatilp oils, anil is fnitliPi- mori^' ilp]ipiiilpnt for earh and pvpry oil upon tlip ilistillinji' tpni])Pi-aturp pmjiloypil. and the i-haiijipalilp ronijiosition of tlip oil : on tliP other liand tliP ratio is tixpil. so that 1) with a snrjilus of stpam the watpr contpiit ill till' mixture of vaiiors ;i-oin^' into the rondenser nia,\' iiidppil lie ini-rpaspil ; 2) in s]iitp of an prononiic sn])]ily of stpam and a ppiierons sn]i]ily of oil the amonnt of the fornipr rannot he derrpaspil. The anioniit of oil whirh is \-olatilizpil with tliP steam, is determiiipil by tlip va^ior liressnres of both at the distilliii;;- tpni])eratiire. The ipmntity of oil in thi> distillate ran lip detprniiiipil pxiipiinipntallv if tlip distillation bp so rondnrtpil that tlip vapor rontains the iireatpst ]iiissililp ipiantity of oil. It ran also be rali-nlated if the va]ior prpssnre of tlip psHPiitial oil at t lip di.stillinp- tpnqipratiirp bp known, for the ]iarts by volume in the mixtnrp of tlip \a]iors of two imniisrible liqniils, are to earh other as the va]ior ]irpssurps of these liquids at the bnilin^- tpuijiPi-aturp of the mixture; or the jiarts by wpifi'ht arp to parh otlipr as tlip vajior iirpssurps multijilied by the xaiior dpusities or the unili'- rulai- weii;hts. If ni\ = the molerular weip-ht of one of tlip liquids. />! — tlip va]ior ]iivssurp at tlip distilliiip- teinperaturp. A'-i = tlip ]iart by weip-lit in the xaiior. 'JlieorHtii;il B;hsis fur Olitniiiinf^ Volntile Oils, etc. 91 and hirtlipi- ;h2. l)-2- g2. 1"' tlii^ ciiri-pspoiiiliiii^' xiilups of the nther liquid then ;^'i : fX-2 = nil pi : m-2P2- As an exani])le of such a calculation, the distillation of caraway oil with water va](or under atnios])hei-ic ])ressui-e may be taken. Caraway oil consists of a mixture of liun)nene and carvone in nearly equal jiarts by weii^ht. Its lioilini;- temiierature by distillation with steam under at7nos])heric ]iressure, namely ?(>(> mm., is a few dei;rees below 100°; at the l)e;iiiniin,i:' of the distillation somewhat lower, toward the last uearly 100°. The vajior (iressuiv of the linionene (uiolecular wei<;ht l;i()) at .")7.-")° amounts to 12 mm., that of the water (molecular weij;ht IH) at the same temjierature is '['■V2 mm. At the distillinc' temperature of "i ')° . there will, thei-efore. be in tlie distillate for evei-y lOO k. of water, 70 k. of linntnene. At 17(i°. the lioiliuji' ]i()int of the linnniene undin- 7()0 mm. ]iressure. the water exerts a vajior ]ii-essnri' of ()!)()2 mm. of mercury; therefore at 1 7()°, with 100 k. of water there distill over MH k. of liuionene. According- to, this, at a distillin k. of oil for evervlOOk. of water, but much less. Acco7-din! ]ia7-ts by weicht of oil. and ]iast tlie middle of the distillation ]iaits by weight of oil to evei-y loo ]i!ll-ts by wei^ilit of wate7-. Afte7- the heat effect of the steam foi' tlie distillation and the 7-elatioii of watei- and oil in the distillate have lieen dete7-7iiine(L the heat iiecessarv fo7- obtaining' a. ceitain a7nount of di.stillate 7-e7iiai7iK to be asce7-tained. ilL' Geufv.-tl I'.irt. Aside from the lu'nt i-oiisniiKMl in Wiiriiiiuj;- tlir distilliiifi' a.])]);irorization is jiroportional to the absolute teni])er- ature of the hoilinji' ]ioint. Vnv linionene the calculation j^ives (l.").."! cal., f(n- cai'vone (!() cal. for the mat of mass. To lie sure, these are the heats of vaiioi-ization at the lioilin.")1.7 cal.. yield in the most favoralile case of a caraway oil distillation l.:ik. to 1.1 k. of distillate. Or when the heal re(|uired is based only on the volatile oil. 1 k. of caraway oil <-osts in the course of the distillatiroiiiisinii' investigations have been recorded, is made (]uite freijueiitly. The jirejiaratioii of the volatile oils from the jilants was i-onsidered to be a well known operation not only (jO years ac'o. but also a little more than a decade aji-o. Now, that this industry has so enormously develo])ed tliroueh successful investifi-ation of the voliitile oils and with the aid of better mechanical appliances, when out of the former "Destillirkunst" there has ;irowii a scieiitiflcally con- ducted industry, which, combined with commercial experience has reacheil unthou;j,ht of results, we know, that this development is by no means comjdeted. The following- may serve as the most imjiortant characterizations of the different ]irocesses of distillation for oil-containinc- material, or for the rectiflcatioii or fractionation of the oils themselves: ,■() Dry steam distillati(ai with saturated steam under i>ressure. /)) The same, but with suiierheated steam. I- ) Water distillation. (/) Distillation under diminished pressure. p) Continuous distillation. Throufili modiflcations in the conductinji,- of a certain i)rocess of distillation in an apjiaratus with the reipiisite construi-tion. further throujih suitable combination of these main ]n-ocesses, acc. p. 24.1 Tlieiv is 11(1 limit to tlip sizp of tlip ii]i])ar)itns. If tlif ciioriiioiis niassps of ilistilliiiii' nuitpriai aiv at liaiid. wliic-li sncli an a])]iaratns ivquircs inv its fcoiioiiiic oppi-atiou. tiiwe is iiotliiiij:' in tlii' way iif fi-ei'tiiiji' as lar^p an aii]iai-atns as ina\' 1ip ilpsiivd. Cooling and condensing of the vapors. Oolil water is used in fiPiiPval foi' coolinii' and i-ondpnsin^i tlip va])c)rs t'T'oia tlip distillinji' ap])aratns. Tlip vajioi-s arc condnctcd into tlip condenser tlii-ou-ent fetid odor of the stems of nniny blossoms are verv a])t to cover the odor of a mild smellinfi' volatile oil which is ])resent in only small quantities. This may take place to such an extent, as to make the product wholly worthless. From this it will lie seen, how numerous the causes are for the deterioration of the volatile oils. The foreio'u odor which is thereby ^i'iveii to the oil. was formerly and probalily is even miw called ••Blasen<;erucli."' This is an old. very inaiiiiroiiriate tei-m. which arose at a time when the various causes of this odor were still unknown. The Mocalled ■'Blaseufieruch" was formeily the distin<;'uishinerty of everv ci'ude oil. If it was slifiht. attenijits were made to T-einove it b\- lone- ex]iosure of the oil in open vessels. The more easily volatile 0(i (wTiPViil I'.irt. iiiiiiuritiHs nT;i(ln;illy p\';i])i)i-iitp dnriiii;' tliis treiitiiieiit. siii-li ns .snl]ilinr- ctted li\(lr()j;eii. iicptiildrliydr, erly conducted a sinc-le I'ectitication should be sntticient. THE MORE COMMONLY OCCURRING CONSTITUENTS OF VOLATILE OILS. Till' vdlntile oils :\iv widf'ly distriliiitf'd in tlip vp^^ptuble kiii;:il(iiii, iiKiVP ]);u-ticiil;ii-ly. liciwevpr, in tlie ])haiipi'i)i;ani.s. From the ci-yiitoiinnis, ii volatile oil lias so fai' lieeii obtainpil only from the male fern. In most rases tile oils exists ])ref(jrmeil in the varions organs of the plant, the leaves, tlowei's, fruits, stems and roots. They ocriir secreted either in inlands or in canal-like, intercellular ivcejitacles. Only a few are formed liy hydrolysis during- the jiroi-ess of preparation fi-oni other sulistances in the plant, e. g. bitter almond oil from amygdalin, nmstard oil from sinigrin. Nothing detinite is known with regard to their function or their ivlation to the other constituents of the ])lant organism. It ap])ears. however, to lie well estalilisheil that they are excretions formed during the life ]irocess of the plant, which are of no furthei- im]iortance in the ]ii-ocesses of metaliolism. It does not follow from this that tlie.\' are therefore useless, foi- they act as a means of attracting insects that bring about fertilization, they alsletelv of Thf Mors Commonly Occufiinfj; ('onst'iUwntH of Volatile Oik. 99 hvdi'ocarboiis ('loHiu of tlip tprppue sfi-iew. A siierific >>Ta\-ity liiiilipv than 0.90, as is t\w rase with most oils, indicates a mixture of terpeues and p(jssiV)ly tlieii- oxy<;en derivatives; wliereas a specific gravity of more than 1.0 indicates the presence of compounds of the aromatic .series, or if tlie compound contains sulpliur or nitroo-en, of suli)liides, nitriles. ov isosulphocyanides. Tlie optical properties, rotation and refraction, are of less importance unless pure chemical compounds are to be examined or adulterations to be looked for. The optical activity of an oil indicates the presence of a compound oj- compounds with one or more asym- metri<- carbon atoms; a high index of refraction the presence of a .sub.stance or substances with double bonds. When exposed to low temperatures, a nundier of oils deposit one or more of their constituents in crystalline form. 8ome oils, like rose oil, contain crystals even at ordinary temperature, others, like orris oil are butyraceous in consistency. These substances have been designated stearoptenes or camphors and are paratflns, higher members of the series of fatty acids, such a.s lauric, myristic and {talmitic acids, and derivatives of ai'omatic and h,\'droaromatic hydrocarbons. Most oils that can be distilled under ordinary pressure without decomposition begin to boil above l.")0°. Exceptions to this T'ule are e. g. those containing sulphur, and the oil of the Digger's pine, which contains normal heptane. In the absence of oxygenated constituents, a boiling point below 200° indicates the presence of terpeues, between 2.'')0 and 21S0° sesquiterpenes, above ;!00° polj'teryjenes. In theii- elementary composition the volatile oils do not manifest great variety. All contain i:-arbon and hydrogen ; most of them alsf) contain oxygen in larger or smaller quantity; few contain nitrogen or sulphur or both. The presence or absence of oxygen can be determined by elementary analysis only. The presence of only a small amount of this element, up to ■") p. c., indicates a high li.ydrocarbon content. The presence of sulphur, which can be oxidized to sulphurii; acid liy means of concenti-ated nitric acid in sealed tubes, indicates sulphides or poly- sulphides. Nitrogenous compounds are converted into cyanides b\' heating with metallic sodium or potassium and recognized b,\' means of the Prussian blue reaction. The inti-ogen content of an oil is mostly due to nitriles. If sulphur is also found, mustard oils are present which, as a rule, betrjiy their presence by their characteristic odor. After the elementary comj)OHition of an oil has been asceitained, a few grouji reagents ca,n be applied to learn whether syiecial attention 100 (iein'ral I'.irt. slioulil 1)1' ^iivfii to (lup cliiss 111- :iiiiitliPi- iif clipmiciil coinpouiiils. If nii nil shows an acid reaction, it fontaius acids nv phenols. Small amounts of fatty ai-iils occur oci-asioi)ally as decomposition produi-ts (jf esters present. Lare'ei- amounts reveal their pivsem-e liv the diminution of volume when the oil is shaken with an aipieous sohttion of caustic or carbonated alkali. The preseni:-e of an ester or lactone can lie ascertained when an oil is heated with alcoholic potassa. of known strenc'th and titrated hack with standard acid. This test ]ii-esupposes the absence of free acids and alilehydes. Alcohols can be converted into acetic esters by heatine' the oil with acetic acid anhydride. iSiib- sequent saponification will then reveid the presence or absence of an alcohol ill the oil. Aldehydes and ketones can be recoj:nizeil by their addition products with alkali bisulphites, or by their condensation products with hydroxylamine. The latter contain nitroR'en and as a rule are ilifflcultly volatile with water vapoT-. Ethers, which are some- times present as ]ihenol ethers, can be reco,>iiiizeil by means of Zeisel's method. After the.se preliminary tests have revealed the jjre.sence of a substance lieloiiii'iny to one of the above mentioned i-lasses, it is sometimes possible to separate it without frac-tional distillation: provided, however, that this method of se]iar:itioii does not chanye the other i-onstituents of the oil. It should also be noted that these methods of separiition neyer effect a perfect isolation liecanse the other constituents of the oil prevent a jiart of the substance to be isolated from reacting'. \\'hen, therefore, the non-reactine- jiortion of the oil is fractionated small amounts of this substance should not be overli.ioked. Thus it is possible with these eroup reiigents to separate aldehydes and many ketones with acid sulphite solution — a reaction that .can at times be facilitated by the addition of alcohol. The crystalline addition proihict is washed with alcohol and ether and the aldehyde or ketone ree-enerateil bv the addition of alkali oi- dihite aiid. Free acids and jihenols can be shaken out with aqueous alkali; indifferent substances are then i-emoveil from the aqueiius solution by sh.ikiiie- it with ethei-. and then the acid or phi'iiol is set free with dilute mineral acid. If acids a,nd phenols are both present, the former are .sejiarated with carbonate solutiiui, Lai-tones yield salts of the correspondine- oxyacids when heated with alci.iholic potassa. They are jirecipitated as lactones or oxvai-ids bv the addition of a minei'al acid. Esters thai maybe present are saponi- tied by this treatment with alkali, aldehydes and ketones, however, ,are niodifled therebv and at times destroyed. Tiie Miitv Conininnlv Orcnrririfi- Canstitiients of Volatile Oils. 101 If noiip (if tliese sliort i>uTs is possilile tlip oil is frai-tiouated eitlipr niidei- ordinary or diiniiiislied pressure. If esters are present, the oil is tirst saponified. It may be talliatic. The lowest hj^drocarboii of the ijanitfin series wliich lias been found ill i\, volatile oil is the normal heptane, C'lHio (h. ]>• !)W°). It constitutes the hulk of the oil obtained from the oleoresin of the Diii'ger'.s pine. I 'in us ,sn hiiiia mi . The hifiher members of the paratKn, and probably of the oletine series a.lso, ajipeiir to be (juite widely distributed in the vegetable kingdom. They eonstitute the waxlike cojiting and secretions on leaves, flowers, fruits etc. In volatile oils, however, they are not met with commonly bec'iuse of their sparing-volatility. 8ometimes they separate in crystalline form when the oil is exposed to a, low temperature, or they remain behind upon fractional distillation. In the oils of rose and chamomile, however, tlie amount of jiaratfln is so large, that the oil congeals even at middle temperature. Apparently these hydrocarbons .seldom occur alone, but as mixtures of homologues arS has been shown in the case of rose oil. Tlieii' melting points .seldom if ever agree with those of known members of the series. "With the exception of tlie heptane referred to, they are obtained jirincipally as white, colorless, laminai'-crystalline ma-sse.s which are with ditflculty soluljle in cold alcohol, but readily soluble in hot alcohol and other organic solvents. They are remarkable on account of their stabilitv toward concentrated acids nnd oxidizino- agents at ordinary temperatures. The rose oil stearoptene melts at '-i'y" and when di.stilled in vacuum can be i-e.solved into two fractions melting at 22° and 40 — 41° respectively. In addition to this solid mixture, parattin (or oletine) hydroi-arbons have l)een found in the following volatile oils: Sassafras leaf oil M. P. .58° Oil of gaultlieria " 65.5° nil of sweet bireli " 65.5° Oil of wild berg-aiiiot '■ 62° Dioleflnic hydrocarbons have so far not been found in volatile oils. The hydrocarbon isoprene, C-jHs, which belongs here and which i.s closely related to the terpenes, has been found only as adecomposition product of caoutchouc and of tni-pentine oil. Fdi- its ])reiiaration consult Mokiewskv's recent woi-k.' .Vrnica Hower oil... M. I'. 03° < 'ha;inon!ilc oil ' • 58- ■ 64° 51 Dill oil ' <'araway oil (from lierb) Neroli oil ( .Un-ade) ' • 55° 1) ('hem. reiitrlil., 70i. |). ."iSH. 77(p Mm-p Cojiiiiiniily Ocvurviug CoiiNtitnt'iit.s of Volatile Oils. KCt However, chain liydroi-arboiis of the foviiiuhi of s;t1ui-a.tion ('„H-„-4 with three double bonds have Ijeen found. In composition tliey agree with the terpenes but differ in liavino- a lowei- specific gravity and in their index of refraction. These liydrocarlions wliicli have been termed ■■olefinii- terpenes" by Semmler liave not yet been well character- ized. They show a. .tireat tendency to resinify, especially when distilled under oi-dinary pressure. The first representative of this class was found in oil of bay by Power and Kleber' in ISO.' and termed niyrcene by them. It boils at 167° with partial resinification, UTider 20 mm. pressure at ()7— ()1S°; di .5° = O.M()2:i ; n„ = 1 .4(57:i. The only known i-eaction by which, in the ab.sence of crystalline ad- dition products, it can be identified is Ijy means of its hydration with ;i-lacial acetic and sulphuric acids at 4(»° according to Bertram's method. 2 Myrcene is thereby converted into an acetate of lavender-like odor, which upon saponification yields linalool. Permarioanate oxidizes myrcene to succinic acid. Similar hydrocarbons have been found by C-liapmanS in oil of hops in 1.M94; l:iy Gildemeister-t in Smyrna, oi-iganuin oil in IH!)."); and tinally by Klel)er-'' in sassafras leaf oil in 1.S9(). I). Aroiiiiitic and liydroaromatic. A hydrocarbon of the aromatic series of the composition CioHig was isolated by Lunge and Steinkauler" in IHSO from the oil of the needles of the nuvmmoth fir. Sequoia giganten and was termed sequoi- ene by them. It consists of laminar crystals which melt at 10.")° and boil at 200 — 800° (uncorr. ). It is not identical with fluorene and other liydrocarlions of like composition. Styrenk. The simplest !ii'omfi,ti(/ hydrocarbon with an unsaturated side chain that is found in volatile oils is styrene, ('hH.^. (:H = CH2. It occurs in storax oil and i-ecently has been found in xanthorroea. resin oil. it is prol)ably formed by the decomposition of cinnamic acid. Styrene is a colorless, highly refractory liquid of a pleasant odor, whic-h polymerizes to a transparent, glasslike and odorless mass, meta- styrene fC.sHsln- by l)eing kept for some time, anil more rapidly liy 1) Pharm. RundHch., 1;!. p. <>1. +) -irch. cl. I'haiMii., 2:!«, p. 1.S+. 2) G. I. P. 80711. =) Bericht S. & Co., April ISIIIJ, p. 71. 3) .rom-ii. Chcni. Soo., (>7, p. ." + . «) liericlite, l.'t, p. Ifi.'JIJ: 14, p. 220L'. 104 GeiiPinl Part. lieatiiifi' (ir wlien in rdiitact with aciils. Tlie lioiliiip' pdint of pniv styiviie is 144—1-1-+..")°. As to it.s physical ])roperties, tlie followinji- statHiiiPiits liaA^- bt^pii iiiailp : H, p. 140° at TOO mm.; don =<». 0074 ; n„ = l..-,40:!0 (Briilil.i lSN(i ). H. p. 14().2ro(luct ( Kelbe. di-y distillation of colophony; Wallach. ilehydration of fenchone ; Baeyer, splitting off hydrogen from sylvestrenc). ]i-i-vniene is a fre(pient constituent of volatile oils. U|) to the ])7-esent it has lieeu found in the volatile oils from Thymine vjilgtiris, Tli. spi-pylluiu. 111. rnjtit.-itus. S;iturpj;i liortensi.s. S. tlivmhrn. .\[oi, ;inl;t jinnrtnfn . Ptyrliotis ;ij(M\;in, in oi'iganum oil from Trieste and Snivrna. in Roman caraway oil fi-om Cuiniiinin i-yinuiiuii. in thi' oil from the seeds of waterdiemlock. ('icut;i vifos;/., a,nd in the oil from I'Jiii-;ilyptu>' li:wiii:ist(nii:i. Like m-cymene it has also been fre(|uently obtained as a transformation ])ro(luct. Formerly it was thought that idl terpenes were ivlated to this hydrocarbon; that they were its hydrodei-i va fives. .\ccording to recent investigations, however. 1 his coucepticm is not wholly cori-ect. Jt is worthy of mention, that se\-eral conipo\nids of the foi-mula ('ii)Hi«(.) can be changed to i)-cymene by the abslraction of water, for instance, camphor and citral. 1) I.iebi^'s .-\ iiiKilcii. IIH"). |i. i;-!. -') Ltel)is'« .\]iniilcn. 221. p. (111. '^) (iazz. clnni., l.'j. p. .^)1»: .lahrcstM'i-. f. clicin., 1SS.~, p. ;!1J-. Jl Lipliifi's .\mi,'\k'n, 210. p. 2s,s. Tlw Morr Conniionly Orciininfi ConstitiwntN of Vol,-i1iIe Oih. 105 OynipiH^ is a colorless, pleasant siiielliii<;- li(iniil. whieli possesses tlie peculiarity of bei-oniiu-i- tiivbid. with sejiaratioii of water on standing- for some time; the reason for this behavior is not known with f-ertainty, perhaps it is due to a firadual oxidation. For connnon i-yniene was found ; B. ]). 17.",— lT(i°: d,.-,:=<».NC,(l2 (Widman.i l.SOli. K. p. IT.'i.iJ— 17.',.()° (at 752mm.); d-{'' =().,S.-,.-,l ; ,i„ = l .-l-,s4(i."', (Briilil,-' l.Si)2). B. p. 17:i..",— 174..",° (at 7(;:i mm.); di.-,: =()..s,",<).", ; di(,o = 0.,s.-,SS ; n„ = 1.47!) (AVolpian.« isixi). The pure hydrocarlioii is optically inactive. Dilute nitric acid and chrcmiic acid mixture oxidize it to ])-toluic aciil and finally to terephthahc acid. Potassium permanganate acts on it oidy with difficulty and chanues it. ])articu]arly with heat, into ])-(,xyisopropylbenzoic acid (m. p. l.j.") — l."i(;°) which with dilute hydroi-liloric acid yields p-isopro- ],enylbenzoic ac-id (m. p. 2.",.",— 2(i()°) by splitting off watei- (E. Meyer & Kosicki.J^ iHSr! ). (_)xyiso])i-o])ylbi'nzoic ai-iil is chai-arteristic for pi-cymene and is used for its identification. F(,r its jiivparafion Wallach in ISOl giive the following directions : •' 2 g. at a tiiiic (j[ the li.vilri, carbon, |irc]iai-ed as ]inrc as ]iiissililc, are heated ■\\itU a .solntioij of 12 g. of |,i)ta.ssinia pei-inaug-aniUe in ;!.30 g. of water on a \vaterl>atli with refinx condi'ii.scr, the mixture t)eiiig freqiientl.v agitated. When tile oxidation is com]ilete, tiic filtrate fi-om tlie oxides of manganese is evaporated to dryne.ss and tlie saline residue l)oiled with alcohol. The potassium salt wliich is soluble in tlie alcohol, is dec<,mposed in aqueous solution witli dilute snlplmric acid and the precipitated ai-id reer.vstallized from alcohol. The barium Sfdt of the sulphimic arid produced b\' treating the hydrocarbon with concentrated sulidiui'ic acid is also characteristic for cynieue. It (('i(,Hi:!. S(.)a)2 Ha crystallizes in sliining, difficultly soluble laminae and c(,ntaiiis three molecules (,f water (,f c i-ystallizafion which can be ci,nipletely dri\'en (,ff at 100°. The snlphone amide which i-an iie ]irepare-'. +) Licbis's .\lliJHlen. 21",,, p. L'S2. -) Bei-icliti.', L'.*, 1). ITll. •' I Tjiebi^'".'^ Annalen, 2(;4, p, 10. 3) Phiirlii. Zcitsclir. f. Itiissl.. ;!r,, p. ll.".. 10() ■ aenerni Pnrt. "terppiies ])r()iier." As to tlifii- foniiatidn in tlip plant organism notliin;^- detinitp i,s known. They possibly aiv genptically relatpd to oxvaeniited clinin (-oniponnds from wliicli liydrorarlxms ('iiiHio ran 1)p prejiared artiflcinlly l)y splitting off water. It is remarkable, however, that the terpene content of an oil is greater the less developed the ]ilant was at the time of distillation. Tlie nmjority of the known hydrocarbons of the ter])ene group are fonnd ready formed in nntnre: viz.. jjinene. ca,mphene, limonene, di]:>en- teiie. pliellandrene. sylvestrene. ter]iinene. Witli exception of the racemic di])enteue and the inactive terpinene. these hydrcjcarbons occui- in both o]itical moditications, though in different volatile oils and with a varyinji' degree c(f rotation. It might appear doubtful, therefore, whether dipentene and terpinene are natural hjnlrocarboiis or decomposition products of readily cliangeable terpenes. To isolate a terpene in pui'e form from a volatile oil by means of fractional distillation is mostly im])Ossible. Neither is it necessarj'. for , it suffices to remove oxygenated compounds from the fraction loO — 180° by repeated clistillation over sodium. The physical constants can then be deterinined and a characteristic crystalline derivative piepnred. These will be described under the individual hydrocarbons. Fix EN K. Pinene is the principal i.'onstituent of the distillates from the resinous ex(.-retions of different species of Piiiiis. which occur in commerce under the na,me of turpentine oils. In smaller amounts, usually togetlier with other terpenes, it has been found in a large number of volatile oils. Both opti(;ally active modifications occur; American tuqientine oil, German nnd Swedish pine needle oil from Finns nilrestris. the tar oil {Kienol) from the san}e s])ecies and the distillate from the needles of I'inij.s cenihru c-cjnsist inainly of d-pinene, while French turpentine oil contains mostly 1-piaene. d-Finene (australene) has been shown to lie present in cvpress oil, star anise oil, camphor oil, oil of laurel leaves and l)erries, mace oil. fennel oil, giilbanum oil, coriander oil, niaouli oil, myrtle oil. oil of c-heken leaves, eucalyptus oil [E. glolmlus). French basilicum oil, spike oil, and tansy oil. 1-Finene (terel)eutene) occurs in the following coni- ferous oils; in the oil from the leaves and i-ones of Ahien nihil, in the pine needle oils, in the oil of /'. ntontuna Miller, in English pine needle oil from P. nilvf^triK, hemlock oil, in the oils of Abien .sibiricn and .1. c/inndfn.sis. further in canella oil, olibaiium oil, cajeput oil. valerian ami The Moiv Coimnonly OccuiTing t 'oii.sthiieiits of Volntilf Oils. 107 1vesso-VD0t oils, in tlivme oil, spearmint oil, in the oil from the fruit of Petroseliiium sativum (parsley seed oil), and the oil of Asiirum mropaeum. In small amounts pineue has also been found in elderberi'y oil, thuja oil, nutmeg oil, massoy bark oil, sassafras leaf oil, rosemary oil, in peppermint oil, sage oil, lavender oil. and the oils of Tljyiuuv f-npitatu.v, SatureJH tbvmbra. and Asafoetida. Pinene is one of the few terpenes which can be obtained in a eom- parativel.y pure state. It is obtained, although optically inactive, by treating the solid pinene nitrosochloride with aniline in alcohohc solution (Wallach,! lS8i) and IMOO). The pinene thus olitained shows the following properties: B. p. 1.").")— 1.")(;°; d2o° = <).,S.-i,S; nD2i° = l.J-G.'').",;! (Wahach.i' 1H!)()). For the preparation of the active modification of pinene, American or French turpentine oil is used, the fraction boiling Ijelow l(j()° being- purified by fractional distillation until the hydrocarbons obtained coin- cide in boiling point and in the othei- properties with i-pinene. The highest rotations so fax- ol^served are : for d-pinene from the oil of the needles of the Biberian cedar, Pinm cembrn (Flawitzky.s 1892) [,/.]d]s-=== + 4."').0-1-° (B. p. l.")(;° rorr. at 7.'):i mm B. ; d-??!^ = ().H.-,S."1) ; -^ for 1-pinene from French turpentine oil (Flawitzky.-^ 1M79) [,,]d2o»= — 4-;!.J-° (B. p. l.').')°; d2o» = 0.iS.-)H7).i If it is necessary to employ solvents in determining the direi/tiou and magnitude of the rotation, tlie influence which these exert must be considered (Landolt,^ 1.S77 ; Rimbach,« 1.S92). Pinene is a colorless, mobile liquid which, like all terpenes, takes up oxygen from the air on standing and becomes partly resinified. It is readily converted into other terpenes, thus it is changed by a higher temperature (250 — 270°) or by moist hydrochloric acid into dipentene and its dihydrochloride re.spertively ; by alcoholic sulphuric acid into terpinolene and terpinene, probably with dipentene as an intermediate step. By treating pinene monohydrochloride with sodium acetate or aniline, (^amphene is formed, pineue nitrosochloride, however, yields under the same conditions ])ure pinene. In contact with dilute mineral acid.s, pinene is converted in time into terpin hydrate 0i(iHi8(OH)2. H2O 1) Lieblg's Annalen, 2.52. p. 1.42; anil i) Berichte, 12, p. 2857. 2.18, p. .848. ''^ Liebig-'s Annalen. 189. i>. 811 — 817. 2) J,iebig's Annalen, 258, p, 84-)-. "I Zeitschr. ph.vH. Ohem., '.), p. 701. :<) .Journ. f. pr. Cheni.. 11, 45. ]). 115. Ids (Icneval I'.irt. (111. p. IKi— 117°). :iih1 liy liydratioii with sulpluirir acid and f;lacial acetic acid it is converted into tcrpineol. Oxidizing- aj^ents act differently oii ])inene. \^'llile concentrated nitric arid produces so violent a reaction that ignition often talces place, dilute nitric acid, like chromic acid mixture yields besides lower fatty ai-ids and other jiroducts. terephtlialic arid (:8Hn()4 and tereliic acid ('tHkiOi. Entirely different results ai-e olitained with potassium ijermanganate; very dilute jiermanganate solution induces, as the investigations of Wagner^ (lSi)4 and l.S!)()) lia.ve shown, chiefly the formation of neutral oxidation ]iroducts. such as pinene glj^col, etc. hy employing a concentrated solution a nionoliasie keto acid ('iiiHioO:i, pinonic acid (m. ji. 1 (Ki— 10.")°) is formed (Tienmnn and Semmler- iNi).'.— lS!)(i ; Haeyer-MSilC, ). This on the one hand, yields Anally tei'eliic acid, on the other hand the same "Aliliau" products as those formed liy the cixidation of the derivatives of cam]ilior. Pinene is an unsaturated liydrocarlxin with one double liond which may be rennived tiy addition. By conducting dry liydroi-hloric ar-id gas or hydrobroniic acid gas into perfectly dry and cooleil pinene. the monohydrohalogeii derivatives of pinene are formed, of wliicji the h\dro- i:-hloride. ('mHioHCl, called ■"a.rtiflcial camphor" on accinmt of its ca.niphorlike odor, melts at 12."i°. the hydrobroniide at '.)()°. Both are converted into canijiliene on s]ilitting off the hydrolialogen. If liromin in a dry sohvnt is allowed to act on pinene. one molecule is rcailily taken tip with decoloration. On fui'ther addition the alisorption takes jilace only very slowly and is acconqiatiied by evolution of hydroliromic ;irid. From the )irodtict formed by the addition of one molecule of bromine to jiinene a dibroniide melting at Kit) — 170° may be obtained by distillation with water vapor + (Wallach. 1S<)1). A larger yield of this dibroniide is obtained by treating pinene with hypobromons acid"' (Wagner and Ginsberg. IN'.Xi). By splitting off hydrobroniic acid bv means of atiiline the dibroniide is changed to cymeiie. while when treated with zinc dust in alcoholic solution it yields a new terpene of the melting point (j-"i — (i(i°. tricycleue" ((iodlewski and Wagner. 11S07). The conip(.)unds which are best suited for the ch;ira,cterization of ]:iinen(> are jiini^ne nitrosochloride, formed by the addition of uitrosvl- chloride 1o pinene. and the nitrolamiiies which may be |irep,areil fi-om it le 11 lU-l-iclllr. 27. II. L'l-'TO: L>'J, |1. SSI. 4| I,ii_.l,ij;'s .\lllial01l, !■(; + . |1. -'I r.i'rirliti'. lis. |i, 1:14.". : i.".i, |i|i. ."li".!. :!(jlI7. -" i Ik-iit-hti', 20. p. s'.iii. :'] I'.prichti'. 2'.l. pji. 22, :C2(1. T.IUT. 1'.I2:!. " I ('Ii.mii. /A-itun,s-, 21. |i. VIS, 77;p More Coinintiiily Ocfuniug CoiisfitiwiitN of Vohit'ilp Oils. !()!> by tiviitment with orf;aiiii- liases. Fur the pi'eporati(.in of tlie nitroso- chldi-ide ^^'alla(:■h ( IS.SS ami llSN!)) has jiiYen the followiiin' dii-eetidiis : i A mixture of 50 jj,-. each of turiieiitinc oil (iiiiiuaterial whether laevo- or dextrogyrate) glacial acetic acid and ethyl intrite- are well cooled in a freezing- mixture and 15 cc. of crude (33 percent) hydrochloric acid are gradually added. The nitrosochloride soon separates in a crystalline form, and is obtained in a fairly pure state when it is filtered off with a suction jiump and well washed with alcohol. From the fiHra.le some more idti'osocldoride sejiai'ates on standing in the cold. It is i)rot1tal)l<' in regard to yield to woi'k with small quantities, as only tlien <-an the low temperature lie maintained which is necessai-y for the sa.tisfactory conduct of the i-euction: large (|U!intities of ])iiiol ('loHirjO are foi-med as a by-product. The nitrosochloride is a. white crystalline powder, which is readily soluble in chloroform and may be ayaiu .sepat-ated from this solution by raetliyl alcohol. The meltiuii' point of the recrystallized compound is 1 03°. Like it.s derivatives it is optically inai/tive. According' to observations by Baeyer-' pineue nitrosochloride is a bisnitroso compound (<'i(iHHiFl)2X;;(J2, which in ethereal solution is idianged by hj^drochlorie acid into hvdrocldorcarvoxime.J^ By splitting off hydrochloric acid with alcoholic potassa, it is ccjnverted into nitrosopinene (m. p. 1;!2°)-"' which has lieen recoft'nized as the oxime of an unknown ketone CioHiiO." Aromatic bases, such as aniline and toluidine split off nitrosyhddoride. i-egenerating- pinene with the formation of amidoazo-com]iounds. (2uite different is the behavior of the nitrosochloride to bases of the fatty series and those whiidi possess their (diaracteristics. as for instain'e, benzylamine and ]jiperidine. With primary liases as well as with piperidine nitrolamines result ; the secondary bases, like diethylamine, however, produce a, splitting' off of hydrochloric acid and formation of nitrosopinene. As the nitrfjsoehlorides cif different terpenes show very similar melting points and besides decompose very i-eadily,' they are less suitable for (■haracterization than the nitrolamines, which are very stable and crystallize rea-dilv: tlie.se have been prepared in lai'ge numbers, although the compounds jjroduced liy the reaction with benzyhimine and piperidine 1) Liebis's .4niialeii, 245, i). ■Jol : 27,3, \t. 2."it. 2) This is ea.sily uiitaincd li.y allowins' a mi.xtm'e of 2(10 «■, of iimceiitratccl suliiliuric acid, 1.5 liters of A\ater and lee o. of alcohol to flow into a solution of 2,j0 s'. of sodium nitrite in 1 liter of water and 100 g-. of alr.diol. The ethyl nitrite which forms at once mnsi he condensed in well cooled receivers. iWallach.) 3) nerichte, 28, p. G+8. ■1-) Berichte, 29, p. 12. .-•I Wallach & I,orentz, TJeliiK's .ynnalen, 208 (1X91 I, ]i. I'.is. ''<) I'rban & Kreniers, Amer. Cliem. .rouni., 10 (1894 . p. 404, I'.aeyer, llerichte, 28 (IS'.*.';), p. 640; ,\Icad ^- Kr ers. .\mei'. Chem. .Iimi'ii.. 17 (18'.l.-|. p. 007. 11(1 Otni-iril I '.lit. tii-f preferal )ly used. Fov their preparation ^ the iiitrosocliloriile i.s treated in excess with tlie base dissolved in alcohol and heated on a water bath; the nitrolaniine formed is separated by the addition of water. The nieltin<^' point of piiiene nitrolpiperidine is UN — 110°. tliiit of tlie nitrolbenzvlamine 122 — 12;!°. Camphexe. Cam]ihene is the only hydrocarbon CmHio known in tlie solid form. In spite of this apparent advantage it has, with the exception of a single case, not been possible to separate it as a crystalline body froin a volatile oil. Camphene is found in the vegetable kingdom in both active moditications : as d-ca,mphene (a.nstracamphene of Berthelot) it is contained in ginger oil and spike oil; as 1-camphene (terecamphene- of Berthelot) in citronella, valerian and kesso oils. It has also been obtained from rosemary oil. camphor oil. French and American turpen- tine oils, as well as frouL the oil of Pinus sibirira. but only from the last in the solid form. Artificially camphene is obtained in various ways, generally liy splitting off hydro(ihloric acid fi-om pinene m(.)nohydro- chloride or bromide, or bornylchloride (borneo camphene). It is most readily prepared from isoborneol by the abstraction of water with zinc chloride. It is a wdiite, crumbling, cr3^stalline mass with a faint camphorlike odor, and shows a, great tendency to sublime, but otherwise is much more stable than the other terpenes toward air and light. As it is obtained in a solid form and may be freed from adhering liquid bodies by dissolving in alcohol and carefully adding water, it is one of the few terpenes which can be i)repared in a ]iure state. The following constants are given : for borneocanipheue : M. p. 4.S— 4<)°; b. Ji. KiO— 1()1° (Widladl.-l IMS.-,); d+.so = l(.S.-,((; nc4,s- = 1.4."..")."> (Wallach,t l.SH.S): M. p. .-.:?.. -.—-.4°; d'^^lf =:0..s;!,S(),S; nD.-,s.o= = 1.4.->:n4 (Hriild,-' 1S<)2); for ciim])liene from pinene cidorhydrate : M. p. .-.]-.-.2°: b. p. l.-.s..-,-l.-|'.)..-,°; . 2:54. p. i-'."i;i; 2.")2(1S89), p. 1.30. 4i liebig'.s Animleii, 2+.".. \,. 21i). -') Camphene pi-eparetl fnim pinene h.vdni- .■■) Berichto, 25, p. 164. rhloricle is also Bonietinies designateil a.s o i Bei'iehte. 2.'"i. p. 1(12. Icrcraiiipheiie. T/ie .\[(>iv Conunrnily (JvciUTWg CoUNtifiieiifs at' Voliitile Oik. lit for caniplieiit^ from iisoborneol: M. p. r,()°; 1,, p. !.-,<)— 1(;()° (Bertram cV: Walhanm.i 1S!)4); .",(j° at l.'num. The rotation of the liydroearbou artiflciallv prepared from pineiie hydrochloride or boniylehloride varies aecordiii;;- to the extent of the rotation of tlie material used and the height and length of time of the temperature employed during the reaction; thus Bouchardat and Lafont- (ISST) obtained hydrocarbons whose rotation [a],, was between — l-f(»°87' and — ;!()°;iu' by treating 1-pinene Tuonohydrocliloride (['/-]ij = — 27°. Oxidizing agents, such as chromic acid mixture, permanganate and nitric acid, do not act in like manner on the hydrocarbon. Thus dilute permanganate solution in the cold .yields first c-aTupliene glycol (anHifi(0H)2, melting at 192°. On further oxidation it produces camphene-camphoric Jicid CkiHujOj., small quantities of a ketone, cam- phenilone ('»HiiO (m. p. H(i — 88°), homolog'ous with, camphor, and principall.y an acid (WoHioO:! of the melting point 171—172° (Wagner's camphen,ylic acid, Bredt's oxvcamphenilanic acid). i\itri(.- acid oxidizes camphene principally to the tribasic camphoylic acid (Marsh and Gardner) C10H14.O0 (Bredt's carboxyl-apocamidioi-ic ai-id). Acconipanv- i| .Journ. f. pi-iikt. chi'iii. II.. 4!.i. p. s. 2) Coiiipt. rend.. 104. |]. 604: Bull. Soc. cliiiii. II., 47. p. 4SS. :M Liebip:'H Annalen. 107, p. 97. i) .liinger & Klagcs. 1896. Boric-htf. liO. p. 544: Uf.vfhler. ilild. jj. liiltj. -■) LifbiK'.s .\niiMlen, 200, p. :Mii. 112 (h'liei-.il I'.irt. mix this nri.' small qiiniititii^s of tlii^ kf'tinip ('!iHi4() alreaily iiu-iitionpil. ( 'liromic acid mixt lire yields foi- the main jiart caiiqilior with a little ra,ni])horic ai-id and other |)r()dui-ts. All of these derivatives of i:-ampiieiie, however, do not admit i:)f lieiiig used for its characterization. If fairly pure c-anijiheiie fractions are under consideration, the hydrocarlion may be separated in the form of its clilorhydrate. ('ain]ilieiie may. howevi'r. lie better identified by converting' it into isoborneid. Only when larmier (piantities of ])ineiie are present at the same time with the can]])hene the detection is unsatisfactory even with this method, because the iiiactivi' terpineol which is formed at the same time with tlie isob(n-neol retains the latter in solution and a se])aratioii of the mixture can be only ]iartially accomplished. According to Bertram and \\'albauin (lNi)J:j i.-amiihene can be cou- \-erted into isoborneol ac(/ordiii. 7.-,-,. ■i) Itunlit. rend., 1]:'.. \i. ."..".:'■; IL'."!. ]). 112. The More Coiiuuonly Occurring C'oiistitneiitN of Volatile OUn. IIM i-hlovie acid from fenchji chloride i (AVallacli 1S91 ). It is a liquid terpeiie. Tccallinji,' cainpheiie in odor, and is known in both optically active modifications. As constants have been found : B. p. 154— 1 .",5°; di8o = ().,SG(j(»; ncis^ = 1.4:<5!»:i■ B. j). 155— ir,(5° ; di„or= O.SOTO; nDi,s= = 1.47047; 2 ,,D= + -1° (^^'••'^ 1S<),S). Kepeated experiments in the laboratory of Sehinnnel & (.'o. oave the follo^Ying constants : B. p. 154— 15(;° (7()5 nim.); di.-,o = ().,S(;(;i)— (».,S<;(;5 ; nDiu^ = 1 .4(;7:i;!— 1 .4C>s;i2. Fenchene yields no c-haracteristic addition produ(;ts with halofiens, hydrolialogens, or nitrosylchloride which might 1je used for chararter, ization. Like caniphene it can, however, be hydrateil with glacial acetic acid and sulphuric acid to an alcohol CmHisO, isofenchyl alcohol (m. p. ()1.5 — ()2°) which with phenyl isocyanate yields a phenyluretliane melting at lOii- 107°. ^ Ldioxexe. Limoiiene is a. very widely distributed terpene. Besides the de.xtro and laevogyrate forms it also oci-urs in the inactive modification, called dipentene. As some of the dipentene derivatives are different in properties from the corresponding limonene derivatives it is usually considered as a separate liyilrocarlion. d-Limonene (citrenej is contained in the citrus oils, in larger quantities in the oils of orange peel, lemon, and bergamot, in mandarin oil, in Italian limette oil, in neroli and petitgrain oils, further in caraway, dill and Macedonian fennel oil, in celery, erigeron and kuromoji oils. 1-Limonene does not oc<-ur as frequently. It has been found in the oil from the needles and cones of Abies albu, in Russian and American spearnnnt oil anil American jjeppermint oil. Since the optically active limonenes could not be regenerated fi-oni solid derivatives, recourse had to be taken for their preparation to the fractional distillati(jn of orange peel or cai-away oils, and in the case of bhmonene, of oil of Abies alba. The most carefully purified hydrocarbon possesses a pleasant lemon like odor, which in thedistilhites obtained from caraway oil or oil of Abies a.lbii dianges after keeping for a short time, the odoi- then reminding of the oils used. Tins is pr()l)al:)ly due 1) Liebig's Annalen, 263, !>. 1+S. :') Liebig's Annalen, 802, p. 376— :i77. 2) Liehig's .\niialeii, fiOO. p. 313. *) Bei-ioht yon S. & Co., Oi-tober 1 898, p. .-|6. 114 ■■ (ienernl Fnrt. to the pi-eiseiire of small quiintities of foreign .substances. Tlie jiliysicil constiiiits obtained from sncli fra° (in ali-ohobc or chlorofornnc solution). ;ind Tilden :ind Williamson ^ in'lcS!):! found n similiir value ["■]!.=: — lnc,°. (]uite recently Godlewsky ■"' ha,s regenerated linionene from the tetra- br(,mide by recUietion with zinc dust. The limonene resulting liad the f( ,lli , wing pr( ,pei-ties : 1',. ]>. 177..',^ at 7.",!»mm.; d]^ = ()..S.-|,s.", ; il'J" = ().,S.-,S4 ; d"]*' = ().S42.", ; [«]„ = + 12.",° ;{(;' at 20°. The regenerated liTUonene again added bromine to fm-ni the tetra- bi-omide melting at 104°. The two limonenes are completely alike in their chenncal behavior; bi,th give the same derivatives, differing i)nly in their o])tic'al ri,tation. By mixing eipial amounts (,f d- and 1-limonene dijientene results, which hydrocarlion is also formed when the optically active limonenes are heated to a high te7U])erature or treated with acids. In a completelv dry state limonene absorbs one moleculi' of liy(b-ohalogen with the foinnation of li(|ui(l, opti(/ally active compounds" (Wallach). By replacing the halogen atom by the hydroxyl grou], tliis yields optically active teriiine(,l" (Semndei-, l.S'.)."i). (.)nly in the ])resence of moisture (h)es an addition of two molecules of hydi-ohahigen take place, with the formation of derivatives of di]ientene. Limonene takes up four atoms of bromine .and forms the optii'ally active limonene tetra.bromide (see p. 11.",) meltitig jit lO-l- — 10.",°. By tlie addition of niti-osylchloilde there result two (-/- and ,5-) niti'oso- chlorides'^ (^A^■dlaclL. l.S.SOi which ar(^ ])re],ared in a sinnLai- mannei- to |,inciie niti(,S(,chloi-ide and ;\vi' to be considered as ]divsical isomers. 1) Liebin's Aimaleii, :J-tG, p. 222. .'i Clieni. ('™tibl., Tin, p. 12 + 1. -I .\ii,L'i-. Clieni. .Toni-n., 17. ]i. G'.l2. u i .\unalen, 270. |p. 1 ss. •i| I.ii'liiB's Aiinaleii, 24(1, p. 222 ; «iillmii ■) Iterichte. 2s, p. 211ie, A: Coiii-aily, iliiilcm 252. p. 1+5. ni l,i,>l,io-'„ .VmiaU-ii. 2.".2. p. Ili'i. 1) .loui-ii. (.'hem. Soc. 6;i, p. 2'.).-t. Tlif Morp Coiiiiiionh- Ori-iUTinu; Coiistitiwnts of Volntiif Oils. ll."i Thf iiitrosocliloi'iiles ;irp perfectly alike in chemieal bebavioi-. liotli are chaiiiied to carvoxirae ineltiiig at 72° liy tlie abstraction of liydrorliloric acid witb alcoholic alkali, and yield wben tre;\ted witli bases the same (two) nitrohiminesi (Wallacb, l.Sl)21. Linionene is converted by dilute permanfi'anate solution into the saturated tetratoiiiic alcohol linionetrite (ni. p. 101 .5—1 02°) - (Wa.uner. l.SOd). A i-liaracteristic derivative of linionene, wbii-h is often used for identitication, the tetra bromide, is ]irepare(l accordinfi' to Wallach's tassium bisulphate-' (Walla.ch, IS!):',). Dipentene is distini^uished from limonene in its ]ihysical properties only by its optical activity; boiling point, -^ specific gravity, and index of refraction are identii-al with the data determined for linionene. ^^lr dipentene from caoutchouc the followinn' data have been foiunl in the laboratory of Schimmel & f'o. : B. p. IT.'i— 17C>°; d2(i' = , 1 IS Ceiii-rnl Purl. Syln'EKTKEXE. Sylvesti'die is one of the rjirely occurinji' terpeucs. Up 1 o 1 lie present time it has been found in Gei-nnin and Swedish jjine needle oil from I'inus .sUvestvis, in the oil from the leaves of Piiius montnnn. in pine tar oil and P^iiniish turpentine oil. In all of these it occurs in the dextroijiyrate nioditi(/ation. It may ])e obtained in a compai'atively ]iure state by ])re]iarin,ii' tlie dihydrochloride from fractions rich in sylvestrene and decomposin,i;' this liy hoilin;^' with aniline' (\\'all;u-h, USH.")), t_n- sodium a(.'etate and .U'laeial acetic acid- ( W'allach* 1^>87). The liydror-a.rbou thus obtained resendiles limonene almost ccmipletely in its physical a.nd chemical jiroperties. Like this it possesses a ])leasant odor, remindin<^' of lennm and berjiamot oil, and its specific ,i;ravity and boilin,n' ]3oint are almost identical with those of limonene. Atterl)erjj,-, the discoverer of syl\-estrene, a,scertained the following' pliysical constants : B. ]). 173— lT."i°; ill,,: = ll.N. 17.')— 17(1°: din = . 24:!. :l) Hel-ii.'llte, 10, ii. lliOH. -') Lic'liis'K Annnlcii, i!;!ii, p. 2.-.: 24.-,, ii Liebis's .\mi.alpii. 24.1, p. T.)T, P- t'.*~- '•) I>iol)ij;:'!,! Anilaleil, 2.~»2, p. 149. 77ip Mure ('oiiiiiioulv Occnrriiifj: i'lniHtitiieiits of Vol.itilr Oils. 11!) For the separation of sylveHtreiie from niixtiires, as well as for iilentificatioii, the diliydroi'liloride is Ijest suited and is prepared as follows : The fraetioii dihiteil with an equal vuhiine of etlipi- is strongly eooli'il and saturated with liydrocbloric acid gas. After sTandiuK for ahout two days the I'tlier is distilled off and the residue induced to crystallize by strongly cooling. The crystalline mass is freed from oily by-products on a porous plate, and the hydrochloride, tii-st recrystallized from an equal weight of alcohol, is purified by fractional crystallization from ether: the melting point of thi' ])ure diliydro- chloride is 72° (W.,i '1S5). It must be observed, that in the presence of diiienti-nc or such terperies as aiv changed to dipentene dihydrochloriilc, mixtures of dihydroidilorides are obtained, the melting point of which is the lower. I he greater the amount of di|>entene dihydrochloride |iresent. If sylvestreiie be dissolved in acetic anhydride and a few ilrop.s of concentrated snlphnric acid added to the solution, a heautiful blue coloration is produced. This reaction may be used for the easy detection of sylvestrene, but it is only successful when the fractions to be tested are rich in th-s hydrocarbon. Terpi.n'ene. This h\'drocarbon is very similar to dipentene, yet sharply differ- entiated from it. Accordinji' to Weber^ (18H7) it is contained in car(lamom oil and recently it has also been fciund in marjoram (.>il liy 15iltz.-5 It may, however, appear doubtful, whether this terpeue is really found in nature, or whether it is formed by the influence of the heat durine- the distillation fi-om other comp(.)unds contained in the i-es]iective oils, Artitici.ally. this hj'drocarbou, which distinguishes itself by its stability toward dilute mineral acids, is rjbtained by the action of boiliuo- alcoholic sul])huric acid on terjjenes, such as dipentene and phellandrene, or on o.Kygenated compounds, such as terpin hydrate, terpineol, dihydro- carveol ami cineol. Besides dipentene it is also formed by the action of formic acid on linalool and geraTiiol. It is further foi-med, besides isomeric hydrocarbons (!]iiHi« a,ud itymene, by the hiversion of pinene with alcoholic sulphui-ic acid or when turpentine oil is shaken with snmll amounts of I'oncentrated sul])huric acid, avoiding too violent a reaction-' (Wallaeh, 1HS7). The last named method is used wdien it is desired to olitain tractions containinK terpinene. As terpinene has up 1) Liehig's Aunalen, 2:io, p, 2-t] ; 2;!',l, |p. 2."). -■) l>iebis'N .Annalen, 2HS, \i. 1(17. :t) I'eber das iittierische < )el airs Orignnritn nin^jorniin. inauft-.-niR,serl . i;ivil'w\A'Jiliebif>-'s .\iinalen, 2M0, )i. '^x'. 12(1 GeiiPTu! Part. to the present not l)een regenerated from a solid derivartive, the statement of the physical properties of this hydrocarbon refei-s not to the ])ure substance but only to terpinene-containing- fractions. For a terpinene obtained from terjiin hydrate and dilute sulplmrir acid Wallach i-eports: B. ]). 17!)— 1H2°; d =().N.-).-,i and for a purer preparation from dihydroi-arveol and sulphuric acid: B. p. 17H— 1,S()°; d = (1.847; n„ = 1.4S-l-.'',8.2 Terpinene has an odor reminding- of cymene and resinities quite rapidly on standing; it has not yet been ijossilile to i-onvert it into isomers. It is therefore very similar to dipentene, but the two liydro- carbons differ in their beliavior toward bromine and the hydrohalogens, with wliich terpinene yields liquid addition products only. A lutroso- chloi-ide of this terpene is not known, but nitrolamines can be prepared from the nitrosite mentioned latei'. By chromic acid mixture (prepared according to Beckmann) terpi- nene is readily attacked and completely destroyed (Baeyer.-' 1S94). even in the i.-old. This behavior may be made use of when terpinene is to be removed from nuxtures of pineue, camphene, limonene. terpineols. cineol or ]iiiiol. as these conq^ounds are fairly stable toward the oxidizing agent in the cold. The derivative of terpinene which may serve for the detection of this hydrocarbon is that formed liy the addition of nitrons acid, terpinene niti-osite CioHuiN;;()k. It is ol)tained liy the action of nascent nitrous ai-id on the terpene diluted with a solvent. In order to determine rajiidly whether this hydrocarbon is present in a fraction of the boiling point of terpinene. Wallach (1SS7) directs^ to proceed as follows : A mixture of 2 — 3 g. of the fraction with an (Minal volume of ]iptroleum etlici- is poured on top of an aqueous solutiou of 2 — 8 g. of so(hum nitrite and the anionnt of acid necessary to decompose tlie latter is added in small portions; when all acid has bi-en added the vessel is immersed for a moment in a hot waterhatli and then allowed to stand in the cold. AVlicn terpinene is pipsent, the insoluble nitrosite will separate in a few liours, or at latest in the course of two days. This is freed from accomiianj-ing oily products by spreading on porous plates, dissolved in glacial acetic acid, again preci]iitated by water and finall.v reorystallized from hot alcohol. The inn-itied comi)Ound melts at 15."i°. M Lii'l)ig'K AnnaliMi. 2ao, ii.2.")3; 2:!'.l, p. ii:!. :i i lierk'lite, 27, p. SI,-,. = ) I'.erichtc, 24. p. MtiSJl. i) I.iebifj'.s .Iniialuii. 2:t;), p. 3(5. Tlip More Coiiiiiionly Om-iirrins- Constituent!^ of Volatile Oils. 121 The nitrosite reacts with bases, such as piperidine a,nd beiizylainine to form nitrolammes. The nitrolpiperidine base melts at 15;! — A~A°. tlie iiitrolbenzylamiiie base at 187°^ (Wallach). Phellandrese. Pliellaiidrene occurs in nature in both optically active modifications. As d-phellandrene it has been found in bittei-- and water-fennel oils, as well as in Macedonian fennel oil. in elemi and schinus oils and in the distillate of the wood of Cttesalpmia siippan. As 1-phellandrene in Australian eucalyptus oil from Eucalyptus anmgchihuH . in ])iue needle oil, the oil from the needles of Finns inontanu, in star-anise and schinus oils. Besides these, it is contained in a kirji'e nmiiber of volatile oils, althouf>'h in small quantities, for instance in the oils of ging-er, curruma, pepper, <-amphor, sassafras leaves, (Jeylon cinnamon, ang'elica root and seed, in the oils of German and English dill, in that of dog fennel, wormwood, golden rod,' lemon, bay and peppermint, as well as in the oils of Enca- lyptu.s risdonia and Aiidropjogoii laniger. It is one of the most unstable terpenes. and for this reason pliel- landrene containing oils nmst never be redistilled under atmospheric pressure, but are best fractionated in a vacuum when it is desired to detei-t and isolate this hydrocarbon. The preparation of pure phel- lanilrene has not yet been accomplished; the only compound apparently suited for this purpose, the crj^stallized nitrosite, decompcjses indeed, by treatment with alkali- (Wallach, 181).")), but no hydrocarbon CioHio is formed by the reaction. Fractions as rii-h as possible in phellandrene, viz. the portion boiling between 171 > — 172° are thei'efore taken as representinfi' fairly pure liydrocarbon. Pesci (1H.S()), who found this hydrocarbon in water fennel oil and named it after its source, reports the following properties: B. p. 171—172° (7(;()nmi.); d]„ = , 142+. 3) I.iebiK's Annalen. 2S7, ]). 374. =) Liebig's Annalen. 'JH7, p. 383. :!) (ii\7.7, chilli, itai. \l>, |i. 22.'.. 6) Archly il. I'harm.. 23.j. )i. 591. 122 ■ Gcni-r.-il Part. Pli(41ini(livii(j is vi^vy rpiidily cliaii.uvd; even hy lietitiiiji' ti) its bniliii;^- teiiipevature it ixilymerizes. Still more ivndily is it ehangeil into inactive isoiiiei-s by the action of acids, thus by hydrohalojj,-en into dipentene, l)y alcoholic sulphuric acid intc; terpineue. AVell characteri^.ed addition pi'oduets with halolciiin ctlicr is ponrcd on a. sdhition (jf a g, of sodium iidritc in s g. of water and liic amonnt of gkxcial acetic acid (a cc. ) necessary to lilicrate the nitrons acid is added g-radually with frccjncnt sliaking: the ^olnniinoiis ci'ystaUiae mass (irodnccd is filtered off with the aiil of a,ii ail- i)uni|i, washeil fii-st with water and then \vith methyl alcohol, and [jui-ified l)y repeatedly dissolving in chloroform and |irei-i|>itating with methyl alcohoM (Wallach and (iildemcister, ISS.S). The brilliant Aviiite (uystals thns obtained allow of being- recrystallized from acetic ether -\vithoiit deeom])Osition ami melt at 10."i°-' (Wallach, 1^951. The crude compound (hanges easily and is freed fi-om the oily b.y-pi'odncts only with difficulty; by dissolving in a, little acetic ether and ]a-ecipitat.ing- with (iO percent alcohol the niti-ite can be obtaineil at once in the form of white crystals-' (liertrani and Walbanm, 1.S93). Botli phellandrenes >x[y9 nitrosites which are identical as to external ap])eara.nce and in their meltinj;' ]ioint. but which differ in this respect, that the compound olitaiued from cb])hellandrene is strongly laevo- gyra.te. that from l-].)hel]an(]rene on the other band, strongly ilextro- g-yrate. By mixing e(]ual parts by weight of il- and 1-phellandreue nitrosite in solution tjie inactive compound is formed, which in its ]iropei-ties is identical witli the optically active mocbtications. I'hellan- dreue nitrosite. in opy.iosition to terpineue nitrosite, cannot be changed to nitrohiniines with bases. If the licpiid reaction product formed by treatment with sodium etbyla.te is redui-eif there result, as well as liy the direct reduction of the nitrosite, derivatives of the by(b-ocarvone ,sei-ies+ (Wallach, iND.'i). The ))re,seneeof hydrocarbons of the formulas CmHis and ('leHje in \-olatile oils has not yet been ileiinitely established. The statement made by Andres and Andreef-"' (1,S<)2) that a hydrocarl)on CioHts. ]iresumably the menthene derivalile fron\ menthtd, occurs in Kussiau pe|i]iernnnt oil has not lieen verified. i| Lieblg-'s Aiaialcn. 24i;. |i. 2SL.'. i) I.ieliie'K Aiiiaileii, L'S7. |i. :iS(l. -1 Llebig-'K Annalen. 287. ji. :'.74. r.\ lUa-iclitt', 'J't, p. CIG. •■•1 .U-cliiv (P Phfiini.. 2:11, |i.2'.is, r. =1 Clifiii. ZeitiiiiR'. 1/!, p. Ttr,H. 124- Geiiprnl I'.irt. ('adiiipup can be pivpaivd in a comparatively pure state, iiw it yields a solid well crystallized dihydrocldoride, from which the hydrocarbon may be regenerated by sphttini>- off hydrochloric acid by heating- with iiniliue or sodium acetate and j;lacial acetic arid' (Wallach. IHST). For the hydrocarbon pnrifled in this manner AVallarh found the followin<;- constants: B. p. 272° (uncorr.);-' 274— 27."!° ; il-.w- = l».!)l H ; n„ = l..",()()-l-7 ; [«]„ = -!)is..-,(;°.« Up(jn continued heatinji- with dilute sulphuric acid cadinene is chauR-ed, while when treated with hydrohalogens no ai)precial)le influence is noticed, as tile ojitical activity remains unchanged. Especially characteristic are the crystallized addition products ff)rineil with two nn)leeules of hydrohalogen, of which the dihydro(diloride and the (liliydrobiomide are used for identification. F(ji- llic ]ii-cparatioii of tlie dihydrochloridc the fraction boihiig between 2()0— 2H0° is (liltitcil with twice tlii> voUuiie of ether and saturated with liydro- cliloric acid gas in the cold, .\ftcr standing for some time the ether is partially removed by distillation. With the coniiilete evaporation of the solvent, crystals of the diliydrf)chloride .separate from the residue. These are freed from oily by-pnjdncts by spreading on porous plates. They are then washed with al<-ohol, and reerystallized from acetic ether in which they are readily soluble while warm. The melting ])oint of the pin-e com]ionnd is 117 — llSi°. It is optically active. The dihydro(dilori(le nmy also be prepared l)y using glacial acetic aciil saturated with hydro(-hoi-ic acid in the cold. This method of ])repiirntion — treating a glacial acetic arid solution of the sesquiterpene witli :\ glacial acetic arid solution of the respective hydrohalogen — is suitable for the preparation of tlie diliydroln-ondde (m. ]i. 124 — 12.")°) and the dihydroiodide (m. ]>. 1 ().')— l()(j"). The nitrosocldoride and niti-osate ha ve l>een ])i-e])ared within the last year by Sclu'einer anil Kremers.'t Of the latter the uiaisually large yield of ovei- forty per cent was olitained. The nitrosochhu'ide melts at <);!— <)4°. the nitrosate at 10.')— 110°, both with deconii)osition, Cadinene is chararterized by a color reartion, whicdi nndei- some cir- cumstances nmy serve to sliow its presence in oils. The reaction is prettiest when the hydrocarbon, sligditly changed by standing for some time, is diss(dved in glacial aretic a,eid and the solution treated with a little concentrated sulphuric a.cid. The gi-eenish coloration tii-st pro- duced soon (dianges through blue to red. 1) Liehig'fi .\nnaleii. 2MS, p. S4. ai Liebig's .\iinnlen, 2.".2. ]i. !.">(); 271, |i. 2'.)? '-'I r.ieliig's .\T)nalon. 271, p. Mo:!. ii I'lim-iii. Aivli.. 2, i). 24'.). The Moiv Coiiniinnly (k-ctitrinfr (.'nnstitnciits of Volnt'ih' Oils. 125 Caryophyllexe. The !sei-ond well characterized sesquiterpene is carvophvllene. So far it has been found in the oils of cloves and clove stems, the oil (jf copaiba balsam and that of ('anella iilbn. It has not yet been prepared absolutely pure. The physical constants recorded pertain to distilUites from clove oil and the oil of clove stems. Caiyophyllene prepared from clove oil merely by fractionation contains some benzoyl enfj;enoP wliii-h i-an be removed by saponifii-ation. In the sesquiterpene from the oil of clove stems this impurity is not found. The physica,! constants have been ascertained by several observers, viz. : Wallach^ (l.s<»2):.b. p. 2.'>.S— 2()()°; di.v = D.OOS.', ; n,, = !..")( l(i!)4. Erdmann« (1S<)7): b. p. 11')— 12(1° at 1) mm.; 12:-!— 124° at 1:! mm.: 2.jS— 2.")!)° at 7r)2 mm.; da^o = ().()(»;),S. Kremers* (1S!»,S|: dao" = <».!)():52, Ud^o" l.')<»()li) ; [«]d2c-' = — .S.T4°, Srhreiner and Kremers-i (iHi)!)): li. p. l:!(i— 1;!7° at 20 mm.; [,/]i,:,,,o = — S.!)(i; nD20° = l. +!»!»"(); d2(,o = (). !)();!(». The laevogyrate hydrocarbon yields optically active iis well as inactive derivatives, the nitrosite e, jj,-, l)einy stroii from cubebea.mphoi- 2r,5— 2()()° — — — Guajeue" from guaiol & ZnCI^ 1 ,"l <> *= ■' ' (13 mm ) 0,91(1 (20°) 1.50114 — Ledene" from ledumcamplior i dil. sulphuric acid 2.-1.-,° — — — Patchouleue'* from ])atchoulica.m]ihor and KHSO.t 2.-I-I— 2r,(i'= (1,939 (23°) 1.5()((91- — Santalene" from santalol and Pl.O.-, 2(i0" — - i| ( 'haiMilaii. .Jcnrn. choiii. Soe., l>7 (18U -) Chaiuiiatl t^ Itui'^ess, ('hem. Xe\\s, 7+ 3) ItouKKPt, Bull. Snc. chim. III, 17 (1 S'.l 1) Walter, l.leliiff'e Aniuileu, 3U (1S41). lirninel & Co., CJctaber 1S07. i». 12, footin ""•) Schmidt. Berlchte, Id (1.S77|, p. IS'.). 6) Wallac'h & Tuttle, Lieliig's Amialen, 2 "1 Hjelt, rierichte, 2,s (189,'",), p. 30N7. M Wallach * Tattle. Lleliis's .\Tinalen. 2 '■)) ('ha|,i,teaMt, Hull. Soe. chim. 11, ;i7 (t , ), p. .--1- & 7S (l.S ;iG), p. i.,:1. 71. p. 4S,-,. p. 247 ; 4S ,te. 7'.i 1 1S'.,4). p. 71, (ls<.14l, p. SSL 1. |,. :Hi;!. U'S + Hl, p. 'ei-iclit \-(.ni Tlir Mdiv Coninioiily (Jci-nrriiiii: fiiiistitiipiifs of Vol:ttUf Oils. '[■21 cloveiie, is tormed. This iliffers materially from caryophelleTie ainl has not yet been found in volatile oils. Besides these two sesquiterpenes may lie mentioned the fairly well i-hara<-terized Immulene. It derives its name from hop oil from whicli it was pre])ared by Chapman' who first prei)ared its nitrosochloride, its nitrosite (existing' in a blue and a white variety) and nitrosate, also tlie nitrol benzylamine (m. p. 1H()°) and tlii' nitrol iiiperidine (m. p. 15;!°) bases. It is characterized l)y the nitrosite. the blue variety of which (m. ]). 120°) chanoes upon repeated recrystallization from ali-ohol to the white vai-iety (m. ]i. Ki-'i — 1(;!S°). HuTimlene also occurs in oil of pojilar buds. Fichtei- and Katz- identified it liv means of the above mentioned derivatives. There T'emain , to be mentioned cedrene occuring with cedrol in cedar oil, as well as other hydrocarbons f'].r,H24 produced by splitting off water from sesquiterpene alcohols. Theii' properties are, so far as known, given in the table on the ]ireceding page. Polyterpenes, namely di- and triterpenes, occur in vegetable balsams and resins. They are possibly formed by polymerization of hydrocarbons C-jHs and ('idHm and may therefore be found in the higher boiling- fractions of volatile oils. The diterpenes are viscid liquids boiling above ;!<)()'', the triterpenes resinous masses. Hence they do not invite exa.min- ation and their ])roperties have been even less investigated than those of the sesquiterpenes. Alcohols. Of the monatomic alcohols of the paraffin series only those with less than eight carbon atoms have so far been found in volatile oils. They occur seldom as free alcohols and are mostly combined with fatty acids as esters. The occurrence of fatty alcohols and acids is mostly due to saponificati. Kins. 21 liHrichti', M-'. p. :nM;t. ... . . . . , , li'H Geneva] Pnrt. As esters and ethers methyl alcohol is widely distributed: as methyl sahc,ylate iu numerous plants, as methyl ether e. g. in eugenol which is ]ik(>wise widely distriliuted. Aci-ordinjj;' to Goe])pert (1859). ethyl alcohol as acetate is tlie odoriferous principle of ALignolia fuscata Andrews. i This statement has not yet been verified. It has been found as ethyl ester of caproic, i:-ai)rylic, capric lauric. ])almitic and oleic acids in the volatile oil of saw palmetto liy Sherman and Brifygs.^ As butyi-ate ethyl alcohol is found in the oil of H. sphondilium. Isobutyl alcohol (isoprrjpyl carbinol) occurs as ester nf isobutyric and ancelii- acids in P^OTuan chamomile (lil; amyl alcohol (of fermentation) as caprinate in eofi-nac oil and as ester of angelic and tiglinic acids also in Eoman chamomile oil. Norinal hexyl jiIcoIxjI is found as acetate and butyrate in the oil of Hernrleum f(igantpum, also as acetate in the oil of H. uphoiidylmm. Optically active hexyl alcohol (methyl ethyl propyl alcohol) has lieen found com))ined with angelic and tiglinii- acids 171 Roman chamomile oil. Octyl alcohol is found as acetate in the oils of H. sphoudylium and H. gjii-antfum ; as l)ut,\'rate it is the princi]3al constituent of the oil of Pnstiuac!) sntivn. Besides liexyl alcoliol it is also reported to occur in the oil of male fern. Of greater interest than the saturated fatty alcoliols are the oletinii- alcohol citronellol, CrmHooO and the two dioleflnic alcohols t'loHifiO. linalool and geraniol. LlX.\LOOL. Linalool ("Licareol" c)f Barbier) is quite Avidely distriliuted. It is optically active anil occurs in Ixjtli modifications. So far d-linalool lias been found in but one oil, viz. i-in-iandei- oil and is, therefore, sometimes designated coriandrol ; 1-linalool, alone or mixed with a little d-linalool, partly fi-ee, partly as ester, ff)rms a. constituent of the oils of lignaloe, berganiot. neroli, petitgrain, tlie Italian limette oil, Palermo lemon oil. of the oils of spike, lavender, muscatel sage, thyme, of Russian S]iear- mint oil, German and French basilicinn oil, Cretian origanum oil, ylang- ylang oil and of sassafra,s leaf oil. To regenerate linalool frcun a crystallized derivative has so far been nnsui.'cessful. Fractional distillation of the oils, which have previouslv been saiionified, is used for its isolation. The constants given for linalool refei-, therefoj'e, always to the products obtained in this manner. If the alcohol ol)tained is to be freed from indifferent compounds, for instance tei-])inene, it ma-y be converted into the sodium salt of the ai-id phthalic 1) I.ieljig'.s .iiiiuili'ii, HI, |i. IL'T. -■) I'hanii. .Archives, 2, |i. 110. The Morp ComuLonly Occurring Constituents of Volatile Oils. 129 ester according to Tieinann i (1898). This is soluble in water and can be saponified by alcoholic potassa. The regenerated linalool must be removed from the alcoholic alkaline solution with ether, since it suffers changes when it is distilled from the alkaline solution hj steam as the decrease in the rotatory power shows. According to the material employed and the method of preparation, products are obtained which show slight differences in their properties ; in judging the purity of a prepai'ation the following data may serve as a basis : for 1-linalool : b. p. li)7— 109° ; 85— 87° at 10 mm. ; dis" = 0.870— 0.875 ; nD2o= = l.lG30— 1.4G90 (Stephan.^ 1898). B. p. 86—87° at 11 mm. ; d2o° = 0.8G22 ; dd = 1.16108 (Tiemann.s 1 898) ; for d-linalool: b. p. 85—86° at 12 mm.; di7..5° = 0.8726 ; nD=l. 46455 ( Gildemei.ster,^ 1895). The rotatorjr power is not constant, the greatest deviation so far ob>served for 1-linalool is [«]d^= — 20°7',3 for d-linalool (coriaiidrol) [Jo = +15°l' (Barbier,6 1898). Tiemaiin reports for d-linalool [a]D = + 13° 19'. Artificially, linalool is obtained, although only in the inactive state, when geraniolis heated with water to 200° in an autoclave, or when the different chlorides produced by the action of hydrochloric acid on geraniol, are treated with alcoholic potassa (Tiemann''', 1898). A third method of converting geraniol into linalool consists in passing steam through an aqueous solution of geranyl phthalate of an alkali which is either neutral or rendered slightly alkaline by the addition of an alkali carbonate (Stephan,** 1899). As unsaturated alcohol with two double bonds linalool also shows a capacity for addition. It combines with two molecules of bromine, as well as with the hydrohalogens. With the latter it forms compounds such as CioHisO.HGl, CjoHisCla whicli, however, being liquid, are not suited for characterization. The unsaturated tertiary nature of this alcohol shows itself in its behavior toward i-eagents. Whereas alkalies scarcely act on it in the cold," organic acids change it either into geraniol or, especially in the presence of small amounts of sulphuric acid, into terpineol. Mineral 1) Berichte, 31, p. 8.ST. ») Berioht von S. &f'o., April 189.S, p. 2.":. 2) .four. f. prakt. Chem., II, .58, i>. 110. 7) Berichte, 31, p. .832. 3) Berichte, 31, p. 834. s) .Journ. f. prakt. Chem., II, 60, p. 2.52. 1) Archir d. Pharin., 233, p. 179. ») Bull. Soc. Chim., 21, p. 54'J. = ) Compt. rend., 116, p. 14.59. 130 General Pari. acids, by the abstraction ov addition of water, pi'odiiee compounds with a cycMc structure. Thus terpin hydrate is produced bj' shalving with 5 percent sulphuric acid (Tieniann & Schmidt,i 1895). By lieat- ing- witli glacial acetic acid and acetic acid anhydride there results besides geranyl a,cetate the acetate of solid terpineol, the rotation of which in ojjposite in direction of that of the linalool used. Formic acid, at the average temperature of 20°, also converts it into the esters of linalool and of the solid terpineol with opposite rotation (Stepha.n,^ 1H9,S). With moderate heat, however. (60— 70°), water is split off with formation of the hydrocarbons dipentene and terpinene (Bertram & AValbaum,^ 1892). Toward various oxidizing agents linalool behaves differently. AVith very dilute permanganate solution polyatomic alcohols are pi'obablj^ first formed with simultaneous addition of water. These cannot be isolated in a pure state, and are split up by further oxidation with permanganate or chromic acid mixture into acetone and laevnlinic acid (Tiemann & Semmler,* 1893). In accordance with this result and in consideration of the fact that linalool is optically active and. therefore, must contain an asymmetric carbon atom, the formula, of a dimethyl- 2 , 6-octadiene-2, 7-ol-G ( 'Hs . C(CH3) ; CH . CHa . CH2 . C(CH3)(0H) . CH : CHl> has been suggested for this alcohol.''' If linalool is oxidized with chromic acid mixture only, it first suffers a rearrangement owing to the acidity of the oxidizing agent and is tlieii changed to the aldehyde of geraniol, citral (Bertram & Walbaum," 1892). The oxidation, how- ever, usually goes further and "Abba.u" products of citral are also obtained, namely methyl hepteiione, laevnlinic acid, etc. The crystal- lized derivative observed by Bertram & "Walbaum when oxidized with peroxide of liydrogen has been shown to be terpin hydrate, the forma- tion of whicli is in all ]n-obability, iwimarily due to the presence of mineral acid in the peroxide of li,ydrogen. Linalool does not add hydrogen when heated with reducing agents, but readily loses its oxygen with the iiroduction of the unsaturated hydrocarbon hnaloolene (JioHis. This is formed, when linalool is con- verted into its sodium compound, or treated with metallii- sodium in alcoholic solution, or when heated with zinc dust to 220—280° (Semm- ler,T 1894-). 1) Berichte, 28, p. 2137. 5) ibidem, p. 2131. 2) .Journ. f. prakt. Chem., II, 5S, p. insi. H) .Vourn. f. prakt. Clieni., II, 45, p, ,j'jn. 3) .Journ. f. prakt. Chem., II, +5, p 601. ') Berichte, 27, p. 2520. i) Bericiite, 28, ji. 2i:!0. 7'/ie Move Commonly Occurring Constituents of Volatile Oils. 131 A.s already mentioned, linalool is found not only in the free state, but also as ester of fatty acids in volatile oils. Particulai-ly important is the acetate, which possesses the characteristic odor of bergamot and constitutes the principal constituent of bergamot oil. In larger or smaller amounts linalyl acetate has been further found in French and English lavender oil, in Italian limette oil, in muscatel sa,ge oil and sas- safras leaf oil. Of the other fatty acid esters, the butyrate and probably also the propionate and valerianate are contained iii lavender oil. The valerianate also occurs in sassafras leaf oil. The esters of linalool that occur in volatile oils, are liquids of a inoi'e or less strong and pleasant odor. They cannot be distilled under atmos- pheric pressure without decomposition. Their synthetic preparation meets with difficulty in so far as linalool is fairly sensitive to acids and suffei's reai-rangement so that, while the products obtained by the heating of linalool with acid anhydiides or by the method of the German Imperial-Patent 80,711 consist for the main part of esters of linalool, they contain also tho.se of geraniol and terpineol. For the acetir ester isolated from bergamot and lavender oils the following properties are recorded by Tiemann and Semmleri (1892): B. p. no— 1(».-.° at 1.") ram. : d2(i° = 0.89.".l ; b. p. 97— 10.5° at 1.") mm. ; d2(i° = 0.8972. For a, preparation containing aljout 88 percent of acetate distilled from limette oil, Grildeniei.ster^ (189.'i) found: B. p. 101—103° at l;! mm.; di5° = 0.898; 6(di5 = — 9°.'52'. Bertram and Walbaum^ (1892), however, determined the following- constants for the acetate prepai-ed by boiling linalool with acetic acid anhydride, which probably also contained the acetic esters of geraniol and terpineol : B. p. 10.-)— 112° at 11 mm.; di5>' = 0.912. While the ester isolated fi-om volatile oils rotates polarized light more or less strongly to the left, the synthetic preparation is either almost inactive or dextrogyrate. The dextrorotation incT-eases with the quantity of linalool that has lieen changed to terpineol. As linalool yields no solid derivatives, which are suited for identifi- (;ation, it is necessary for this purpose to convert it into citral by oxidation, a,nd to chara,(/terize the latter by the citryl-/?-naphtocinchoninic acid discovered by Doebner (see citral). 1) Berichte, 2.j, pp. 1184 & 1187. 3) .Jour. f. prakt. Chem., II, 45, p. .58 2) ArchiT d. Pharm., 23:1, p. 181. l;i2 General Part. Geraniol. The dioleflidc alcohol CioHisO geraniol ("Lemonol" Barbier and Bouveault; "Ehodinol" Erdmann and Huth, Poleek) is isomeric with lina.lool, but differs from it by its opti(.'al inactivity, higher l)oiling point and higher specific gravity. It is also found in the free state as well as in the form of esters and occurs rather fi-equently in volatile oils. While it constitutes the main part of palmarosa oil as well as of German and Turkish rose oil, and is (-ontained in appreciable quantities in geranium, citronella and lemon grass oils, it is found in many oils only in small quantities, as in neroli and petitgrain oils, lavender oil and oil of spike, in lignaloe oil, ylang-ylang oil and sassafras leaf oil. As primary alcohol geraniol produces a crystalline double compound with anhydrous calcium chloride (Jacob.sen,i 1871), which is insoluble in solvents like ether, ligroin, benzene, chloroform, and is dec(.)mposed by water into calcium chloride and geraniol. This property makes the preparation of chemicallj' pure geraniol possible in a A'ery simple manner (see below). For the isolation of this alcohol from mixtures with hydrocarbons, etc., several other methods have been reported. All of them involve the preparation of an acid ester of geraniol either by the action of phthalic acid anhydride on the sodium compound of the crude geraniol (Tiemann and Krueger,^ 1896), or by heating geraniol with phthalic acid anhj^dride in a water bath (H. & E. Erdmann, 3 1897), or in benzene solution (Flatau & Labbe,-* 1898). This acid ester is saponified with alcoholic potassa either as sucii or its sc^dium salt which can be obtained from the silver salt purified by crystallization. These metliods, however, possess no advantages over the calcium chloride method. On the contrary they are more complicated and yield no purer product than does the simpler method of Jaeobsen. Geraniol prepared by one or tlie (jtlier of the above methods has a roselike odor and is a colorless, somewhat oily liquid which on lono-er standing in contact with the air changes through the absorption of (jxygen. Its pr(iperties are reported as follows : B. p. 11(»— 111° at 10 mm.; 121° at 18 mm.; 2:50° under atmospheric pressure (Bertram and Gildemeister," 1897). B. p. 120..5— 122.5° at 17 mm.; d2o» — 0.8891 (!); noan" = 1.47GG, (Tiemann and Semmler," 189-3). 1) Liebig's Annalen, 1.57, p. 232. t) Compt. rend., 126, p. 172.5; Bull. Soc. -') Uerichtc, 2!), p. 901. ohim., Ill, 19, p. 633. 3) .rouru. f. priilit. Chcni., II, 50, =) .Jnurn. f. prakt. ('hem., II, 56, p. 50S. I'- 17. 6) Berichte, 26, p. 2711. Tlie More Commonly Occurving Constitneiits of Volatile Oils. 133 B. p. 110.5—111° (coiT.) at 10 mm.; d^ = 0.8812, (H. and E. Erd- mann.i 1897). d],-' = 0.880—0.883; nDi7=>= l.-tTG6— 1.4786, (vStephan.a 1898). As primary alcohol geraniol is converted by oxidation into the corresponding- aldehj'de citral, and can be again obtained from this by reduction (Tiemann,^ 1898). Sini.'e citral can be prepared synthetically, geraniol must therefore be idso classed with the compounds which can be obtained synthetically. Geraniol (besides terpineol) or its acetate are produced by isomerization from linalool, when this is heated for some time with acetic acid anhydride (Bouchardat,* lS9;i ; Stephan," 1898). Obversely, geraniol can be changed to linalool by heating with water in an autoclave to 200°.** At a higher temperature hydrocarbons and their polymerization products are formed. The same result is obtained when the chlorides produced by the action of hydrochloric acid on geraniol are treated with alcoholic potassa (Tiemahn,"^ 1898). A third method consists in decomposing the phthalate mentioned under linalool (Stephan,8 1899). In general, geraniol is not acted upon by acids to the same extent as linalool. Thus it is (juantitatively changed into the acetate by boiling with acetic acid anhydride, but not isomerized. On shaking with dilute sulphuric acid it is chtmged like linalool, although with greater ditliculty, to terpin hydrate (Tiemann and Schmidt." 189.5). Con(jeiitrated formi(; a.<;id exerts, like potassium bisulphate or ])liosphoric acid anhydride, a ilehydrating action on geraniol. While with i)otassiuni bisulphate a cliaiu hydrocarbon is said to be formed iSemmler.i'' 1891), the other reagents produce terpenes. Formic acid produces dipentene and terpinene (Bertram and Grildemeister,ii 1894 and ll-(96). According to Stephan,!^ formic acid, also a mixture of glacial acetic acid and sulphuric acid, convert geraniol as well as linalool into solid terpineol melting at 35°. Alkalies scarcely act on the Jilcohol in the cold. If, however, heated t(j 150° with a concen- trated alcoliolic alkali solution, a tertiary alcohol CsHigO is said to be produced (Biirbier,^^ 1898) by the splitting off of carbon dioxide. 1) .Jouru. t. prakt. Chem., 11, rB09 ; [a]D = -f°40'. According to Tiemaun and Bchniidt." (1896), d-citronellol formed by the reduction of (;itronellal possesses the following properties : B. p. Ill— nH° at 17 mm.; di7..-,° = 0.8.">G.") ; noi-.-.o = 1.4.J659 ; Mdi7..-,» = + 4-°. 1-Git.ronellol, prepared from rose oil by the phosplnjrus trichloride method, boils under a pressure of l-")mm. at 113 — ll-t°, has d2(io=0.8612, no ^ 1.J:-")'''89 and turns the plane of polarized light 4:° 20' to the left.''' For the alcohol obtained from geranium oil from the island of Eeunion by a method similar to that of AVallacli, Schimmel & ("o.** found (1898) : B. p. 22.'— 22()° at KU.rj mm.; di5° = 0.8(52; nD23= = 1.1-')(511 ; [a]D = -l°40'. 1) rheni. Centrbl., 70 i, p. 1094. tivige zur KenntnLss aliphatischer Terpeii- 2) Amer. Chem. .Tourn., 11, p. 46^i. verbinduDgen. Inau^. - Diss, (iotting^en, 3) Berichte 29, p. 906. 1896, p. .'36. i) Liebig'H Annalen, 27S, p, HI 6; 296, 6) Berichte, 29, p. 906. p. 129. ') Ibid., p. 923. 5) Xaclirifliten d, Kgl. Ges. d. Wiss. zii S) Bericlit von S. & Co., Aprli 1808, Oottingeri, 1896, I, p. 64; .\a.schoid, Bei- p. 62. 1 ;!s General Part. Citi-onellol is mucli more stable tliaii geraiiiol and is not aftVcted by lieating witli alkali. AVhen shaken with 10 percent sulphuric ai'id it is converted by the addition of water into a diatomic alcohol, from which dehydratinineol from niaouli oil [«]„ = — 2° 10' (Bertrand," 1893). With artificially prepared 1-terpineol [a],, has been observed as high as — 117..')° (Ertsdiikowsky'O). In their chemical behavior the inactive and active modifications are completely alike ; for a few derivatives, however, slight differences in the melting points have been oljserved. Terpineol is a tertiary unsatu- rated alcohol, which yields with bromine and nitrosyl chloride addition products, of which the latter as well as the nitrolamines produced from it b,y treatment with bases, are very well suited for characterization 1) Compt. rend., 104, p. 997. 2) Berichte. -'S. p. 2189. 3) .Tourii. fl. rii.ss. phys.-clieni. (iew., 2S, p. I;t2; Abs. Bull. S()c. rliiiii.. Til, It,, p. 15X4. *) .Jonrii. [. prakt. Chem., II, 58, p, 100; II, IJO, p. 242. ■"•) (;)bservationK in the laboratoi-y ol S. & Co. 6) See p. 110. 7) Liebig's Annnlen, 275, p. 104. s) Iterioht von S. & Co., Oct. 1897, p. 9. 9) Bull. Soc. chiiu.. Ill, 9, p. 4:ji>; ('onii>. renil., 116, p. 1072. i'>) Lot", eit. Conii). also . *) Bericlit von S. & Co., April 1897, p. 0. 2) I^ieljig's Annalen, 275, p. 104. Thf More (Jommoiily Ocvurriog Constituents of Volatile Oils. 143 BOKNEOL. Borneol occurs in the free state in both optically active modifications, in the form of ester Tiiostly in tlie laevogyrate modification. Tlie borneo-camiihor from Dryobalanops camphom consists of d-borneol, while the Ngai-camphor (or Ngai-fen)'^ from Blumea bal.sa.mifera, is the laevogyrate modification of borneol found in nature. d-Borneol has also been found in spike and rosemary oils, as well as in Siam cardamom oil; 1-borneol occurs as esters and also in the free state in citronella oil and the oil of Matricaria parthenium as well as in valerian and kesso oils. In the two latter oils it occ-urs as acetate and isovalerianate. Further, boi-neol has been shown to be present in golden rod oil, in the oils from sage and thyme, as well as in the oils from Aristolochia serpentaria and A. reticulata, but no statements as to the dire('tion of rotation of the liorneol found are recorded. The a(;etate of this alcohol possesses the characteristic fir odor and forms a large c(.)nstituent of many coniferous oils. Artificially, bcjrneol is most readily obtained from d- or 1-camphor by reduction with sodium in al<;oholic solution (Wallacli,^ 1885) or in indifferent solvents (Beckmann,* 1888); the borneol thus prepared is, however, never pure, Imt is a mixture of borneol a,nd isoborneol. In alcoholic solution less isoborneol is formed than in indifferent solvents. In the latter case there is obtained as by-product about ."> percent of camphor pinacone (Beckmann,* 1897). From the mixture of the two borneols pure borneol can, however, be separated by acetylization, aiid saponification of the bornyl acetate which crystallizes out. Pure Ijorneol, recrystallized from ligroiu, forms brilliant laminae or plates, which belong to the hexagonal system (Tra.ube,-'' 1894). It possesses an odor somewhat similar to that of camphor, and reminding of amber. It melts at 208—204° (with preparations containing iso- borneol at 20G — 208°) ; the boiling point lies at 212°. Like camphor, borneol is also somewhat volatile at ordinary temperature, but not to the same extent. The specific gravity is reported by Plowman" (1874) to be 1.011 for d-borneol, 1.02 for l-borneol. Beckmann ''■ ('89 & '97) found the rotatory power of d-borueol to be -)- 37,44°. In agreement with this are the statements of HallerS (1889) 1) Bericht S. & Co., April ISD.j., p. 74. t ) Liebig-'s Annalen. 250, p. :ir,:i ; 2) Liehig'H Annalen, 230, p. 22,5. .lom-n. f. prakt. Chem., II, 5.5, p. Ml. 3 1 Berichte, 21. Ref. p. .321. «) Compt. rend., 109, 30: see alHO 1) .Toiirn. f. prakt. Chem., 11, 35, p. 31. Haller, ('onipt. rend., 112 (1891), p. 143, 5) Journ. f. prakt. Chem., II, 4-0, p. 3. on the influence of the solvent on optical 6) Pharm. .lourn., III. 4, p. 710. activity. U4 GeiwiYil Part. who deteriniiied for the alcohol refj,enerated from tlip rrj'stallized acetate, [«]d to be + ;!7.G3°. Natural 1-boriieol possesses according to Beckniann,! [a]D = — ;!7.74°, according to Haller,^ (1889) [«]d = — 87.77°. A slightly higher rotatory power, namely [«]i, = — 80°2r/ was observed for the 1-bonieol occnring under the name of Ngai ffn (Schimmel & Co.sj. The dextro- and the laevogyrate modifications of borneol are completely alike in their chemical behavior. Although borneol is a saturated alcohol, it forms loose addition products with bromine and hydrohalogens (Wallach,* 188.")), which, liowever, are not suited for characterization. As secondary alcohol it is first converted tiy oxidation into the corresponding ketone CiiiHuiO, camphor, a reversal in rotation not taking place. By using niti-ic acid as oxidizing agent, oxidation products of camphor, like camp^ioric acid etc., also occur. Toward dehydrating agents, like zinc chloride and dilute sulphuric acid, boi'neol is very stable (Bertram and Walbanm,'" 1894). In this respect it differs greatly from the isomeric isoborneol. Phosphorus pentachloride converts it into bornyl chloride. When this is boiled with aniline, hydrogen chloride is split off, and camphene is produced. As already mentioned, borneol also occurs in combination with fatty acids in volatile oils; more commonly as the acetate of l-borneol. which has so far been shown to be present in the oil of Abiei< nJlni. hendock oil, oil of Fieea, nigra, in oil of Piuus ledehourii as well as in the oils of Abies bahamea and A. cahadeimis, further in valerian and Icesso oils. In addition to these it lias been sliown to be present in the oils of Pinu.s inontana, golden rod, Satureja thjmbra, and Thymus capitatus' but it is not known in which modification. Bornyl acetate is the only fatty acid ester of boi-neol which will crystallize. From petroleum ether it is obtained in rhombic hemihedral crystals, which melt at 29° (Bertram and Walbanm," 1898). Since borneol is fairly stable toward acids, its esters can lie jirepared either from borneol and acid chlorides or anhydrides. They all pos.sess an odor similar to the acetate, the intensity of which diminishes with increase in the molecular weight of the acid. Tschugaeff ''' (1H98) reports on the jiroperties of the fatty acid esters of l-borneol as follows : 1) Meblg's Annalen, 250, p. .353; .lourn. M Lu'bis's Annnlen, 280, p. 226. t. prakt. Chem., II, 55, p. iU. o) .Toiirn. t. prakt. Cliem., II, 49, p. = 1 Coinpt. rencl,, lO.S, p. 456; 100, p. 45(3. I'l Arcliiv d. Pharm,, 2.31, p. 30.3. 3) Bei-iolit von S. & Cci., April 1805, p. 74. 7) Berlchte, 31, p. 1775. The More Commonlr Occurring Constituents of Vnlntile Oils. 145 B. p. ( 15 umi ) df [«-]i. 1-Borneol Form ate .ict'tate PropioTiati' n-l!utyrate Ti- Valeri an ate 97° 107° 118° 128° 189° 1.0058 0.9855 0.9717 0.9611 0.9588 — 89.00° — 40.40° — 44.40° 1 — 42.06° — 89.15° — 87.08° Hiniilar statemeiit.s were made by Bertram aiid Walbaum- in 1893. For the cliaracterizatioii of l)orneol the bornyl iihenj'hirethane pro- (lui-ed hj the action of carbauil is used. It melts at 1:{8— l;-{<)°:i and is optically' active in the same direction as the borneol from whieli it is prepared. The addition produ'-ts formed by tlie combination of borneol with chloral and bromal. (jf which that of the chlf)ral melts at -lO" (Ha,ller,-t 1891), that of the bromal at 105— 109° (Minguin.s 189;-!), can also be used for the detection of borneol. Borneol may also be converted into carajihor by oxidation with Beckmann's chromic acid mixture and this identified by its oxime. When acted on l>j' formic aldehyde in the presence of sulphuric or hydrochloric acid, borneol is converted into diborneol formal (('ioHit. 0)2f'H2 (Brochet," 1899). Occasionally it is necessary to separate a mixture of borneol and cani])hor. The separation can be effected according to Haller's^ (1889) method by heating- the mixture with sui-ciTiic acid anhydride. Borneol is thereby <'(jnverte(l hito the acid succinic acid ester, the sodium salt of wliicli is soluble in watei- ;in(l. therefore, easily separated from the camphor. Instead of succinic acid anhydriile the corresponding- dei-iva- tive of plithalic acid may be used. The esters of borneol formed by lieating- with benzoic or stearic a<-id anhydi-ide are difficultly volatile and can lie se]iarated from (;ain]ilior by distillation with water vapor. The camphcn- may also lie coiivei-ted into its oxime and this removed from the mixture by shaking- with about 25 percent sulphuric acid. Mk.\thoi^. Menthol is found only in tlic laevogyrate modification as tlie princijial eonstit\ient of the pejijiermint oils, from which it sejiarates in 1) The same value was found by Haller ill ISSil fill- the acetates of the borneol from vali'i-ian oil anil Drrohnlauops ]ireiiai-ei] by fMiiling with acetanhydrtile. Coinjit. rend., lOi), iJii. LMI & 80. 2) Archiv. d. Phariii., 231. |i. 3l>r,. 3) Journ. f. prakt. Clieiii., II. 4° under 7-"!.'> mm. pressure (Arth.-^ 188(;): M. p. 42. .•!°; b. ]i. 212..",° under 742 mm. pressure (corr.): d|{^ = ().8<)() for solid. d^^7y° = (1.8810 foi- licpiid menthol: [«]di.;" — — 40.8(3° for molten menthol ( Lon,ii',+ 1802); P>. |i. 21.").."° under 7."i8 mm. pi-essure; «d:jo' == — 4;'>°4.')' for menthol in an cnercijoled molten condition ( P(.)wer and Kleber."' 1804). M. ]i. 4;!°; ['/.]d = — 40.3° (in 20 ],. r. alc(^holic solution) : — .",7.7° in 10 ]>. c. alcoholic solution (Heckmann," 1880) ; nc4:r-= 1.4470 ( Briihl." 1888). Menthol is a saturated secondary alcohol, whidi by the alistraction of watei- with potassium bisul],liate, zinc chloride, etc., is converted into the hydrocarbon meuthene (lioHis. By reduction with liydriodic aciil and jihosphorus, hexahydroi-ymene C10H20 is produced ( Berken- heim,*^ 1802). Fjion oxidation with dinimic acid mixture the coi-re- sponilin;^' laevo, ;t25. 77/e Morr ('oiiniionlv Oi-rtirring Constittipiits of Volntilc Oils. - / ■ f'H 147 CH2 CH ^CHOH I I ('Ho\ /CH2 \/ CH i CH3 luihi been given to ineuthol. .Tiinger and Klagesi coiToborateil this formula in 1S06 by the eunversion of nientlione into 3-chlorc.vniene. That menth(jl yields cymeue when heated with anhydrous copper sulphate to 250—280°, had previously been found by Briihl^ (ISOl). Of the fatty acid esters of menthol, which c-an be obtained in the Siune ma.nner as those of borneol, the acetate and isovalerianate have been found in peppermint oil. They have been investigated by Tscdmgaeff s (1.S08) with site(.-ial consideration of their rotatory power. According tfj this investigation, the lower esters possess the following properties: B. p. ( 15 mill) , 20° [«]i. Formate-'- 98° 108° 118° 129° 141° 0.9359 0.9185 — 79.52° — 79.42° Propionate ii-Butyrate u-Valeri ai 1 at e 0.9184 ; — 75.51° 0.9114 , — 69.52° 0.9074 — 65.55° Powei- and Kleber" (1894) report that menthyl a.ceta,te boils a,t 228° under 7G2 mm. pres.sure and that «d = — 72°ir)'. With formic aldehyde meiithol forms dimenthol fcjrmal 0H2(0CioHi())2 melting at 56.5° (Brochet") The methyl ester of menthylxanthogenic acid (m. p. 39°) and menthyldixanthogenate (yellow crystals) are of interest because they can be converted into menthene of a high rotatory power (Tschugaeff.T 1899). With its peculiar physical ])roperties the identification of menthol will hardly offer m\j ditficnlt.y. If it does, however, the menthylphen.vl 1) Herlchte, 29, p. 30-t, 2) Berichte, 24, p. 3.37-4. 3) Berichte, 31, p. 364. *) Solidifle-s at a low temperatiu-e and melts at + &°. 5) Pharni. Kundschan, 12, p. ArchiT d. Pharni., 232, p. 653. 6) Compt. rend., 128, p. 612. 'I Berichte, 32, p. 3332. 148 General Fart. uretliane pi-ddiicpd by the action of phenyl isoeyanate may be useil for thin pnr])Ose. Tliis CDmpcnind, first prepared by Leui.-kart, ineltis at 111—112°, and is o])tically active in the same direction as the menthol from which it is prejiared. AVhen heated with sodium ethylate menthol is reg-enerated, but also inactivated (Beckmanu.i 1897). A furtheT- derivative, by means of which menthol is easily character- ized, is the menthyl benzoate produced by heating it with benzoic acid anhydride. The ester is difticultly volatile with water vapor and melts at 54.5° (Beekma]ni,2 1S91 and l.S!»7j. The separation of a mixture of menthol and menthone may be accomplished in the same manner as that given for bnrneol ( Beck- mann,'^ 18!)7). As previously stated, the sesquiterpenes are fre(piently accompanied by so-called sesquiterpene alcohols CL^HoeO, which upon dehydration yield hydrocarbons ('15H24. They are colorless, and when pure mostly odorless. With the exception of the liquid santalol they have a mai-ked tendency to crystallize. The following table contains a compilation of tlieir physical properties to<;et.lier with those of several other alcohols of different c<.)nq_)osition. 1 P^oiinula ir. p. B. p. Optical behavior Maticocam pli or C12H20O 94°^ 300— ;!(12° [ajD = — 28°5 Kessylalcoliol 6 C14H21O2 ,s.-,° 155—1 5()° (11 mm) laevogyrate iSaritalcain]ilior' C,..Ho.i.O, 104—10.")° — — Cedi-ol CisHidO ,S.-| — ,S6°s 282° 9 ('i-,l ]•>«() (i.-,_(;7oi() 248° 11 laevogyrate GiiOiioP- CsHoeO 91° 288° 14S°(10iiim) Leduinciiniplioi-i3.... t'lollaiilt 104-10.-1° 2,S2— 28.3° a], == -1-7.98° Patclioiilialcoliol Cl5H2(.0 .^G"!! — [«]r, = _n,s°i5 Scsqiiiterppiilivch'atc I'rmn jipppcri" (',oHi„.2HoOV 164° — Santaloli' t'lsH^i-.O liquid (d,5°=<>.980) Km— 1(V.)° 1 10—1 2 mm 1 ['/.]ri to — 31° .Iiinipcrcaiujilior '"... — 1G5-I(i6° — Ylaiig-vlaiiK- caiiii)liori" — i;i8° — — 1) .rolirn. f. imikl. ('hem., II, .^>."i, p. 29. -) Linbiff's Annnh'n, 2r,2. ji. .31 ; .Tuurn. f. |ii-akt. ClK-iii., II, .'-.5, 1). 10. 3) .Iduni. f. in-iikl. Chfiii., II, .-j;-, |>. 17. *) IviiKlL'i-, Itericlitp, IC. ji. 2S41. -'1 Trniibf. Zeit.si-lii'. f. K i-ystall(isi-., 22, r. 47. '•) Bertram & (iilili'iiiei.stcr, Arcluv d. riiariil., 228, p. -ISS. 7 — It*) See next })ap;e. Tlie More Comiiionlv Ucvunhiir Constittieiits of Vohitilf Oils. l-H) Aldehydes. Anujiig' the uxygeiiated constitueiits of volatile oils characterized by a strong odor are several aldehydes. Of the fatty aldehydes, acetaldehyde is found in the distillate of almost all seeds. Isovaleriaiiic aldehyde and acetaldehyde have also been obsei-ved in the distillate of various eucah'ptus oils, of i-ajeput oil and peppei-mint oil. The aldehyde of oleic acid has been found in orris oil. Of much greater importance, however, are the so-called aliphatic terpene aldehydes, citral, ('loHmO and citronellal, ('kiHisO; and the aromatic aldehydes, benzaldehyde and (-innnmic aldehyde. The former are also of special interest on account of their relation to important alcohols oceuring in oils, the lattei- liecause of the large percentage present in some oils. ClTRAI.. Citral is the only aldehyde corresponding to the formula t'ldHiiiO, which has so far lieen isolated from \-olatile oils. (.)n account of its close relation to geranial, being its first oxidation product, it is also called geranial. It ot-curs quite frequentl,y in nature. It was first-*' found in the oil of Ilnrklionsin citi-iudor;i and as it proved to be identical with the constituent to which lemon oil owes its odor, it wsi.s called citral. In larger (piantity (70 — ISO jjercent) it is contained in lemongrass oil a,nd occurs further in orange oil. mandarin and cedron oils, in West Indian limette oil, in the oils of vei-bena, balm, b;iy, pimenta. .lajianese pepper, sassafras leaves and of Encniyptns i^t:ni>vrhni!i. From all the.se oils citral can be isolated by means of the crystalline bisulphite ilonlile compound (.see lateTM, which, after previous puriflcation by washing with alcohol and ether, yields citral in a ])nre state l)y decomposing it with .alkali carbonate. 7) Bei-ioht von S. & Co.. Oct. TS'.Jl, ],. 13) Hjelt. Berichte 28, p. :H(iS7. ;J4 : Berkenheim, Cheiii. Ontrall)!., 04 1, i*) Wallach, Liebig's .\inialen. 27'.), p. OSG. p. H!)4. 8) BeriKht von S. & Co.. Oct. 1,S97. i=) Mon tgolfier, Conipt. venrl., 84, p. Sll. p. 12. I'^ootnote. ^6) Pcinemann. Archiv d. T^harni., 2:{4, 9) Walter, rjiebi;2,''s ,\nnalen. :^0, p. 247; p. 241. 48. p. 8.">. '7) OIjHcrvations made in the iaborji- 10 1 Schaer & W.vss, ,\rchrv il. I'harni., tor.v of Schimniel & Co. 20G, p. 316: Winckler, IJeliiff'.s .Vnnalen, iS) Bericht von S. i; Co., Oct. isy.". 8, p. 2H0. I'- -t6. 11) .Schmidt, Bei-iclite, 10, ij. ISO. iS) Il)idem, ,A.]jrii 18116, p. 62. 1-) Bericht von S. & Co., ,\pril 1802, j). 20) y^T the histor.v of citral wee Tie- 42; Wallach, I,iebig'« .Annalen, 279, p. 3f)6. mann, Berichte, .SI, p. .'{278. 15(1 General I'.irt. Artificially, citral is obtained with a yield of 20—40 pereeiit by the oxidation of gei-aniol with chromic acid mixture (Tieniann.i 1.S98). The tertiary alcohol linalool also yields the same oxi*raniol first takes place by the action of the acid oxidizuig a<2,ent. In a purel.v synthetical wa,y citral has lieeii obtained by the distillation of a mixture of calcium gereniate and calcium formate (Tiemann.s l.SOH). Citral is a mobile, shglitly yellowish, optically inactive oil of a penetratinii' lemon odor, whiili boils at 22.S — 2-!^'° under atmospheric pressure, not entirely without deconi])ositi(>n. Its properties were jilven by Tiemaini and Semmler-^ in 18i);{ as follows: P.. p. 110—112° at 12 mm.; 117-119° at 20 mm.; 120—122° at 2:^mm.; di.,c = O..Si»72 ; d2-- = 0.H,s44 ; iini.-,o = l .l<):n ; nD22' = 1 .18()11. Observations made in the laboratory of fSchimmel i.V: Co. on an aldehyde carefxilly purified by means of the bisulyjhite compound gave the following results ; P.. p. 110-111° at 12 mm.; d,.-,o = ().,s'.);i ; nui7' = 1.4901 .",. As diolefiuic aldeliyde, citral takes up 2 molectiles of bromine, but yields with it no solid eompounil. Toward acids and acid ivgents it is very sensitive and is greatly changed by them. Dilute sul])huric acid and potassium bisulpliate a.ct very energetically with abstraction of water and formation of cymene. Alkalies also act on citral. When boiled with ])otassium i-arbcmate solution it is split up into acetaldehyde and methylheptencme CgHi-iO (Verley.-t 1,S<)7 ; Tiemann."^ 1,S9<»). This ketone also a(;compa.nies citral, e. g. in lennnigrass oil, and is alst) foiined from it by gentle oxidation. ('itral shows all the properties of an ahlehyde; thus it is changed by reduction to geraniol (Tiemann," 1S9,S) and reacts with the well- known aldehyde reagents. It shows a. peculiar behavior toward sodium bisulphite solution (Tienmnn and Si'niniler,''' 189:5; Tiemann.'* 1898). If the solution does not contain too great an ann)unt of free stdjihurous acid, there separates ujiou shaking at a low temi)erature the ditticultly solnlile, normal crystallized double comixnmd CnHi.- . ('II(OH)- S(.):!Xa, wliidi camiot be i]uantitatively split u]i by sodium carbonate or (■a.nstic soda.. If the crystallized compound be nllow(;d to stan Berlchte, .31. p. .S2S. 3) Berichtc, 2(), p. 2709. 7 1 Berichte, 21), p. 2710. i| I'.nli. S.>e. chilli., III. 17, p. 17,'5 »! Berichti', 31, \\. 3:>,lii. Thr Moiv Cininiiiiiily Occurv'niy Constitnpiits of VohUilf Uil.s. 151 solved with the foniiatioii of a dihydrosuliihouic acid derivative of ritral, CtiHiT. (S08Na)2 • CHO. wliieh no longer regenerates citral with alkali carbonate, but (loes so with caustic alkali. If the temperature ri.ses too high during the solution of the cry.stallized (/ompomid, caustic alkali also fails to separate citrjd from the liquid, a so) Berichte, HI, pp. S21 , 281."). ') Ibidem, p. 2128. ■i) Berichte, .HI, ji. H.'iHI . lri'2 Cenevnl Fni't. , irone of orris oil, and wliicli likt^ tlip InttM' haw the oilor of violets (Tiemanii and Ki-ueger.i 1M9;!). Inasinueli as citral possesses a ])enetratiu,i;' odor, tliis in itself atti-acts attention to its ]>resenre in volatile oils. P'or more pf)sitive proof the separation of the aldehyde by its Ijisnljihite compound is tried. The ref^-enerated oitral is converted by condensation with pyro- tartaric acid and ,J-naphthyla.mine into the «-citry]-,5-naphthocinchoninie a.i-id discovered bj' Doebiier- in tH!)4 wlio directs tliis cliaractei-istie oom])ound to l)e prepared a,s follows: '20 j)i;i citniiiloi-i." (.'oruE: Citral in ]jure oil of lemon. ^ 1) BtTifhte. HI. |>. .33l!!l. i) Bull. Soc. f'hini.. IHJ, 21, ].. 41il. -} ITeber Conden.sationen inittelst arc- 5) n)i(ieTn, p. 02.8. raatiHCher Basen ii. k. w. Inaiig. I)i.MK. «) BnU. Soc. Chiin., [:■!], 21. p. il;!.''i. Heiflelberg, p. 24. 'I C. & D., ai. ji. (;.-|0. ■■i General Part. Flatau : Ksseiitial oiLs of lemon-grass and citronella.i Flatav & Labbe: Metliofl for separation of citronellal and citral.^ TjAbbk: On leraongi-ass oil." A i)olynieride of citral.-' On barium acid salpliite addition jiroducts of nitia.l and citronellal. = Stikhj. ; Three lemoiigrass aldeli.ydes." Tikma.xn: Oh the action of alkaline and acid 7-eageiits on citrnl." On the behavioi- of citral purified according to different methods toward seiiiicarbazide.'* On the li.vdroxysulphonates of cinnaniic aldehyde, citi-onellal and citral. a On the separation of citral from citronellal and methyl he])tenone.i" On the three lemongrass aldehydes of Jlr. W. Stiehl.'^ On natural citral and tin' C(jm]iosition of oil of lemon glass. '- ,V number of these articles by the late I'rofessor Tienmnn have been published in book form. VEltLE^ : Action of acids on citral.'-^ Condensation of citral with cya.nacetic acid.!-"- Condensation of citral with malonic acid.'^ The rep(n-t of Professor v. Baeyer as ex]iert in the ionone proceedings has been published by A. W. Sehade of Berlin. " ('iTlio.XEl^LAL. The second aliiiluitic nl(leliy(hj with ten i-nrliDii atoms foiioil in volatile oils is citronellal ('icHisO. wliicli occasionally oi-curs aci/onipa.m'- in<:- citral, the dihyrtroderivatiye of which it appears to be. Citronellal i.s distinanished from citral by bein^' optically aitive, bnt has up to the present been fiaiml oidy in the dextroii'.yrate modification. It is probable that citronellal with a low rotatoiT power is a, mixture of both optically active modifications. d-Citronellal is found in citronella oil and in the oil of Eui-iilv])tuK nmvulata var. ritrioilnr;!. Its presence has also been shown ill the oil of Eucalyptus ile;ilh;it:i. in balm oil, and besides citral, in lemon oil. AA'hether it is <-ontained in mandarin oil has not been definitely determined. The isolation of this aldehyde from the oils rich in citronellal (citronella oil, oil of Enr,'ilvj>tu8 rnneulnt.-i) offers no ditticulty, sinc-e citronellal can be readily .se])arated in the form of its iTvstalline bisulphite eompound. As citronellal is very sensitive to acids, as well 1) null. Sec. Ohilii. [8]. 2], |i. l."S. !M Hull. Sec. Chilli. [:',], L> 1 . |i. I'.IC,. 2) Cheiii. Ceinrbl., 70i, |i. 10'.i4. i") r,cTi(hti\ :V2. p. sl-_>. ■■<> Hull. Kof. Chilli. [3], 21, p. 77. H) Ihldi-m. p. Sl27. 11 Ibiileni, p. 407. 12) Ibidem, p. 830. ■') Ibidem, ]). 102B. Ki) Hull. Soc. Chilli. [3]. 21. [i. 4()s;. ») .reurli. pr. ChiMU.. 1117. p, 4'.I7. l l) Ibidem, p. 413. 7) Iterlchti'. 32. p. 10? l.i) llildeiii. p. 414. ■•1 Ibidrm. p. 2.111 Thf Movf ('iiiiiiiionly (Ivi-urrinir ('(>iif — '07). This is isfuneric witli tlie alcohol pulegol ('niHigO, resulting upon reduction o' pulegone, and fields when oxidized a ketone CinHiiiC), wliicli can be inverted to natural pulegone. For correi-ted physical cwnstants of pule- gone and isopulegone the more recent work of Harries and Boeder'^ should be consulted. Whether isopulegol, wliicli lias been found in commercial citronellal by Tiemann'* occurs in the natural oils from whii-h citronellal is obtained or whether it is formed upon standing has not yet been determined. Lalibc'' is of tlie opinion that whereas i| Liebig's Annalen, 27S, ii.;!17: 206, p. lai. 6| Berichte, 2!l, p. '.Iiy; ;i(l. p. 22. 2) Btn-ichtf, 29. p. 9115. ') Berichte, 82, ]i. :Vir,7 . :') Amcr. Chem. .rDiirri., 1+, p. 203. 8) Berichte. «2, p. S2.-. J-i Loc. cit., p. '.mk;. '■>> Bull Si, I- Chilli, [aj. 21. II. 102:i .'■>) Berichte, 2-I-, p. 20s : 20, r'- 2256. 15G Gi'niTiil Part. citroiiellal when mixed with terpene.s and tei'peiie alcohols is relatively stable, when pui'e it is easily i-onverted into its isomeric cyclic com- pounds. Toward sodium liisnlphite citrcjnellal lieliaves much as does citral. Besides the crystallized noi'mal addition product with one molecule of NaHSOs, in which the bisulphite ha-s added itself to the aldehyde group, it also yields hydrosulphonic acid derivatives with one or two molecules of NaHSOg. The addition may take place at the double bond only, or at both the double bf)ud and the carbonyl group (Tiemann.i 1898). With liydroxylamine i-itronellal forms a. liquid oxime, whi(;h by the abstraction of water is converteound. by recrystallization frinn cliloroform and ligroin is obtiiineil in white leaflets, melting at IS4° (Tiemann and ScliTuidt.-^ lNi)7). By energetic oxidation citronellal .yields the same products a.s citronellol, i. e., acetone anil |i-methyladipinic acid (Tiemann and 8i'hmidt.^ 1N!)()). (_!ori-esponding to citronellc)! the aldehyde is to be regarded as dimethyl-2,6-octene-2-abcS CHri . ('(CHn) : CH . CHo . CH^ . CHfCHa) . ('H2 . OHO (T. & 8-). Like citral, citronellal reacts with pyrotartaric acid and ,J-naphthyl- amine yielding '/-citronellyl-^J-naphthocinchoninic acid ( Doeliner." 1S1(4) which can lie use2.j Tlie .Uo7-e ('onniionlv Oct-nrrinfi- Constituents of Volntile Oils. 157 Of aldehydes with eyehe structure FURFUHOL ('4H4C) shouh;! first he mentioned, the occurrence of whicli in oil of cloves and oil of clove stems has been observed. Its formation is probably due to the decomposition of a carbohydrate-like compound. Inasmuch as it possesses the property of gradually becominfj;' darker in color it is surmised that the darker colf>r acquired by some oils upon standing is due to the presence of this substance. Furfurol has recently been also found in the oil from musk seed 1 and that of caraway seed. 2 It is identified by means of its hj'drazone and by tlie color reactions it ])roiluces with aniline and p-toluidine. The following carl)Ocyclic aldehydes have been found: Bexzaldehyde ( 'eH.-, . CHO in the oils of bitter almond, chei'ry laurel, wild chei'ry bark and of Indigo- feni galegoides. It possibly also occurs in the oil of cinnanicjn leaves. Salioylk; aldehyde ('cHi. OHra . OHOC'] (o-oxybenzaldehyde) in spirea oil from Spii-aea ulmaria. Sji. filipeiiduhi, Sp. digitatsi, Sp. lohata, and in the oil of Crejns foetidti. Anisic aldehyde C«Hi. OC^HsC^l . CHOH] (p-oxybenzaldehyde-methylether) in old anise and fennel oils, in which it is formed by the oxydation of anethol. CUMIXIC ALDEHYDE CiH-t . ('sHtW . CHOCH' (p-isopropylbenzaldehyde) in cumin oil, in the oil of ('ii:uta. virosa., also in various eucalyptus oils {E. Jiacma^tomn, odorata^ oleosa, popiilifeva). Vanillin (m-methoxy-p-oxyl)enzaldehyde) (^oHk. OHC-i] . OPH.sCai . CHOt'l and Heliotropin (protocatechuii- iildeliyde methylene ether) ('oH.s . OCX^HoW'-^l . CH()[i] in spii-ea oil. Cinnamk: aldehyde ('(1H.5 . C'H : CH. CHO in cassia oil. (Jeylon cinnamon oil. the (jil of cinnamon leaves and roots, also in the oil of Ciiinamomvm loureirii. o-OuMARic aldehyde methylethbr (o-methoxycinnamic aldehyde) ('oHi . OfB.st^l . OH : OH . CH()W in cas- sia oil. i| Bericht S. & Co., Oct. 18'.i'.J, p. 3(1. 2) lliideiii, ji. 32. ION (leiieral P/irt. Ketones. The iilipliatic ketones ;ii-e representeil in volntile oils Ijy a. few iiieiiibers only. Of the Ha.turated ketones onlj- acetone CHg.CO.CHsr methyl aniyl ketone flH^.CO.OsHu and methyl nonyl ketone CHs . CO . ('hHih; of the unsatui-ated only methyl heptenone (.'8H]40 has been fonnd. Jn the distillate, especially of leaves, acetone has frequently been observed together with methyl alcohol, e. g. in that of patchouli, coca, and tea leaves. To what reaction this ketone owes its orifiin is not known. Methyl amyl ketone is contained in the low-boiling- fractions of clove oil and iiajjarts to it a pleasant odor. Methyl nonyl ketone is the ])rinci])al constituent of oil of rue and separates from this upon cooling- (m. p. 1.'°). and can tdso be readily sepaivited by shaking with bisulphite solution. ilETHYL HEPTENOXE. Of greater interest than the saturated ketones named is the unsaturated methyl lieptenone CgHi^O, which occurs as' a constituent of stmie volatile oils and Is also obtained as a decomposition pr(.)duct of related compounds. Accompanying the bodies i-losely related to it, linalool, geraniol and citral. it occurs in lignaloe, citronella. and lemon- grass oils. It evidently owes its existence to the decompositimi of these comi.)ounds, which can also be brought about artiflciaily by mild oxidation. Et can be easily isolated by means of its liisulphite addition liri^duct from the fraction 160 — 180° of the oils named. As a. product of decompositicm it was first observed liy Wallach (iJSyO) in the dvy distillation of cineolic acid anhydride.^ It was also obtained as a saponification product of geranic acid nitrile (Tiernann & Sennnler,- IH!);^) and as oxidation product of citral 3 and finally by the splitting up of the latter with alkalies (A^'erley,' lSf)7), Synthetically, it has been prepared from amyleiie bromide and acetyl acetone (Barbier & Bouveault.5 ISlXi) also from the iodide of acetopropyl alcohol, acetone and zinc dust ( Verley," 1H!)7). It is a colorless, mobile, o]itically inactive liquiii, with a pmiet-rating ainyl a,cetatedike odoi-. The physical consta.nts. asgiveii, do not wholly agree. Wallach '^ (liSiX)) found for the ketone formed from cineolic acid anhydride : 1) Ijlebig's Aniiiilen, 258. p. ;i2H. S) Coniiit. renil., 122. p. 1422. 2) lierichtc*, 2li, p. 2721. S) Hull. Soc. chim. Ill, 17, p. 101. 3) Ibidem, p. 271'.i. 7) Liebig's Annalen, 2.58, p. 325. J) null. Sof. chhii. Ill, 17, p. 175 77;f Moiv Ctiunnoiily (>ccuri-uif>' (JoiiKtitiieiits of VuliitUi' Oils. 159 B. II. 178—174°; do.io = ().H.-,;i ; nj, = 1.44:( »();?. Tipinniin ami Kriiiier^ (lSi)r>) determined foi- n;itiiral iiietliylliepteiKiiie : B. p. 170—171°; d2oo = y sjjlittinj;- up citral; B. p. l(;s°; S4° at 5(; mm.; di^o = O.DIU ( 1) ; udsi" = 1.487. Acoordinii' to oliMorvations made in tlie laboratoi-y of Schimmel & (Jo. methyllieptenone. whieli iia.d iieen isolated from lemon^-rasn oil and re<.^enerated from the hisul]iliite compound sliow.s; B. p. 170—171° (7.'„S mm); di.-,= = O.H'>,S ; nDir,o= 1 .44;i8,s anil a pre]iaratii)u made from citral by boilinii' with ]iotas.sium carbonate solution ; B. ji. 178—174°; di.-,o = O.H(;.j6. Upon reduction with sodium in alcoholic i-iolution methyl heptenone is reduced to the secondary alcohol, methyl heptenol (Wallach.s 1K98), which is obtained as decomposition product of <;-eraniol, also by the sajioniflcation of yeranic acid nitrile. It combines with bisulphites to form crystalline addition ])roducts ; with hydroxylamine and phenyl- hydrazine to form liquid condensation prodni-ts and with scmicarlia,zide to form a crystallized seTtiicarbazone, which can be used for identification. Iji)on oxidation, methyllieptenone decomposes in correspondence with the formula f'Hs . C(('H:i) : CH . OH2. CHj . CO . CH.s (methyl-2-lieptene-2-fjne-G) into acetone and laevulinic acid (^-,H8U8 (Tiemann and Semnder,* l!S95). Dehydratinj;' agents, like zinc cldoT-ide, etc.. convert it into dihydro-m-xylene CsHio (Wallach,-' 1)S90). , Methylheptenone is easily recofj-nized by its characteristir- aniyl acetate-like odor. For purjioses of identification it is converted into the semicarbazone, which, like the corresponding citral compound appears to be a mixture of isomers, but is nevertlieless obtained of a constant melting' ]ioint when it is prepared according to the directions given by Tiemann and KriigerS (1H95); \ solution of 12 g. of seinicarbazide hydrochloride and 15 ;e. rarvone occurs pi-in(.'i])ally in its optically active variety in volatile oils. Tlie earlier supiiosition of Wallaidi, that inactive carvoiie is con- tained in the high lioiling fractions of thuja oil, has been cori-ected l)y this invesTigator, who ha,s more recently shown that it is not carvone but a hydrocarvone OniHinO. which has probably resulted u]iim rearrangement from thnjone. The dextrogyrate modification of cai-vone is found with d-limoncne in caraway and dill oils, the laevogyT-ate in s]iearniiut and kuromoji oils. In order to separate the ketone in a ])ui-e state from the resjiective oil, its projierty to combine with liydi'ogen sulphide to freviously been s\ig?,. 2 1 Berichte, 27, p. 811. .s| Bei-ichte, 2S.. p. 6-tO. 3) LiebiK's Annalen, 2S(i, p. 11'.). 9) Liebig's Annalen. 27.5. p. lie. + 1 Bcrichto, 17, p. 1,'')7S. loj T,iebig'8 Annalen, 279, p. :i77. •'"') Berichte, Is, p. 222"; LiebiK'.s H) Berichte. 27, p. 121S. Anuaicn, 245, jjp. 256, 2(;8; 246, ji. 226. 12, Berichte. 27, p. 1493. ») Berichte, 27, p. 811; nee al.so i:i| Beridite. 2S. p. 2148. — 24:(J° with a strong solution of alkali, being changed to carvacrylamine (Wallach,^ 1893). By adding carvoxime to concentrated suljihuric acid it suft'ei-s rearrangement to p-amidothyniol iWallach,* 1894). When carvon.e is heated with ammoniimi formate dihydrocarvylannne is formed (Leuckart & Bach, 5 1887; Walhich,o 1891); the same com- pound results when ca-T'voxime is reduced with sc^dium in alcoholic sohi- tion (Wallach." 189;{). If, however, the reduction is carried on in ah-oliolic solution with zinc dust and glacial acetic acid, carvylamine CkiHi^NHo results in two isomeric forms (Goldschmidt & Kisser, » 1887; G. & Weiss," lH9;j; (i. & Fisher.m 1897). Carvojie has such a characteristic odor, that it can be recognized withfjut difficulty. If it is to be seyjarated in a pure state from fractions of :i volatile oil it is converted into its hydrogen sulphide addition product (see above). It may be inentioned that this compound does i| Uei-iclite, :i2, p. 2.T.50. ») Berichte. 24, p. .T.)S4. -( Berichte, 32. ri. 1.510. '^I Liebig's Annalen, 27.5, ]j. lli). 3) Liebig's Annalen, 27."., p.ns: 27ii. p.871. s) Berichte, 20, p. 4S(;. i) iAebig'H Annalen, 27!i, p. -360. '■') Berichte, 26, p. 20S4. ■■"•) Berichte, 2(1, p. lia. '") Berichte. 30. p. 206!!. 164 Opneral Part. not melt at 187° as reported by Beyer,i but at 210 to 211° (ClauM & Fahrion,2 1889). In order to jirove tlie presence of c^arvone, tlie simplest way is to prepare the oxime, taking- care, however, that not too great an excess of hydroxylamine be employed, as in this case the oxime may add a second molecule of hydroxylamine foi'ming a compound ('i(jHi4N0H,- , NH2OH (m. p. 171— 175°) (WallachctSchrailer, 31891; Harries,* 189,S). If tlie freslily prepared oxime does not ci'ystallize at once, it can some- times be brought to crystahize by distilling it over with steam. ' Camphor. In order to distinguisl) d-camphor from Borneo camphor (d-borneol)y it is also called Japan (jr laurus camphor. Besides camphor oil, it is obtained in large quantities by steam distillation from the wood of Cjnncunonniin cainphorn. In smaller amounts it is contained in tlie oils of camphor leaves, sassafras leaves, cinnamon root, spike, rosemary, and in the oil from basilicum root from Reunion, l-f^amphor occur.s only in the oils of feverfew and tansy. Like d-i-amphoi' it results upon oxidation of the corresponding borneol with nitric acid. Synthetically, camplioi' has been obtained by the dry distillation of the lead (Haller,s 1879 and 189G) or calcium (Bredt & Rosenberg,« l.S9(j) salt of honiocam])horii- acid (Haller's hj'droxycampliocarbonic acid). This synthesis is, however, only a pai'tial one, since up to the present homocamplioric a.cid has lieen prepared only from a derivative of camphor. Camphor forms a granular, crystalline, colorless, transpai-ent mass, with a great tendency to sublime. It is readily soluble in organic solvents and has a characteristic odor. Its pr'operties, according to different observers are as follows : di8° = 0.98.'58 (determined on 1-camphor by (.'hauta.rd t). M p. 176.3— ITC;..")"; b. p. 209.1° at 7.59 mm. (mercury tliread com- pletely in the vapor) ( Fi'irstei-,* 1890); M. p. 178.1°; [r/Jr. = + 11.41° and — 12. 7(5° (Haller,« 1SH7). — M. p. 17.-)°: b. p. 201° (Landolt.i" 1877). 1) ."Vrctiiv (1. Pharm., 221, p. 28.5. e) Liebig's Annaleii, 289. p. .->. -') .Joiini. f. prakt. C'lierii., II, :^i), p. :SG.T ; 7) .lahresboiii'ht f. Them., 1868. Bei-icht von S. & Co., April 1898, ji. 2'J. ii. 55.">. 3) Uebig'e Annalen, 279, p. 368. s) Berichte, 23, p. 2983. •1) Hericlltl^ 31, p]). 1384, 1810. 9) Compt. reiiil., Ki.j, p. 229. s) Coiitrlb.M'StiKloclucaiiiphre. ThSse. Xaiic.Y lO) Llebig'.« Annalen, 189, p. 333. 1879, p. 34; Hull. Soc. chlm.. Ill, 1.5, p. 323. The More Commonly Occarriiifr Constituents of Volatile Oils. 165 M. p. 175°: b. p. 20-1:°; [a]D = +44.22° in 20 percent alcolujlic solution (Beclvmanu,! 1889). Camphor has always been of interest to chemists and the experi- mental material on it has grown to fairly large pi'oportions. In harmony with the purpose of this work, only those compounds especially suited for its characterization will be considered. According to its chemical nature camphor CioH](sO is a ketone, which does not combine with bisulphites. Hydroxylamine reacts upon it with the formation of an oxime, from which, however, the pure ketone cannot be regenerated, for when treated with acids water is split off and the nitrile of campholenii' acid CtiHi.5 . CN is formed. If camphor oxime is reduced with sodium in eth,yl or better amyl alcoholic solution, two isomeric bornylamines (m. p. 168° and 180°) are formed (Forster,^ 1898). A similar base, melting at 1.59—160° is obtained by heating camphor with ammonium formate to 220 — 280° (Leuckart & Bach,8 1887; Wallach & Griepenkerl,* 1892). Upon reduction camphor is converted into the alcohol CifiHigO, borneol. In indifferent solvents there is also produced some isoborneol besides camphor pinacone (Beckniaun,^ 1894 and '96), while in alcoholic solution a mixture of borneol and isoborneol is principally obtained (Beckmann.« 1897). The oxidation with nitric acid leads to the dibasic camphoric acid CioHieOj, (m. p. 187°) and further to the tribasic caraphoronic acid C9Hi40« (m. p. 189°). From the constitution of the decomposition pi'oducts of these acids man,)' conclusions have been drawn as to the constitution of camphor. Of the many formulas suggested for this ketone, that of Bredt^ (1893) CHo — CH — CHa II' ICHa-C-CHsl I 1 (JH2-(-: - CO 1 CHa is at present considered most favorably. 1) Liebig's Annalen, 2.50, pp. 3.52— .3.5 .t.— 3) Berichte, 20, p. 104. On the influpnce of the concentration and the *) Liebig's Annalen, 269, p. 347. nature of the Hoh'ent on the rotatory power s) Berichte, 27, p. 2.348; Liebig's see Landolt loc. cit. and Rimbach, Zeitscbr. .Annalen, 292, p 1. t. phys. Chcm., 9 (1892), p. 701. «) Journ. f. pralit. Chera., II, 55, p. 35. 2) .Jo\irn. Chem. Soc, 73, p. 3S(;. ') Berichte, 20, p. 3049. 166 OfripniJ Pnrt. Deliydratinfi' ai^ents act very energetically on i-amiilior. Tlius phos- phoric acid anhydride produces p-cymene; sulphui-ic aciil and zinc chloride yield other substances besides this hydrocarbon. By the action of iodine cai'vacrol is obtained. For the identification of camphor the oxime is used. This com- ];)Ound, discovered by Nageli i in bs,s;! is pi-eferably prepared according to the method of Auwers,- (l.SSO): To a .solution of 10 parts of caMi]ilior in 10—20 times tlie amount of 90 liercput alcoliol a solution of 7—10 ])arts of fiydro.xylamine hydroehloride and 12 to 17 parts of soda solution are added. Tlie mixture is lieated in a boiling water bath until the compound iirst pi-ecipitated by water dissolves completely in the soda solutioTi. The oxime precipitated by water is recrystallized from alcohol or ligroin. It melts at 118—119° (Bertram & AA^albaum," 1894; Bredt & Roscuberg.-t 1896), and, when prepared from d-camphor is laevogyrate, whereas the oxime of 1-camphor is dextrogyrate (Beckmann,^ 1889). For identification the seniicju'birzone of camphor melting at 2;U) — 288° may also be employed, further the compound produced with p-bromphenylhydrazine melting at 101° (Tiemann," 1895). F'ENCflONE. Fenchone CioHmO is a. compound xi^vy similar to (/amplior, but liquid. It occurs in both optically active mollifications in volatile oils. d-Feu- chone is c-ontained in fennel oil, while l-feni;hone is a constituent of thuja, oil. For its preparation in a pure state the fenchone-contnining fractions, boiling at about 10(1 — 10.")° :ire freed from impni-ities by oxidation with concentrated nitric acid or pei'nmiigaiiate solution (Wallach.'^ 1891). Fenchone is very stable toward oxidizing agents and is only slightly aided upon by this treatment. If the fenchone has been fairlv well ]iurifled by this treatment it will solidify in the ciild and I'an then be (■ompletely purified by crystailizntion :ind removal of the liquid parts. Artificially, fenchone c;in be obtnincd by tlie oxiihitioii of fenchyl alcohol. Alisolutely ]iure fenclmne is a lini]iid, somewhat nily liqniiL whiih possesses an intense camphordike odor iind a bitter taste. Its physicjil liroperties are given by Wallachs (1S91— 1,S9:!) as follows: M. p. + .'. to (1°; ili,,o = ().94(;.-,, do:,o = ().!)4;{; udih = 1.4(i:i(»(;; [".]d = + 71.97° and ()().94° resp. (in iilcoholic solution). 1) Beric'hte, 16, p. 497. ■"■ ) (jieliis'K Annalen, 2.")ll, p. ^34. 2) Berlchte, 2a, p. 60.^ "l Bcru-hti'. 2S. p. 21111. 3| .Journ. f. pralit. Cheiii., il, 4'.i, \t. lii. 7| i.k-hia'.s .Vimalfii, aiia, p. l:!o. i) I.ii.'big's .\nnalen, 2S'.I, p. li. si I.ii'biR's .\iinnlf n, 2lia, p. 1 31 ; 272, p. 1 1)2 The More Commonly Occurring ConvtitJientu of Voliitile Oils. 167 With the exception of the c-liaracter of rotation, the optically aeti^-e modifications corresjjond completely both physically and chemically. Feiichone does not combine with bisulphites anj' more than does camphor, but is also indifferent toward phenyl hydrazine: with hydroxyl- amine, however, it yields an oxime melting at 1(54 — 1()5°, which can be used for characterization (Wallachi). The fenchone oxime behaves like camphor oxime in so far as bj' splitting off water it is converted into the nitrile of fencliolenic acid C10H15N, isomeric with campholenic acid. Coi:-kbui-n3 obtained two fencliolenic acids. Upon reduction fenchone yields fenchyl alcohol OioHisO (Wallach-), which melts at 4.")°. By this treatment a change in rotatory power takes place, so that d-fenchone yields 1-fenchyl alcohol and the reverse. Upon oxidation with permanganate fenchone yields besides acetic and oxalic acids dimethybnalonic acid (CH8)2. C(C00H)2 (Wailach*). When concentrated nitric acid is used isocamphoronic and dimethyl tiicarbal- lylic acids are also found. (Gardner & Cockburn,^ 1891S). Whereas camphor, when dehydrated with phoHphori(.' acid anhj^dride, yields p-cymeue ; fenchone, upon hke treatment yields m-cymene. Fenchone therefore appears to be the m-compound corresponding to camphor as the p-(:ompound (Wallach <*). Concentrated sidplmric acid acts on fenchone with the formation of acetyl xylene (JeHs.CHgfi]. CHafs] . CHsCOfJ] ( Marsh T). For the identification of fenchone tlic oxime is used, wliich is best prepared according to the directions given by Wallach.'^ To a sulutioti of ."> p;. of fenchone in 80 cc. of absolute alcohol a solution of 11 g. of liydi'oxylaniine liydrochloride in 11 g. of hot water and g. of powdered iiotasli ai-e added. After standing for some time when some of the alcohol has evaporated the oxime cry.staliizes out, wliich should be |iurified by recrystallization fi-oni alcohol, acetic ether, or ether, Thu.ione, Thujone ('niHioO (tanacetone Semmler) together with 1-feiichone is a constituent of thuja oil, but has also been found in the oils of tansy, wcji-mwood, a.nd sage as well as in the oil of Artemini;]. hnrrelieri. in all of them it occurs in the dextrogyrate modificaticin only. From oils rich in tliujone like tansy oil, and the oil of Artemisia bmivlieri. the ketone is conveniently separated in the form of its Ijisulphite compound. whi(di yields pure thujone by decomposition with soda, 1) IJebig'8 ,\nnalen, 263, ]>. IHl; =) Journ. Chem. Soc. 73, p. 70K. 272, p. 102. 8) Liebig's Annalen, 27.5, p. l.">7; 28-t, p. Hl'4. 3) .Journ. C'lieni. Soi-., 7.5, p. .">il]. 7) Proc. Chein. .Sue, 1~j, p. 19H. 2) Ibidem, p, 146. *) Llehig'.s Annalen, 272, p. 104. *) Liebig's Annalen, 263. 11. 1H4. UiS General P.irt. Thujone is a colorless, pleasant smelling, somewhat oily liquid, for which Semmler reports the following properties : B. p. 84.5° at 13 mm.; dao" = 0.9126; nD = 1. 1-1:95. i B. p. 2();{°; r/.D = about +68°. 2 Foi- the ketone regenerated from the bisulphite compound and the scmi(;arbazone Wallach found : ^ d iHo = ().917."'> ; n D = l.l.liog ; ,1 200 = 0. 91(1; nD = 1.1507. As is seen from the physical constants thujone is a saturated ketone, yet it takes up bromine with decoloration and is readily affected by potassium permanganate. Differing from camphor and fenchone thujone combines with sodium bisulphite. With hydroxylamine it yields an oxime (Wallach,-* 1893; Semmler.5 1H92) melting at 51—55°, which upon heating with dilute sulphuric acid is changed to cymidine CnHs . G:iR'TW . NH2f2J . CHst*! which yields carvacrol (Semmler"). Semicarbazide reacts on the ketone with the formation of a semicarbazone melting at 1 71 — 172° (Baeyer," 1891). Upon reduction tlmjone yields the corresponding .secondary alcohol f'loHisO, thujyl alcohol (Semmler^), which had been found with thujone in wormwood oil. When oxidized with bromine and soda solution the monobasic tiinai-etogenic aciy M Bei-ichte, 25, p. :!34:!. si Berichte, 2."j, p. 38-lU. 2) Ibidem, 27, pp. Si).5 & S97. ») Liebig's Annaleii, 272. ip. Ill; Berichte, ■■i| Berichte, 28, p. 19(;r>. :((i, p. 423. 1) LlebtR-'s Annalen, 277, p. l.".y. i«) Berichte, 25, p. 3347. =) Berichte, 25, p. 3344. u) Lieliis's Aimalen, 272, p.llG; 275, p. 164. li) Ibidem, 3352. I'J) Berichte, 30, p. 420; 31, p. 2811. 7 1 Berichte, 27, p. 1'.I23. 13| Berichte. 27, p. 895. The More Commonly Occurriuff fonstituentu of Volatile (Jik. 169 prolonged boiling- of the tlmjone, as may be concluded froin the deci'ease ill rotatory power. Another isomeric ketone, isotliujone, is formed by heating- thujone with dilute sulphuric acid (AVallaeh,! IH!).")), For the cliaracterization of thujone tlie tribroniide is well suited, and is best prepared according to Wallach^ (L,S98): 5 g. of tliujoiie are dissolved in a Un-ge beaker in 80 oc. of petroleum etiier ariid to tills Holution 5 cc. of bromine are added at once. After several .seconds a rather violent reaction takes place with liberation of considerable hydro- bromic acid. When this is ended, the solvent Is allowed to evaporate and the tribroniide separates slowly as a crystalline mass, which Is to be freed from adhering- oil by washing with cold alcohol and recrystallized from hot acetic ether; the melting point of the pni-e coniponnd Is 121 — 122°. PlJLElJONE. The oil of European pennyroyal contains about HO percent of a ketone CioHiuO, pulegone, which has likewise been found in the penny- royal oil from Hedeoimi pulegioides and in the oil of I'ycnantlieinuni Imiceolatuiii, in all of which it occurs in tlie dextrogyrate modification. As European pennyro.yal oil consists principally of pulegone, this ketone can be obtained in a fairly pure state by fractional distillation. It can, however, be obtained much purer from the bi.sulphite compound which separates by sliaking the oil diluted with some alcohol {% vol.) with sodium liisulphite solution (Baeyer,-^ lS!)."i). The semicarbazone, decompo.sable by acids, can also be used for the purification of pulegone. Synthetically, pulegone has been obtained in a round-a.bout way from citronellal (Tiemanii & Schmidt,-' 189()). An isomeric ketone, but not identical with natui-al pulegone has been obtained liy Wallach ■"• (1896 & '98) by the condensation of inethjd hexanone with a,cetone. Pulegone is at first a colorless liquid which on standing for some time becomes faintlj' yellow, and has a sweet peppermint-like odor. For the ketone purified only by distillation Beckmann and Pleissner (1891) found :« B.p. 180— l.-!l° at 60mm.; d^ir = 0.9;!2:!; nD = 1.47018; [) Berichte, 28, p. 6.52. i) Berichte, 29, p. 91.3; MO, p. 22. = ) Berichte, 29, pp. 1597, 2955; Llebiff'.s .Annalen, ;!llO, p. 267. «) Liebig'H Annalen, 262, pp. 3, i, 20. ') flonipt. rend., 114, ji. 126. 17(1 flfiif-ral Part. For the pulef2,-(.)iie prepared from the bisulphite (•oinponnd 15aeyer and Heiiricli 1 (IS!).")) determined: B. ]i. lOU— 101° nt l.'j iiim.; [«]d = + 22.0-1-° ami Wa,llai-li-' (l.SO.-,): B. p. 221—222°; d = ().9:5(;; iid = l.-l-«-l-(;. Am a,i) unsaturated comiiouml ])nlegone yields with lironiine a liquid dil)r()niide, with li.vdrochloric and hydrobromic acids ery.stallized addition prcxhiets, which rejivnerate pulegone wdien trea,ted with alcoholic pota.ssa (Beekmann & Pleis.siier.a IHOI; Baeyer & Henrich.-i 1H0.">). It also shows the chnracter of a ketone. TTpon careful reiluction with sodium in alcoholic solution tlie idcohol (HcHisO, puleii'ol, which is diffl<-ult to obtain in a. pure state, is first formed (Tiemann cV: ScViniidt°). Upon tui'ther action of liydro;ieii 1-mentliol ('kiHixiO results (I5ecknui.nn & Pleissner "). Pulefione combines with hydroxylamine. two oximes lieing known, of which the (jne has the normal composition CioHteNOH and melts at n.S— n<»° (Wallii.ch.7). wdiile the other (m.p. 147°, Tiemann & Schmidt,*) describeil l)y Beekmann it I'leissner," contains an additional molecule of water. As has lately been determined the latter is produced l)y the addition of hydroxylamine to the double bond in the ]iulec;-one, so that the compouml camiot be considered as an oxime (Harries it Roeder.^'J 1M98). The semicarbazone formed by the action of semicarbazide melts at 170° (Baeyer ct Henrich." ISO.")). When pulegone is boiled with anliydrous formic acid, or heated with water to 2.")()° in an autockive, it takes np water and is ivsolved into acetone and methyl hexanone ('.7H12O (Walhich,'- iHlXi). The same dei-caiiposition is also brought id)Out by concentrated snl]ihu]'ic acid (Zelinsky,!-^ l.S<)7); also by the addition of bromine and splitting- off hydrogen liromide with the nid of heat ( Klagesi*). In the latter ca.se ni-cresol is also formed. Hjion oxidfition with ])ot:issium permanganate ])nlegone splits off acetone and yields ,}-methyladipiinc acid (VHidOt. In harmony with tliis residt the foi'inul.-i 1) Berichtf, 28, p. (;,5y. k) Beric-li tc, :!0, p. 2<1. -'I Borichte, 2.8, \>. l!»;.'i. 9) Liebis's .\niialt'n. 2i;2, ji. 3 1 IJehiff's Aiiiialeii, 2(12, |i. 21. 10) Berichte, .SI, ]). iseii. O Berifhte. 28. p. ().'■:!. ii) Herichte. 28, \,. (j,-,:!. ■"•) Berichti-. 29, p. Hl-t. 12 1 Liebift-'w .\nnalen, 289, p. B) LifliiK'K .Vmiiili'ii. 2i;2. p. :») i.i) Beriohte, .3(1. p. r.T;!2. -| I.ii'his-',s .\iinalcii. 27T. 11. ir.ii: L'.S'.). p.:U7. itl Berichte. H2, p. 2.-(;4. 7'/jf More Coininonly Occurring ('onstitiientu of Volatile Oils. 171 \/ C II /\ HoC/ \C0 I I I H2C\ /CH3 \/ CH i lias been aw.sigiied to pulegone (Semmler.i l!S!)2) which alwo explains tlie ready decomposition into acetone and methyl hexa.none. Pulegone has an odor very similar to that of menthone. Both ketones can, however, be readily distinguished by their derivatives. For the characterization of pulegone the semicarbazone prepared in the usual manner, or the normal oxime may be used. For the preparation of the latter Wallach,- 1H9(), has given the following directions: To a solution of 10 g. of jiulegoiie in thi'He times its volnmc of absolute alcohol a solution of 10 g. of potassium li.ydrate in .5 g. of water is added. To the liquid warmed to about 80° are added quite rapidl.v with con.stant agitation, 10 g. of h,vdrox,ylamine h.vdrochloride dissolved in 10 g. of water, and the mixture kept for 10 minutes more at 80°. If, after cooling, the mixture is poured into water, the oxime usually separates at once in the solid form. After recrystallization from ether or petroleum ether it melts at 118—119°. According to Ba.eyer & Henrich^ (IM!).")) the identification can be ai/compli.shed moi-e i-apidly with the c:-haracteristic Ijisnitrosojinlegone. A solution of 2 ec. of pulegone or oi] containing pulegone in 2 cc. of ligi-oin and 1 cc. of amyl nitrite is well cooled in a freezing mixture and treated with a very small amount of h.ydroohloric acid. In a very short time the bisnitroso com]iound se]iarates in the form of fine needles, wliicli are obtained pure by spieading on a. porous |ilate and washing with |ietroleuni etiier. Menthone. ]-Menthone occurs together with menthol in pe])]iermiiit oil and prol)ably alsrj in the oil of liuchu leaves. Recently it luis been detected in geranium oil from Reunion. As it does not combine with bisulphite and cannot be freed from accompanying com])Ounds by fractional distillation alone, it can be 1) ISerichte, 2.5, p. S515. ») Berichte, 2R, ]>. (•,.-,4; CDinpare Bai'.vn- 2) Lieljig's Annalen, 289, p. :-!+". & Prentice, liericlite, 2il, p. 1078. 172 General Pni-t. isolated onlj- by nifans of its oxime or semicarbazone. It should be remembered, however, that in the decomposition of these compounds, which is usually effected by means of dilute sulphnri(t acid, the rota.tory power of the ketone is ('lianged. By the oxidation of menthol with the (-hromic acid mixture recom- mended bj' Beckmann it is easy to obtain a 1-menthone with normal rotatory power (Beckmann, i 1889). Pure menthone is a mobile, limpid liquid, which possesses a peppermint odor and a coolinij-. bitter taste. For the ketone obtained by oxidation from menthol Beckmann found: B. p. 207°; d2.i= = 0.H9«(»; nui2» = l.-t')2.'. ; [a]D = — 2H.1H°.2 Binz records (189:!): d24o = ().,si);U; [r/]D = — 27.07°. •' According- to Wallach (189.5) menthone regenerated from the semi- carbazone (m. p. 1H4°) possesses tlie following properties: B. 1). 208°: d = O..S94; nD = 1.449(;.'' If 1-menthonc is treated at a low temperature with concentrated sulphurii' acid, it is converted into the clextrogyrate isomer (Beckmann, ^ which has so far not been found in volatile oils. Menthone belongs to those ketones which do not yield addition products with bisulphites. Upon reduction with sodium 'in alcoholic solution it is converted into the corresponding secondai-y alcohol 1-menthol, C'loHouO There are also formed small quantities of a shghtly dextrogyrate isoraenthol; by using indiffcT-ent solvents mentlioi)inacone also results (Beckmann," 1897). With hydroxylamine in alroholic-aqueous solution it combines readily to form 1-menthoxinie melting at .'")9° (Beckmatni,'^ 1889; AVallach.s ],S9;-5). When this is treated with dehydrating agents it is converted into an alijihatic nitrile C0H17CN, which by further changes yields compounds which show great similarity to the members of the citronellal series (Wallach, » 1894 & '97). Semicarbazide reacts on menthone with the foi-mation of the seuncarbazone, which crystallizes in needles and melts at 184° ( Wallach, i<' 189."); Beckmann." 1,S9(;). ') Liebig's Annalen, 250, p. H2r,. 7) Lieliig'N Annalfn. 2.50, p. :-i.Se. 2) Lielilg'.s Annalen, 250, p. .■!27. ») Liebis's Annaleu, 277, p. 157. ■•"I Zeltschr. f. phyw. Clieni., 12, p. 727. 9) Licbig'a Annalen, 27S, |i. ;!08 : 2;itJ. *t Beriohte, 28, p. 196/!. p. 12o. ■■) Lieblg'H Annalen, p. :!a-t. lO) Berlchte, 28, p. 10G8. '•) .Tourn. f. praUt. cheni., II, .55, pp. ii) Liebis's Annalen, 28'.i, p. :i(;r,. 1 S .V- .30. 'Ihf More ( ommonly Occurring Constifiientu of Volatjh Oils. 173 If menthone is oxidized witli a solution of chroinic aciil in glacial acetic- acid, a liquid keto acid CioHisOs (keto- or oxymenthylic ac-id) is first produced (Beckmann & Mehrlander.i 1896), which, on further oxidation witli potassium permaugauate or chromic acid mixtui-e is converted into the dibasic /S-methyladipinic acid ( Arth's- /J-pimelinic acid) consequently into the same ''Abbauproduct'' which results from pulegone and citronellal (Beckmann and Mehrlander;^ Manasse and Rupe,* 1894). AVhen oxidized with ("aro's reagent (persulphate with concentrated sulphuric acid) it yields the (Corresponding £-lactone (Bae3'er," 1899). When isoamyl nitrite and hydrochloric acid are allowed to act f)n menthone in the cold, there is formed besides bisnitrosomenthone (G10H17O . N0)2, the oxime of keto-menthj'lic acid, the first oxidation product of menthone (Baeyer & Manasse," 1894; B. & Oehler.^ 1890). When bronune ( 2 mol. ) acts on menthone ( 1 mol. ) in chloroformic solution a crystallized dibrommenthone, CioHioBr20 (m. p. 79 — 1S0°) results, which can be converted into thjnriol by splitting off hydroljroniie acid by means of chinoline (Beckmann & Eichelberg.s 1896). Those I'earangements, as well as the conversion of menthone into 3-chorcymene effei.'ted by Jiinger and Klages" (1896) agree with the formula CRsCHs \/ CH H2CV \co HoC\ /CHo \/ CH i assigned to it. This also expi-esses the relation of menthone to pulegone. In order to identify menthone. the semiearbazone or the oxime is employed, the preparation of which is accomplished in the usual manner. For further characterization the ketone may be reduced to menthol and this converted into the benzoic acid ester (see menthol). 1) Liebig's Annalen, 28i), p. 86S. 6) Berichte. 27, pp. 11113 and 1914. 2) .inna.les cle Chiin. et Phys., VI, 7, p. 4.33. 7) Berichte, lii), p. 27. 3) Lieblg's Annalen, 289, p. 878. ») Berichte, 29, p. 418. ■1) Berichte, 27, p. 1818. 9) Berichte, 29, p. 815. SI Berichte, 82, p. 862n. m General Pari. A (liketone, viz. diarftyl ('.H3. GO . GO. CH3 remain.s to l)e ineiitioued. It liaa Ijeen isolated from the (listillate from caraway seeds 1 and in all probability occurs in the distillate from cloves and probably in other oils. It can be identified bv its dioxime meltino- at 284. ."i". Acids, Esters, Lactones, Oxides. The aqueous distillate ol)tained by the distillation of volatile oils with steam oc(;asionally contains free fatty acids, viz. acetic, propionic, butyric or valerianic acid. These acids, like methyl and ethyl alcohol, are probably' decomposition products of esters contained in the parts of plants subjec-ted to distillation. Those acids (-ontained in oils in tlie form of esters ai'e obtained as salts when the oils are saponified. Formic acid is siipposed to be con- taineil in valeiian oil as Ijornyl foi'mate. Acetic acid occurs fi'equently in the form of esters as liualyl, geranjd, and bornyl acetates, which are characterized by their peculiar odor.' Of the other fatty acids, propionic ;uid Imtyric iicids have been found in lavender oil ; butyric; acid as ethyl ester in the oil of Hevndeum aphondrlmiu. as octyl ester in the oil of Pantiniifi) n:ivivn: valerianic acid :ind its esters in the oils of valerian, citronella and angelica root ; methyl ethyl acetic- acid in the oil of angelica root and seed; n-capronic acid in palmarosa oil and the oil of H. .sphondyliuni; i;aprinic acid as ethyl and amyl ester in cognac oil; laurinic acid free in tlie oil of arnica flowei's ; myristic acid in orris oil and oil of nutmeg; and ])almitic acid in the oils of ambrette seeds, vetiver. wormwood, celery and arnica flowers. Of the unsaturated acids, angelic and tiglinic acids occur as esters in cumin oil; tiglinic acid in geranium oil from Reunion; oleic acid in orris oil. Of the aromatic acids, benzoic acid has been found in ylang-ylang oil and in the oil of tolu balsam ; cinnamie acid in storax oil, and as methyl ester in tlie oil of Aljiiiiia umlncrfnsis. Mucli more widely dis- triluited is s.'dicylic acid which occurs as methyl ester in the oils of species of Guulthevin and Betiihi. also those of spiraea, senega root and ten. Mi'thyl salicylate occurs in sni,-ill amounts but is widely distributed in leguminous plants and in other plant fannlies.- In oil of cloves salicylic acid probably occurs as acetsalicylic ester of eugenol. t) Bericht. S. & Co., Oct. 1sfi9, i>. 32. = 1 Comp. Bericht von Schiiiiincl ^i; d.., Oct. IS'.is. p. nj . also .T.-ihreslioricht iles )taniwchen Gartens zu Buitenzorft-, 1S'.)7, p. ;-{7. Tbf More Cninnitinly Occnrvhig ('oiistituents of Volatile Oils. 175 Methyl .salicylate is unquestionably one of the most wideljr distributed plant r-onstituents. Its presenile in a plant is not restricted to any one part. Probably the ester does not as a rule exist as such in plants, but in foi'ni of a glueoside, for frequently the distillate from fresh vefi'etable matter yields no reai-tion for methvl salicylate. Oxyaeids and their anhydrides, the lactones, occur in yolatile oils; oxymyristic and oxypentadecylic acid haye been found in tlie oils of ang'elica root and of angelica seed respectively. Of the lactones, sedanolid from celery oil and cumarin and hydro- cutnarin are characterized by their powerful odor. On the other hand, alantolaetone (helenin) from alant oil and the lactone (_'ioHi602 from peppermint oil have but a faint odor. The oxides are represented by but one compound, cineol or eucalyptol GioHisO. ( 'IXEOL. Cineol (eucalyptol, terpane of Boucliardat and Voiry) like methyl- salicylate is widely distributed. It is the principal constituent of cajepnt oil. the oils of Artemi.sia cimi. arid Eucalyptus globulus and has been found in larger or smaller quantities in the following oils : galangal oil, zedoary oil, different cardamom oils, in tlie oil from the seeds of Amomum melegueta. kaempferia oil, camphor oil, lani'el leaf and bei-ry oils, myrtle oil. in the oils of Melaleuca leuciidenrlron var. lanci- folia, M. acuminata, M. clecussata, and M. uncinata, in cheken leal r)il, canella oil, in the oils of Eucalyptus odovata, crieorifolia , oleosa, duinosa, ainygdalina, rostrata, pojiulit'era, coryinhosa, resiiiifera, haileyana, micvocorys, risdonia., leucoxyloii, ina.cirjtrhyncha, capiteUata, eugenioifJes, obliqua, punctata, loxophleha, cvehva and hemiphloia, in oil of Artemisia vulgaris, milfoil oil. iva oil. in sage and l)asilicum oil, in tlie oil of" Lavandula, dentata, L. stoechas and L. vera, in rosenm-ry oil, as well as in peppermint and Kussiaii spearmint oils. The preparation of this body from oils rich in cineol. like that of Eucalyptus globulus, is not difficult, insofar as the cineol, jiurified as far as possible by fractional distillation possesses the pinpei-ty of crystallizing when cooled. If the object is to detect and to isolat-e small quantities of cineol, the hydrobromic acid compound is used, which by decompositif)n with water yields cineol. 176 Gfiiiernl Part. Gineol has been observed as inversion product in the preparation of terpineol from terpin hydrate and dilute sulpliurie acid ; it i-esults further by boihng- terpineol with dilute sulphuric acid or oxalic arid. Pure cineol is a colorless liquid of cauiphor-like odor, which crystal- lizes in the cold and is optically inactive. For the cineol prepared from its hydrochloric acid addition pr(jduct Wallaeh found : B. p. 17(5°: d2u» = 0.0207; nD = l.J:-'')8:!<).i Accordini;' to observations made in the laboratory of Schinimel & Co. (■ineol purified by crystallization melts at — 1°; it boils at 177° ( 704 mm. ) , and di5o = ().93(,), UDiT' — lArMil. Gineol yields characteristic- loose addition products with bromine, iodine, hydrochloric and hydrobromic acids, ^ phosphoric acid, a- and i-naphthol, and iodol, which can be used in part for its isolation and characterization. By the action of dehydrating agents it is c-onverted into dipentene (Wallaeh & Brass, ^ isH-t). It can also be (^•onverted ilirectly inti) dipentene derivatives by proper treatment ; thus for instance, dipentene hydi'iodide results by merely conducting- dry hydriodi(.- acid into cineol. The oxygen in cineol is combined as oxide oxygen a.nd. therefore, this compound reacts neither with hydroxylamine nor with phenyl hydrazine, nor does sodium in alcoholii- soluti<:)n act upon it. When oxidized with warm soluthm of potassium permanganate dibasic cineolic acid, (JinHioO.i (m. \). 1!)6 to 197°) is formed (Wallaeh & (lildemeister,* 1(S(S8). The (-ineolic acid anliydride produ(-ed by the action of acetanhydride on this acid yields, when subjected to di-y dis- tillation, methyl lieptenone. C8H14O. wdiich also occurs naturally. Cineol possesses a i:-haracteristii" odor, which often directs the atten- tion to it. For rapid detection, the reaction with iodol given by Hirschsohn''' (1H98) is especiall.y suited. In a few drops of the oil to be tested a little iodol is dissolved by moderately heating; if cineol is present, the crystalline addition jn-odnct consisting of equal molecules of the components soon separates. The melting point of the comp(mnd, recrystidlized from alcohol or benzene, is about 112° (Bertram & Wal- bauni," 1H97). 1^ I/iebig's Annalcn, 23'.), ji, 22; 24,"i. p. 195. 2) r.iebig's Annalen, 225, pp. 300, 303; 23l), p. 227; 246, p. 2S0. 3) Lieblff'8 Annalen, 22.5, p. 310. J^) Licbia's Annalen, 240, p. 2ljs. 5) Pllai-ni. ZeltBOhr. f. RuskI.. 32. jip. 49 & (57. ''>) Archiv d. Pharni,, 235, p. 178. Tlip More ('ojiniionh- Occurring Conntitucnts of Volatile Oils. ITT If the i-iueol is to lie isolated as siieli, the ciiieol fraction dihited with about an equal A'ohinie ot petroleum ether is well cooled and saturated with ilry hydrobronuc acid o-as. The white crystalline precijiitate which soon separates is filtered with a force-pump and washed with petroleum ether. The fairly stable liydrobromide thus obtained melts at '><> — 't7° and is readily decomposed by w^ater into eineol and liydrobromic acid. For the furthei- charactei-izatioii the cineolic iicid produc-ed Ijy oxidation with warm potassium permanganate solution may be useil. Phenols and Phenol ethers. Several of the phenols nnd their ethers have acquired considerable commercial inq;>oi-tance and are, therefore, prepared on a large scale. Thus thymol is hirgely used on account of its antiseptic properties, anethol is used in the manufacture of liquors, from eugenol and safrol the valuable vanillin and lieliotropiu are prepared. Of the simpler representatives. ])-cresol methyl ether is found in jdang-ylang oil (cananga oil), phlorol (m-ethyl phenol?) is found as iso- butjn-ic ester and as methyl etlier in the oil of arnica root, the ethyl ethei' of liydroquinone occurs in star anise oil, and the metliyl etlier of thymohydroc^uinone in the oil of arnica root. Of the higlier homologues of jihenol. tlie two isomeric plieuols CioHiiO, thymol and carvarrol ai-e of special interest on aci-ount of their relationship to tei'jiene dei-ivatives. Carvacrol, Carvacrol (isopropyl-o-cresol ), CiHii.CHaLU . OHfs] .CsHTf**!, is the pi-incipal constituent of the Trieste and Smyrna origanum oil. It has also been found in the oils of iSloimnhi. tisUilosa, of thyme and wild thyme, of Sutnrejn bortensis, S. moiitmia and of Pycniintlieinmn Junceo- latuiii, also in speariuint oil and the oil of Sehhius inoUe. Artificially it i/a,n be obtained from the isomeric carvone liy treat- ment with potassa, hydrochloric, sulphuric, phosphoric, and formic acids (conip. p. Kvi); also from camphor by heating it with iodine. When freshly distilled it is ;i colorless, thick oil, whicli solidities in the (.'(jld. Its constants are reported as follows: B. p. 119° at 16 mm.; d20» = <».97y2 ; nD = l..")228 (Semmler,' 1892). 1) Berichte, 2.5. p. »HnH. 12 17'S Gfineml Part. For rarvacrol from orin'Finuin oil, Gildenifistfr ^ (1895) found: M. p. +0.."')°; b. p. 2:i.'..'— 2;'.(;.2° (7+2nini.); (Us'^n.USO, ,l2o= = .V\l:.[^\ .i)Y{\'^^ .V-.H-;^ is found in considerable quantity l.)esides ])-cymene in ajowMiU oil, but also oi-curs in the oils of MunarrJa punctata, Moriil;i j;ifionir;i. and ('iinU,-i ni;iri:iii;i, in oil of wild thyme, and in thyme oil. Its artificial forniiition from dibrom ]nenth(.ine by sjilittuiii' off hyilro- liromic acid bj' means of (|uiuoline is interestini;. Thymol forms colorless, tra.nsparent crystals, having- the odor of thyme which melt at 50—.-,!° and distill at 2;i2° (2:-U.S°) (Pinette,* 1HS(;). Eykmaun-' (1.S93) determhied (hi.(r- = O.nNK;, Na-sini and Bern- heiniei-'' (ISS.-,) i-eport d^° = O.iUJN!)."', jind no = 1 ..")isn:i. Chemically it can be re.-idil,y characterized li,v its nitroso derivative (Khiges," l.s!)0|. The most phenols and i)henol ctliei-s ,-is well as the most inijiort.-int ones belong to the ojefliiic phenols, i. e. phenols witll oletivn(/ side-(dinins. They mostl\' contnin the group CsH.-, either the a llyl or propenyl group ; Tiiyristicin ;ilone a.p]iareutly umkes an ex<-eption, having a butenyl group. AMieu heated \\ith alcoholic potassa cir sodium ethyUrte tho.se substances c(.intaining ,-in ;i,llyl grou]i are converted into tjieir isomers with a propenyl gi'iaip. 1) Arch. (1. Phai-iii., L':!a, p. Iss. ,-,, Reoufil .l.-s li-av. cbini. dps l> -li. 12 -M Berichte, 2li. |i. 20sr,. p. 177 ' ' 3) Bfi-ichte, 32, p. l.Tls. ,;, i;azz. i-liini. itnl.. 1.".. p. r,'.l. .Falu-i'sb. 4) Lii'biR-'K Aunnlcii, 2+:-t, p. 411. (. Clu'iii., 1885, p. 314. ") Bericlite, 32, p, l,"ils. Tht M(jiv Coinnioiily (Icrjii-i-iiiw CouNtitiieiit/^ of Vahitilf (Jils. 179 (Jhavicol. (Uiavicol (p-allyliihenol), OoHj . CsHs"! . OHL-il oci-nrw in lietpl lent' oil friim Java and in l)ii,y oil. It is a (.'olorlei-is liquid. l)oilin<:' at aliout 287° and ;iecordin<^' to Eykiuann 1 has dis^ = l.l>;j;i and no ^ 1 -"i-l-l-l. iMeTHYIj (MAVICOL. .Metliyl i-liavii-ol (estraiiol ) was tirst foniul in anise barl< oil and later also in estraii'on oil.- Accompanying- its isomeric propenyl componnii anethol, it occurs in the oils of anise, star anise, and fennel, and has lieen shown to be ]n-esent in bay (jil, in German and French basilicum oils and in the oil of Peinen <^ratissiiii;i. Methjd cliavicol is a colorless, liquid witli n faint anisedike odor, which boils at 21.")— 210° (corr.) (Griman.\,-' INO:!). At 11..".° d = ().<»79 and nD = l--">214 (Eykman.i 1890). The etlier isolated from estragou oil has, accordin,n' to the oljservations made in the lalioratory of Sdiinimel & Co.. the followini;- projjerties: P>. p. 1)7— 07.-3° at 12 mm., 8(;° at 7 mm.; di-,'^ = ,. .\pril 3) Sitzungsber. il. .Vlvad. d. \A'is.s. Li'i]»ziji-, 18;i2, lip. IT &+1; April, 1894-, ji. 28. 1802. p. 307. ■i| Compt. i-oii'l., 117, p. lOS'.l, ISO (Ipiii'i-al Part. Wlien oxidizf'd witli clirdmic ^icid it is converted inti) nnisic :idd, witli iiotassiiiiu p('i-iiiaiii;;inatc intd ])-iiietlioxy]ili('iiylylyi)xyliL- ai-id (.'(iH-t.OCH;-,. [■»].( lO.COOHl'l (m. ji. si)°). Witli l)i'()iiiiiie tlie well crystal- lized iiioiioliroiu anetliol dibronude Cr.HgBrff^XiHs) . ('8H,-,Br2 (ni. \>- HIT — 1()8°J results (Hell & (iiirttner.i 1895). En^'enol, hetelplieiiol aud safrol are derivatives of allyl- and ])ro]»'iiyl- dioxyhenzeiie respectively, which are not knn\vii as sndi. Eni+ExoL. Enuenol (allyl;j,uaiac(.l), ('eH.s. OsH.-l' I . (JIIHsl-M . OHL-*), is contained in la.rg'e a.iiiounts in the oil of cloves and clove stems. It is a.lsdoi- and bni-nine' taste with the followine' pi-o|)erties : B. ]>. ■2r,-2° at 7-1'.) mill.; 1 2H° at 12—1:! iiim. ( Krdmaini,- 1S!)7|; dii..-o= 1.072; iiD = l.-"'>-l--U» (Eykman,-' IHDO). With ferric chloride in .ali-oholic solution eueenol produces a blue coloration. Upon oxida.tioii (best as acetic acid ester) it yields vanillin and vajiillii' tuud, besides small (|uautities of homovanillie ai-id. For its characterization the benzoic acid estei', m. (i. U'.) — 7l)". which ca.n be pre]iareil with benzoyl chhjride is well adapted. Besifles en^-enol senile aceteugenol is also f)c (lihle- meister,+ iMUl); Eykmami''). With bromine methyl I'u^eiiol yields the ti'ibrimi methyl eue-enol f'liHiHi-. (()('H:i)ii. <':iH.-l!7':., crystallizinu' in pi-etty needli's ineltine- at 7.S° ( \\'assermann ;■' B, ^: It.'i. l'>y o.xida.tion with potassium i>ernia.iieanate it is converted into ilimethyl dioxybenzoic acid (veratric acid) meltine- at 17'.)— l.S()° (Com]). Walla.ch A: Rlieind(u-ff,« l,s<)2). Both compounds are well suited for the iletecliou of metli\l eue-enol. 1) .r.iurii. f. |>]-Mkt. I'lii-iii. II, .-,1, ,,. 41) + . -I, .i.iurii. f. prakl. Cheiii. II, :M>. p. :-!,- + . -•) .Iniii-ii, r. |ii-iikt. Clicni. II, .-C,. |). 14.(;. 5) .lahlvsbtT. f. CIr'HI., 1,s7!i, ,-,20. ■') )!LTifhlc, 2:1, |.. SCL'. 'o) fJchiff's .\limilcll. 271. ij. :!(IG. The More Cominouly IJccurniiif ConsTituents of Volatile Oils. 181 Safrol. Safvfil (sliikiniol of Eykiii:iii).tlie principal constituent of sassalras oil, is (•onta-in(^(l in considerable (piantity in camphor oil and has been found in cinnamon leaf oil, star anise oil and niassov b;irk oil. It is the methylene ether of an allyl iiyrocatechin CoHn. t'^iH.-l'J . ()(-)('Ho[-i.^l. It is :i colorless or fnintly yellow liiphd ^ylLich li;is the followinu; properties, accordinj;- to observations made in the la,boratory of Schimmel i C'O. : B. II. 2:!:-5° (7.")'.) mm.); di.-,o = 1.1<>« ; udit" = 1 ."'^iSHO. (_)ii coolinii it solidities to ;i nniss of crystfds which do not melt until + 11°. Subjecteil to careful o.\idation with potassium pernmn- Jl'annte ;i ^In-coI is first forme]i!ieiiiii (imieral Pnrt. Compounds Containing Nitrogen and Sulphur. (Nitriles, Sulphides, Mustard Oils.) (Joiiipouiids contiiiiiiiiii' iiiti-dMvii mid snl])lmr ocmir fre(|UPntly wln-ii ])firts of plantn Tich in tilbniiiiiious (])i-()topli-i-:i and liiiHgoll'rn f^-nlefi'oiilpn. in the oils of bitter almonds, chei-ry laiu-el and wild cherry btirk. The niti-ile of plicnyl acetic acid constitutes the pi-incipal constituent of the oils of Tr()]i:ii'i>hnn iii.-ijus and of Leiiidiiuii .s;iti\-iiijr. the nitrile of ]ihcnyl pro]iionic acid in the oil of X;intiii-tiuiii ofticinnlf. (iadanier.^' jiowevei-. has recently shown that sevei-al of the cruciferous oils contain- iug nitrites in jjla.ce of isothiocyana.ti's .aiv products of decomposition rather'than |ii-oducts ot hydi-olysis of the underlying glucosidi-s. \\'lien nitriles are obtained ujimi distillation the ferment has uol had an o])]>ortunity to act. Of cai'bon (lisul])liidc small amounts have been foiuid in (he oil of black mustai'il. Dimethyl sulphide has been isolateil fi-(nn the low boilin.U' portions of Amei-icnn ]ie]i]]ermint oil. Sulphides ;ind Jioly- sul])liiiles have been found besides other sulplmi- dei-ivati\'es in the oils of garlic and onion. \'inyl s\di)hide and its ])olysuliihides constitute 1 he priuci]ial constituent of Allium nrs'niiiin. ,Vs a sepa.rate gi-ou|) should be mentioned the estci's of isi >t liiocvanic acid, which are characterized by t hi'ir ]iungent odoi-, and which ,-u'e (ionunonly d(^signated as nuistard oils. Their tyjiical rejjre.sentative is I he common (allyl) mustanl oil from Iir:issii-:i iii^-r;i .'ind /!. jiuii-f^;!. 11 h.is also been found in (he following iil.-ints: Mli;iri:i (itfii-iij:i lis, dijisflhi l)jir.s;i. ii;ustiiris, i'lird-uiiiiif sji.. Sisyniliriiiui sji.. ('()cIili-;-ii-i:i :i nn:i: phenyl ethyl mnstai'd oil has been found in (he oil of mignonette root. M .1 nlircslK-M-ich t lics bol ;\nischcii l!;u-lciis zn [initcic/.nvi;-, Is'.tT, p. :;7. ■■:] .\irluv r. riiar., 2:!7, |c 111. 3. THE EXAMINATION OF VOLATILE OILS. The speeiiU methods of testing the more imjjortnnt volatile oils are described in detail in the following chapters. In order to avoid repetition, however, it will be expedient to discuss briefly in a special chapter the general methods used in the investigation and the most common adulterants met with. The practice of adulteration of tlie volatile oils, wliich is ]>robably as old as the manufacture itself, ha.d in the l)eginning a, certain justifi- cation, a,.s with the incomplete techincal ecpiipment of the early times the addition of fatty oils, turpentine oil, or alcohol was often necessary in order to exti-act from the ])lants their odorous principle. Later, when the pi-eparation of the jiure oils was already known, the practice of making tliese additions was still retained. Even thirty years ago, it was cnstoniary to distill coriander witl) the addition of orange oil and to put the distiUate on the market as coriandei' oil. 8ince pure coriander oil can now be prepared without difficulty, the ])rrKluct olitained Ijy using orange oil, as it is found now and then even at the present time, must be considered as ailultei'- ated and if the foreign ingredient is not nmde km)\vn, its sale is a fraud. The adulteration need not always be by the addition of a less valuable liody, it souietimes (consists in that the more valuable con- stituent of the oil has been partially removed. Tlie effect is the same, whether froiu a ca.raway oil of the specific gravity ().91(J so much carve me be removed tiiat an oU of tlie specific gravity ().8!)() remains behind, or whether the sauie result is attained by the addition of linionene to the same oil. Although the adultei'ations themselves mostly find a sntticient explanation in the pi'oiitableness and the pecunia.i-y advantage to the adulterator, it cannot, howevei', be denied, that often tlie ignorance of IH-t Gen f ml Part. t\w fouMuuiPi', iind above all the desire to buy as cheaply as j)ossible, is the cause of the spurious composition of many an oil. More than once the ]jrodiicer may have been induced to adulterate, because he found no buyers f(jr his pure ])ro) With rcf,rai-il to Uu- niaiii|iulal ioa of the |)olarisc-ope the reaaer is refeiTcil (,, tin' well- kaowii ivoi-l; by IT. I,anclolt, "Das ojitische Drehunssvei'i,iioseii orgnniKrlier Snlistaazcn". II. Hilit., P.i-annKCliweiR-. ISilM. Tlie ExHiiiiiintion of VoJntih- Oils. 187 used. In tlie following-, ao is the ol)serveil iiiigle of rotation in a. 101) mm. tnlie with socliiim liglit, and ['/]ij is tlie s])peifii- rotation as calculated by the formula r'/ln^ -r-^i- where a is the observed an<>-le of I . d ^ rotation, 1 the length of the tube in millinietei-s and d the specific gravity of the liquid. AVlien no special mention is made of the temperature, room temperature is to lie understood. In general it is not necessary, although desirable, to make the observation at a tt\ed temperaturi?, as the natural variations in the rotation of an oil are usnally greater than the differences due to a v;iriation in temperature of several degrees. Exceptions to this are the oils of ieniovi and orange, the rotation of which is relativelj' strongly intlueni/eil by even small changes in temperature. It is necessary, in ordei' to get comparable figures, to deternnne the rotation of these two oils at + 20° or else to reiluce the result to this temperature liy ca.h.'ulation. Tlip details of this will be found in tlip descri])ti(.)n of these oils in the special part. Refraction. The detprmination of the index of refraction nn has been recommended by several investigators for the ex;imination of the volatile oils. Between chemical constitution and refraction there exist, as is well known, (certain relations, and in many cases (conclusions as to the position and inimbei- of double bonds may be drawn from the mole- i;ular refraction. Cheinical indivii.luals cai'efnlly ])uriHed are. howe\er, necessary in ordei' to obtain useful results. As the i-efra.itive coetticienis of the constituents of the volatile (.)ils are on the whole c.)nly slightly different from each other, they are not so well suited for the detection of adulterations as are other niethoils (jf examination. The addition of turpentine oil, for instance, infinen es the refraction of lemon oil only slightly, but changes the rotation to a marked degree.! y^j. f]|p j-pfra' tion changes rapidly with the tem].)erature, this must always be considered in making oliservations of the refractive <;oetticients of volatile oils. Congealing point. With certain oils, es])eciafly anise, stai- anise, fennel and rue oils, the congealing point gives a good basis foi' judging tlie (quality. With the first tlii'ee oils a high congealing (loint sliows a large content r)f anethol, with rue oil one of methyl nonyl ketone. The deterndnation of the conge.aliug point can l)e very well performed with Be(;kmann's well-known a,j)])aratiis foi' the determination of the molecular weight by the lowering of the freezing point. \ few slight changes make it esjiecijilly suited for this jiurpose. 1) Berioht vuii S, i>; (',)., Octiihpi- Is'.).^, 188 Geneva^ Part. Tliey con.sist principally in doing away witli the corli connecjtions which liindcr tlip li-ei' inspection of the mercury thread of the thermometer. Tlie laboratory of Sdiimmel & Co.' liaw the form .shown Iti fig. 52. The battery jar A serves as the recejitacle fui- the cooling li(|nid or freezing mixture. The glass tnbe P) hanging in the metal cover serves as an air jacket for the freezing tube C Olid ]irevents the i>rematnre congenling of the oil to be tested. The freezing tube (.' is \\ider nt the toji and becomes nariowei- at the place wliei'e it rests on the edge of the tube 1'.. In order to retain (' in a fixed ])osition three glass |irojections ai'e faste ;1 on the inside of the tube H, about .'i cm. below its upjier edge. The thermometer, which is graduated into half degrees is held in jiosition in a metal plate |py thi-ee springs which allow of sliding the ther- mometer np or down. In conducting the determination with anise and star anise oil the battery jar is filled with cold water and iiieces of ice, lint with fennel dil ,a freezing mixture of ice .aiid salt is used. Tliiai pmir into the freezing tube so much of the oil to be tested that it stands at a height of .about o cm. in the tube and bring tlie thermonieter, which iiinst not touch the sides of the tube at any place, into the liquid. During the c cc. arv distilled over in such a manner that al'out 1 droji falls in a second, and the distillate tested in the polariscope, as will be described more in detail under the individual oils. When the different constituents are to be isolated from an oil. the fractional distillation must be I'epeated many times and prefer-ably by employing one of the well known distilling columns. It is best, in order 1) Bericht von .S. & Co., 0(.-t(.lipr 1s;iS, p. 46. 190 General Part. to avoid decomposition, to distill the fractions boiling above 200° in vacuum. Oils containiuo- esters must first be saponified, as the acids, which are easily split off by the boihng, disturb the fractionation and may act upon the other constituents of the oils. Solubility. The volatile oils are readily soluble in the ordinai-y solvents, such as alcohol, ether, chlorofoi'm, benzene, acetic ether, carbon disulphide, petroleum ether, parattin oil etc. Mention of this general property is not made in the description of the individual oils. A phenomenon which is sometimes considered as an incomplete solubility mav be mentioned liere. The tni-bidity noticed by mixing certain oils f^? with petroleum ether. ])ai-ntfin oil or carbon disulphide is caused by the small amcmnt of water which the oils have retained from their prepar- ation. The richer an oil is iu oxygen, tlie more water it is capable of dissolving ajid tlie more cloudy does it become with jtetroleum ether. i- The turbidity does not take place when the oil has lieeTi thoroughly dried with anliydrous sodium sulphate. 1) When an oil rich in oxy^-en, siu-li as lievffaniot oil, is mixed Avilti one ricli iu terpene.s, aw tnr]teTitine oil or oranji'e oil, tlie mixture beeonie.s turbid by the sep.^ratioii of water. Tlw Extinvniition of Volatile OHk. 191 Although all oils :ive I'eadily soluble in strong alcohol, only some of then) are entirely soluble Iti dilute alcohol. For the last class this property becomes a pi'actical and rapid means of examination. Tlie presence of the ditHcnltly soluble turpentine oil can, for instance, lie readily shown in this manner in the oils soluble in 70 ])ercent^ alcoliol. The solubility determination is very simple. Bring into a small graduated cylinder (fig. .~)."i ) % — 1 cm:, of the oil to be tested and add small portion.s of tlie alcohol at a time until with vigorous shaking solution is effected. If an oil whi(;h is soluble under normal conilitions does not dissolve, it is sometimes possible to dra.w conclusions as to the adulterant from the chai-acter of the turbidity and the separation of the insoluble part. Petroleum floats on the 70 percent alcohol, wdiereas fatty oil settles in drops at the liottom. Dowzard - suggests that the "solubility value" be deter- mined tiy dissolving 5 cc. of an oil in 10 cc. of alcohol, sp. gr. 0.799, and diluting with water from a burette until the solution becomes turbid. By multiplying the nnndier of cc. of water by 100 the ''solubility value" is obtained. Duyk' recommends the use of a solution of sodium salicylate in water 1 :1. The alcohols, aldehydes, and ketones, ai-e much nu^re solulde than the sesquiterpene hydrates, phenol ethers and esters. The hydro- carbons are practically insoluble. In special cases this solution may prove valuable. Cheiniciil Methods of Testing. The rational examination of a volatile oil in a idiemical manner is only then possible, when its composition or at least its nmin constituents are known. The chemical .investigation must be directed as much as possible toward the isolation and quantitative estimation of the con- stituents recognized as being the most valualile. The methods of testing must, therefore, conform to the analysis of the oil. If this really self- evident supposition hail eailier been genei-ally recognized, those methods of investigation, wliich are designated as quantitative reactions, as for instance the iodine alisorjition, or JIa.umene's sul]ihnric a(.:i(l test, which 1) The Htateiiientw in thi.s hook always refer to volume percent. *.n) pert-ent alcohol correspoQcls to the Spiritus, and 7(1 percent to the Splritus dihitus of the Cierman Pharmacopoeia. 2) Cihemi.it & Urnssi«t. 5."., p. 74ti. 3l Bnll. (le IWcarl. \U,y. de JIt'd. de F.elslqne, 1.809, p. .TO:!; .\nn. do Pharin., .5, p. 34.S. 1!)2 General Part. had given good resultt^ with the t'ntty oils, would not lifi\-e been applied offhand to the volatile oils. The fa,tty oiln aTe a gi-ou|) of ehenucally ehjsely related bodies; they ai-e glycerides of the fatty and oleic acid Keries. The constituents of tiie volatile oils, however, recruit themselves from the gi-ea.test variety of classes of liodies. Among them may be found terpenes, sesquiterpenes, piirnttins, alcohols, aldehydes, ketones, phenols, ethei's and esters. It should be no mattei- for sui-prise, therefore, that the methods of testing which are useful with the fatt.y oils, fail comi^Ietely with the volatile oils. Nor is there any sense in subjecting the fatty and the volatile oils to the same reactions, jnst because they both bear the same designation "oils." The application of Hiibl's iodine addition method to volatile oils has been recommended by Barenthini (1886), Kremel^ (1888), Williams* (1889), Davies* (IHSO) and Snow"' (lS8i)). By a direct coinjiarison of the i-esults of these separate observers it could not have been dithcult for Cripps'' (1880) to show the utter uselessness of this method. The use of l)romine in ]ila.ce of iodine wa.s first suggested Ity I^evalioisT (1,SS4) and later by Klimonts (1894). In Maumene's test the fatty oil to be investigated is nuxed in a certain jjroportion with ('oncentrated sulphuric acid and the rise in temperature which takes place is observed. Its application to volatile oils was i-ecommended by Williams" (18(10) us well iis by Duyki" (1897) lint it hu.s found just as little favoi' in ])ractice as the others named above. \\\t\\ these methods are to be classed also the much recommended color reactions. They mostly (X)nsist in bringing together a volatile oil and e. g. sulphuric acid or nitric acid, whereby some coloration is ])ro- duced, Avhich only in r.ire c.-ises can be ascrilied to a definite chemical eha.nge. As tlie shades of color produced are dithcult to describe, and f)ften (Imnge from one to the other and may therefoi-e easily give rise to mistakes, the c'olor reactions in general are to l.)e designated as use- less. This does imt exclude, however, the (x.'casional use of a, color re.'i.ction in the detection of adulterants. It is, however, never to be considered as conclusive in itself. M .ircliiv rl. Phann., 2l!4. p. N4s. o) Chum. News. (51), p. i!:',r,. 2) Phann. I'list, 21, |)|i. TS',1, S21. 7) Compt. rend., 90, p. ;i77. 3) Clieni. X.'wti, HO, p. 17.-.. 8) cliemikor Zintlins. IS. ii. (;41. i) l-'hai-ni. .rcMivn., Ill, i;), p. SLil. :i| C'licm. .\,.ws, (il, ji. lij-. -) Phann. .h.iini., III. 20, p. 4. lo) Bull. Ju IWcad. my. de nied. de Belgiqiic. The Exiiui'wiitiou of Volntilf Oils. 193 Besides the methods of testing already enumerated, many othei's have been suggested in the course of time, which liowever have acquired as little practical importance as these. Only such methods are here to he discussed as have really proven satisfactory in the investigation of volatile oils. Saponification. Through scientific investigation it has been estalilished tliat many volatile oils contain ester-like compounds, the components of which are alcohols, usually of the composition CmHigO or ('loHooO on the one hand, and acid radicals of the fatty series, on tile r)ther. The estei-s, which are nearly without exception of a. ])lea.snnt odor, are often to be considered as the most important constituents of the oils. Thus, linalyl acetate is the carrier of the odor in bergamot oil ; the same ester is found in lavender oil and also occui-s along with other compounds in petitgrain oil. The esters of borneol, found in tlie different jjine-needl^ oils, play an important part in the formation of the pine aroma. -Menthyl acetate is found in the pepjiei-mint oils and the geranyl ester of tiglic acid in the different geranium oils. The quantitative estimation of the ester is always valuable for judging the oils, even when the esters are of little consequence to the odor. Hut much more important, and really the only rational method as a test of quality is the determin- ation in all cases where the esters a,re the carriers of the cha,racteristic odor, as with bergamot oil and with lavender oil. The estimation is made according to the metliod of quantitative sapcjnification, as it has long been used in the analysis of tlie fats. Its application to the volatile oils was first made by A. Fvremel i (ISH.S). This suggestion did not reach a practical importance until through scientific investigation the nature of the saponifiable compounds was learned. Kremel distinguishes acid numlier (S. Z.), ester number ( K. Z.), anil .saponification number (V. /.). The aciii number expresses how many nig. KOH are necessary to iieutralize the amount of free acid contained in 1 g. of oil. The ester miinber gives the amount of potassa in milli- grams used in tlie saponification of tlie ester contained in 1 g. of oil. The saponification number is the sum of aciil number and ester number. As the volatile oils usually contain only a small amount of free acid, this may in general be neglected. Only old, partly spoilt oils, tend to show somewhat higher acid numbers. It must be mentioned that in all oils which contain aldehydes, the 1| Pharin. I'oMt, 21. PP- 7K:t, M21. 13 v.n (lenenil P;irf. tester determination by sapoiiifleation caniiot l)e made, as a. eoiisuniption of alkali take.s place wliic-h iiici-eases with the leiiji'th of the reaction, due to the deconiyiositioii of the aldehyde, hut wliich ^iveis no iiifoi-mation as to the nuiount of a.hlehyde decomposed. Thi' .sii|i(jiiificMtioii is coiiductfd in a wide necked flask of potash K'ass uf 100 cc. capacity I fig. oGl. A glass tube abont 1 in. in lenKtli and passing tlii-ougli a stopper servfts as a ri'Hnx rondensHi-. About 2 g. of oil are weighed accur- ately (() 1 eg. into such a fl;isk a,nd 10 to 20 cc.' of an lieuii ii()i'ni,-il alcoholic potassa solution ai'e added. I'revious to this tlic oil shonld bt- tested for- free acid, an alcoholic solution of phenolphthaleTii being used as indicator. The flask provided with the condensing tube is he.ated for half an hour- on a stnani bath, and aftc^r cooling, the contents are diluted with about 50 cc. of watnr and the excms of alkali titrated back with half normal sulidiuric acid. From the sa.ponifieatiou nundier found, the percent- age content of estei-s of the formula ('inHi-OGOCH:} III and ('iiiHi^OCOCHm may he read directly in the tables If! to be found on page 204 at the end of this chapter. Acetvlization. Monv volatile oils contain as im- ■h I lin ^ ' .^ , , ,' 1 f +1, ( IOWA Dortant constituents alcohols oi the formula tioHisO Nil ".(, ' and OioHaoO, for instance, borneol, geraniol, terpineol, linalool, thujyialcohol, menthol and citronellol. For the quantitative estimation their behavior toward acetic acid anhydride, with wdiich they foi-m acetic esters wdien heated, may be used. The reaction takes jilace ai'cording to the equation : ('i„Hi.sO + irH:i»"0)20 = ('ioHi7t)C()('H,s + ('Ha('0()H. The reaction is quantitative with borneol, geraniol (Hei'trnni and ^! 1) In most cases 10 ec. arc Hiiftieient, only witli unknown oils 20 or of alkali solntion are taken. 2) Witii ln'i-ji'ii niot oil the sjiponification is i'onii)k'tc within 1 minutes. In oi'iUt to be certain in all cases, tlie heating can be continued somewhat lonaei". Avithout detrimental el^ect. Compare Bericht von Schlmmel & Co., October 1X95, p. 16. The method used by Helbing (Helbing's Pharmacological Record, No. 30, p. 4) of saponifying- in a closed vessel, consequently under pressure, ffare, as the experiments by Schimniel & Co. show, for ber^amot oil froui 1 — 2 percent higher results than did the saponification in an open flask. The reason for this is, that when saponified under pressure the linalool is attacked by the potassa, which is thereby used up, while by boiling with potassa in an open flask the alcohol is not affected. Later (1S95), Helbing and Pass- more (Chem. & Drug., 47, p. 585) coroborated that the saponification in an open vessel with a reflux condenser was preferable to saponification in an autoclave. Neither does the so-called cold saponitication appear to be applicable to volatile oils. Moreover, it has the disadvantage of requiring a longer time. For. according to Henriques. (Zeit- schrift fiir angewundte Chemie, 1897. p. :{99) linalool after 12 hours action of the alkali gave the saponification number 4.2, and geraniol by the same treatment one of 2.8. The Exmnin.ition of Voliitile Oils 195 Gildemeister,! 1.S04) and menthol (Power and Kleber,- liS<)4) and makes an accurate determination of these bodies possilile.^ Less fortunate are the conditions witli liTialool and terpineol as tliese on l)oiling' with acetic acid anliydride are partly decomposed bj' splitting off water with the formation of terpenes. Comparative figures can, however, be also obtained with these alcohols, if the same amount of acetic acid anliydride is always used and the boiling continued for the same length of time. With liiialool thei-e was found as a favorable result after 2 hours of boiling, a deficiency of 13 percent of alcohol.* Terpineol l)ehaves toward acetic acid anhydride as follows: Time of boiling: 10 minutes 30 45 2 hours Tei-piiiyl a(*tate formed: 51.2 percent 75.5 " .S4.4 77.9 With terpineol, therefore, heating longer than 45 minutes has a. detrimental effect. Acetic acid anhydride acts differently on aldehydes. While citronellal is converted qu.mtitatively into iso- pulegol acetate, with citral there ai-e formed indefinite amounts of saponiflable products ■"> as yet unknown. For the qiiaiititative acetylizatioii " 10 to 20 cc. of tlie oil, mixed Avitli an nqual vohniie of acetic acid anliydride and 1 — 2 g. of dry sodium acetate, are boiled uniforndy from 1 — 2 hou7's in a small flask provided with a condensing tube which is ground iiito the neck of the flask (fig. 57). After coohng, some water is added to the contents of the flask and then heated from % to }^ hour on a water bath, to decom- pose the excess of the acetic acid anhydride. The oil is tlien separated in a separating fuimel, and w^ashed with soda, solution and water until the reaction is neutral. Of the acetylized oil dried with anhydrous sodium suli)liate 2 g. art- saponified according to the method described on Fig. B7. 1) .Journ. f. prakt. Chem., II, 49, p. 189. 2) Pharru. Rimdsch., 12, p. 182; Archiv d. Pharm., 233, jj. 65.3. 3) Even with ttiene alcohols an indiscriminate application of this otherwise excellent nieth(jd to all oils contalninp; them ehonld be avoided. It is known that acetic acid comltine.s with terpene.s to form acetates of corresponding alcohols. In fact preliminary experiments sho^v that pinene and limonene may assay in part as alcohol when this method is nsed. E. K. i) Bericht von S. & Co., April 1893, p. 38. = ) Bericht von S. & ("o., Oct. 1890, p. .34. 6) P.ericht von S, i- Co.. Oct. 1894, p. f>3. 190 Gen fir!}] P,-n-t. page 11)4. The aiiioiiut of alcohol, based on the original unacetylized oil, (■ovi-es|ioiidiiig to the Kajjoniticatioii iniiiibei', can be found iii the tables 07i jiage 204 at the end of this r-hajiter. Aldehyde determination. The quantitative deterniinatioii of cinuaniic aldeliyde depends on it,s property to form a water soluble addition yii-oduct with an excess of sodium bisulphite. When a known amount of an oil containing cinnamic aldehyile is shaken snfticiently loTiu' with a, hot concentrated bisulphite solution, the aldehyde content of the oil is about e(pial to tlie decrease in volume. The nninipulation of the aldehyde determination and the necessary apparatus are described in detail under cassia oil (see this), t'iti-al liehaves similar to cinnamic aldehyde, and is able to form a water soluble bisulphite addition ])ro- duct. I he same method is, therefore, applicable to oils rich in citral, as for instance, lemong'ra,ss oil. Foi' the determination r)f the aldehydes in lemon oil this methoil is, however, not suited, on account of the formation of the citronellal addition product, which is insoluble in water and floats pjartly in the acpieous, partly in the oily l.-iyei' and makes an accurate reading- imiiossible. Besides, the liisnlphite method is hardly aecui-ate enough for lemon oil, as this contains only — 8 percent of aldehydes. Anothei- method, to determine the carbonyl oxygen and thus the aldehyde a,n(l ketone content in volatile oils has been worked out by Benedikt and Strache i (1(S93). The oil to be investigated is heated with a, weighed amount of idienyl hydi'azine, after some time the hydro- zone which has formed is separated by filtration, and the unchanged phenyl hydrazine in the filtrate oxidized with boiling Fehling's solution. By this treatment all tlie nitrogen of the phenyl hydrazine which has not taken part in the re;u,-tion is liberated as gas. From the volume of fhe collected nitrogen the amount of the unused plienyl hydrazine can be calculated. From this tlie amount which has gone into condiinafion is known and consequently the amount of the ketone or aldehvde present. The amount of carbonyl oxygen, expressed in Vk, percents is designated as carbonyl number. With bitter almond oil ( benzaldehyde), cumin oil (cuminic aldeh\-de), and rue oil (methyl nonyl ketone) this method yields fairly good results. With cassia oil, carawa\- oil, fennel oil ami lemon oil, however, the determinalious fall far too low.- M .Aloiiat.sli. f. C'heiii., 14, |i. L'Td. 2) Beiicht von S. & Cii., Ocl. 18!)B, [i. 4s. The Examination of Vohitilp Oils. 197 The problem of a general method foi' determining the aldehyde and ketone content of volatile oils, is tlierefore not yet satisfactorily solved. Perhaps it is possible to reach better results by suitable changes in the method described. A method devised bj' Kremers and Schreiner specially for the estimation of carvone in cai'vone-containing oils will be discussed umler caraway oil. Phenol determination. For an approximately accurate phenol determination in volatile oils, the property of the ])henols to combine with alkalies to form compounds which are soluble in water, is used. If a measured quantity of an oil is shaken with a solution of alkali, tlie content of phenols can be approximately determined horn tlie diminution in volume. The soda solution is to be five percent. A greater concentration is not allowable, as stronger phenol-alkali solutions take up relatively large amounts of the remaining constituents of the oil, and thus give results which are too high. The manipulation of sucdi a determination is described under thyme oil. Thymol and carvacrol are determined by Kremers and iSehreineri (11S96) quantitatively in volatile oils, Ijy precipitating the phenols from tlie alkaline solution as tlieir iodine compounds and titi-ating back tlie iodine added in excess. The vajior.s of methyl iodide formed by boiling' from 0.2 lo 0.3 g. of the oil to be investigated with hydriodic acid (8|). gr. 1.70, to which, acecjrdiiig to Hpi-zigi (18JSfSl 8 |i('i-ceiit of acetii' acid in added) a,re first jinssed through somp warm wafer in which some phosphorus is suspended, s'l as to retain any iodine va.jioi's which may have been carried ovei'. .\fter the methyl iodide has |)assed through this apparatus it is jiassed into an alcoholic solution of silver nitrate and the separated silver iodide weighed. A very conveinent apparatus has been designed by L. Khma.nn^ (iNifO) for carrying out tliis determination. firegor-' (1898) has i-ecently suggested to replace the idiosjfliorus suspended in water by a solution of one part each of potassium bicarbonate and ar.senous aciil in 10 parts of water, by which not only tlie iodine va.pors but also any hydriodic acid carried over is retained. For collecting the methyl iodide (jregoi' uses a Vio normal silver nitrate ,s(dution which has been acidified with nitric acid and titrates back the siivei- not used for the ])recipitation of the silvei- iodide with Vio normal potassium sulphocyanate solution according tfj Volhard. ( >f the oils investigated by Benedikt and Griissnei' the followhig gave no methyl numbers: the oils of wormwood, bitter almond, angelica, l)erganiot, caraway, lemon, copaiba-balsarn, coriaiidei-, cubeb, elemi, eucalyptus, geranium, juni[)er, cherry laurel, lavender, spearmint, peppermint, olibonum, oil f)f Finns luuntniiri, savin, East Indian and West Indian sandalwood, turpentine and valerian. High methyl nmubers were given by anise oil, star anise oil and fennel oil on a(.'courit of their content of anethol and methyl chavicol, by clove oil, and oil of cinnamon leaves on account of their content of eugenol. With wintergreen oil the high methyl aunibei' is ciue to the methyl salicylate, with parsley oil to the apiol. The deternn'nation i,s only applicable with oils abs(dutely free from alcohol, as ethyl alcohol itself gives a methyl number, from wduch it follows, that this method may also be used for the quantitative ii ."MonalKh. 1'. Chcniie, 9, p. 544. 3| .\Iunatsli. f. Clieniic, IVI, p. Kili. -I ('lieni. Zeitmig-, 14, p. 1 7(i7. The Exntiiiimtion ol VolntiJi^ Oils. 199 estimation of alcohol in those oilis wliieli in thpii- ])in-e condition do not contain any niethoxyl o-ronps.i The Beteption of Some of the More Common Adulterants. Turpentine oil. Tnrpentine oil may be considered as the adulter- ant most often nsed. ^'ery often it can be recognized liy its cliaracter- istic odor, especially in those oils which contain no pinene, as this is the main constituent of turpentine oil. In general, its ]3resence causes changes in the specific gravity, solubility, boiling temperature and optical rotation, [t must here be remembered that there are dextro- as well as laevogyrate turpentine oils. The positive proof of the preseni-e of tnrpentine oil in oils, which in their pure state contain no pinene, is furnished by the isolation of and characteristic derivatives of ])inene. The ('onstitnents boiling in the neigjboi'hood of 160°, are fractionated out and, according to the method descrilied on page 109, the pinene nitrosochloride, as well as pinene nitrolbenzylamine or jiinene niti-olpiperidine are prepared. If pinene is a iu)rauil constituent of the oil, the addition of turpentine oil (.-.an be recognized by a comparison of the physical properties of the lowest boiling fractions of the adulterated oil with the corresponding portions of the pure oil. The detection of turpentine oil in rosemarj^ oil famishes an example (.see this). Cedar 'W'ooi.l, copaiba and giirjun balsam oils. On account of their cheapness and faint odor, these three oils belong to the most favored and the most dangerous of adulterants. They may, however, be detected without ditficulty in most cases by means of their physical properties, which differ from tho.se of many of the volatile oils, na.mely 1) The methyl nuiriber.s of some of the oils inve.stigated by Beiiedikt iind Griissner can only be explained by the pre.senee of alefjhol. It is greatly to be refiretted, that the physical properties of the investiffated oils are n(jt ffiyen, and their purity cannot there- fore be judged. With the Ceylon cinnamon oil designated as No. 22 in the article cited, Benedlkt and Griissner calculate from the methyl number found, 2.5.7, a eugenol content of 28.1 percent. As pure Ceylon cinnamon oil contains only -t — K percent of eugenol, it follo^V8 from the determinati(^n (proyiding: that the methyl number is due only to euffenol), that the oil was adulterated T\-ith the oil of cinnamon leaves, which is rich in eugenol. From this illustration it may be seen that the rejjorted methyl numbers are to be used with care. It would therefore t)e a valuable piece of investigation to repeat these determinations on oils whose purity could be previously determined in another manner, in order to give to this really fine method the basis necessary for practical purposes. For the scientific inveRtigatir>n of the volatile oils the methoxyl determination s extremely valuable as it gives information ()f the presence or absence of phenol ethers or acid esters, which contain a methyl, ethyl, or projiyl group. •200 Gener.-il Fart. their ditficnilt soliiliility in 70 to 90 percent or even Htronger alcohol, their high specific o-ravity (above 0.900), their high boiling temperature, above 250°, ai.il tiually their rotator,y power. All three oils tnrn the plane of jjolarized light more or less to the left. With co|iaiba balsam oil the angle of rotation a„ lies between— 7 anil — 35°,i with cedar wood oil between —80 a.nil — 40°, and with gnrjun balsam oil lietween — >!.") and — l."!0°(!). At present only copaiba l)alsam oil can be detected in a chemical way, in that the fraction Ijoiling about 2()0° is converted into caryo- phyllene liydrate melting at 94—90°, or into carj'ophyllene nitrolpiper- idine (see p. 12.")) melting at 141—14;^°, or into caryoijhyllene nitrosite a.nd the corresponding nitrrjlbenzylamine base (see p. 12(i). As yet no chai'acteristic derivatives of the sesipiiterpeiies of cedar wood and gnrjun ba-lsa-m oils are known. Alcohol. The addition of alcohol to a volatile oil always results in a lowering of the specific gravity. "When an oil containing alcohol is dropped into water, the drops do not remain clear and transparent, as is the i-ase with ])m'e oils, liut Ijecome opaque and milky. Fcjv tlip detiiiitH identifieatioii of alcoliol tlie suspected oil is heated until it just begins to f)oil,^ and the first few drops that coini' over are collected in a test tube and filtered, to remove^ any oil globules -w liicli may also have come over, through a, filter moistened with water. The filtrate is jiiade strongly alkaline with dilute |)otassa solution, and treated, after heating to .50 — 60-, with a. solution of iodine in ijotassiina iodide, until tlie solution i-emains slightl.v yellow. If alcohol is iiresent small rrystals of iodoform \vill separate in a, short time at the bottom of the li(juid. It must here be remembered that other bodies, such as aldehydes, ac(!tone and acetic ether also yield iodo- form under the given C(jiiditions. [jarger a.nionnts of alcohol may be I'emoved fi-om volatile oils bv .sliaking with water, from which the alcohol may be again removed bv distillation and identified by the iodoform reaction. If the shaking out is done in a graduated cyliiuler, the increa.se of the watery laver ccaresponds apiiro.ximately to the amount of the alcohol. .\ccording to Hager it is bettei- to use glycerin, because with this the two layers separate better, and a more accurate reading is possible. The alcohol content may also be a])])ro.\imate!y calculated if the wpecitic gravity is determined before and after shaking with water. M Ilnmey in IS'.l.-, d'hnnii. .Idiivii.. Ill, l>4. |i. l'1.">i. (duiiiI I he oil of a soculled C()iuiil)n tjHlNain from went .Vfrii/a tn be ilextrosyrate. '/.i) = + 2o 42'. lle.xlrojiyrate ji'iirjiiri balHaui oils a i-e also s;iii] (o exist. 2) .411 aleohol is not removed by heatuiK on a water-batli. The Examhnition of Vohitih Oils. ' fOl As already mentioned on page 198 the amount (jf tlie alcohol in an oil which in itself does not give a methyl number, may be determined quantitatively b\' Zeizel's raethoxyl metiiod. Fatty oil. The volatile oils adulterated witli fatty oil leave a permanent fatty stain when evaporated on paper. With high boiling and difficultly volatile oils, however, similar residues are left, which may give rise to mistakes. Fatty oil is insoluble in 90 percent alcohol. i For the separation of the fatty oil from the volatile oil the latter is distilled off by steam distillation or removed by evaporation in an open dish on the waterbath, where it must l)e rememl)ered that some volatile oils, as bergamot, lemon, orange, anise and star-auise oil leave a residue of several percent even when tliey are not adiilterated. The presence of the fat may lie shown (pialitativelj' in the residue hy heating with potassium l)isulphate in a test tube. Penetrating odors of acrolein show its presence. By igniting the residue on a platinum foil the characteristic odor of burning fat is noticed. As the fatty oils give saponification numbers which lie between 180 and 200, the amount of the fat added can be determined quantitatively either directly in the volatile oil itself or in the distillation residue, by saponification. Oils that have been adulterated witli cocoa nut oil solidify wholly oi- in part in a freezing mixture. Cocoa nut oil has been found in cananga oil, citronello oil iind palmarosa oil and detected in this manner. Mineral oil, petroleum. Minend oil, ]joratHn oil, kerosene, petroleum and petroleum fractions are insoluble in alcohol and can tlierefore be detected without ditflculty in volatile oils ; besides, they are often easily recognized liy theii' hjw specific gravity. Palmarosa oil to which some minei'al oil has been ;idded is only partly soluble in 70 percent alcohol. If the insoluble portion is successively treated witli 90 percent and absolute alcoiiol, :in oil remains, which in the beginning it is true is colored brown by sulphuric or nitric acids, but in general resists the action oi these acids iiiid also of alkalies, and on saponi- fication with alcoholic potassa gives no saponification number. The mineral oils have different boiling points. The hydrocarbons of illuminating oil boil at about the same tempera.ture as the terpeues. Lower boiling fractions are said to be sometimes u.sen of \'ebanon cedar oil. Se(jUfjia gigaiitea — Sequoia oil. Callitris ijiiailrivalis — Sandarac oil. Thnja (icridentalis — Thuja oil. Thuja, orientalis — Oil from the roots. Cnpressns senii>errirens — O.vpreHS oil. Cliainaec.vparis obtusa, — Hinoki oil. Juni/ienis communis — Oil of juniper berries. 1) Accordiiis to Eiigler's S.yllabus. Seciiml eclition. Berlin. 1808. List of Plants, Arranged According- to Families, etc. 213 Juniperus oxjcedrus — Oil of berries. Juniperus pboenicea — Oil of berries. Juniperus sabina — Oil of savin. Juniperus virginiana—Oi\ of cedar wood (cedar oil), oil of cedar leaves. Pandanaoeae. Pandanus odoratissimus — Oil of flowers. GrRAMINEAE. Andropogon schoenanthus—Pei\ma,TOsei oil, and gingergrass oil. Androjiogon citratus — Lemongrass oil. Andropogon muricatns — Vetiver oil. Andropogon nardus — Citronella oil. Andropogon odoratus — Oil of herb. Andropogon laniger — Camel grass oil. Palmae. Serenoa serrulata — Saw palmetta oil. Araceae. Acorus c;]ia7Hi;,s— Calamus oil, oil from leaves, .Japanese calamus oil. Liliaceae. SabadiUa officinalis — Sabadilla oil. Aioe vulgaris — Aloe oil. Xanthorrboea hastile — Xanthorrhoea oil. Allium sativum — Garlic oil. Allium cepa— Onion oil. Allium ursiaum—O'd from entire plant. iRIDACE.iE. Crocus sativus — Saffron oil. Iris Horentina, I. pallida, I. germanica—Ovria oil. Z1NGIBERACE.4.E. Curcuma longa — Curcuma oil. Curcuma zedoaria — Zedoary oil. Kaempferia rotunda — Oil of root. Hedychium coronarium — Oil of flowers. Alpinia ga!anga—Ga\einga\ oil. Alpinia malaccensis — Oil of roots. Alpinia nutans — Oil of roots. Zingiber o fficinale— dinger oil. Elettaria cardamomum-~Oi\ of cardamom (Ceylon), Malabar (Madras) carda- mom oil. 214 General Pnrt. Amomnin cfirdninomuia Siam cardamom oil. Amomum melegusta—OW of paradiBe grains. Arnnmum aroinaticuin — Beugal cardamom oil. Amomiim spec? — Kamfniii cardamom oil. Amomnin angustifolium — Korariraa cardamom oil. PiPBBACEAE. Piper iiigium~Oi\ of black pepper. Pijier Inngum — Oil of long pepper. Piper ovatuiu — (!)il of leaves. Pijier lowong — Oil of fruit. Piper f/(;sii^.\schanti pepper oil. Piper cubeba — Oil of cubebH. Piper angiistifolium—MsitKO oil. Piper betle — Oil of betle leaves. Potomoiphe umbellata — Oil of leaves. Artantlie genieulata — Oil of leaves. Ottonia anisum — Oil of roots. S.VLICACKAK. Popiiliis iiigi'a — Oil of buds. Mykicacbae. Myric-a gale — Oil of Dutch myrtle. Myricii cerifera — Oil of bay-berry. Myrica asplenifolia — Oil of sweet fern. JU(iLANT>AOEAE. JiiglaiiK regia — Walnut leaf oil. Betulacbae. Betula lenta — Oil of sweet birch ( wintergrei'n oil). MoK.U!EAB. Hiimiiljif! lupnhis — Oil of ho])8. ('annabin sativa — Hemp oil. Santalacbae. Santa Imn album— CiW of sandalwood (East Indian). Santahiin preissianum — South Australian sandalwood oil. Santahim cygnoniin— West Australian sandalwood oil. Santaluni yasi — Fiji sandalwood oil. Unknown species — African sandalwood oil. Arihtoloi'hiacbae. Asanim eiwopaeiini — Oil of root. Asaruni canailense—OW of Canada snake root (wild ginger). List of Plants, Arranged According to Faiiiilien, etc. 215 Aristolochia, serpentaria — Oil of Yir-ginia snake root. Aristolochia clematitis — Oil ot roots. ChENOPODIACE AE . Chenopodinm amhrosioides var. anthelminticiun — Oil of American worniseed. ■Raxuncitlaceae. Paeonia moutan — Oil of roots. Nigella sativa — Oil of seeds. Nigella damascena — Oil of seeds. MAflNOLtACEAE. Micheba cbampaca — Charapaca oil. Michelia longifolia — Oil of flowers. lUicinm rerum — Star anise oil. Ulicinm nnisatum — Japanese star anise oil. Drinijs winteri — Oil of Wintei-'s bark. Anonaoeae. Vananga odorata — Ylang ylang cjil and eananga oil. Myristicaceae. Myristica fragrans — Oil of mace, oil of nutmeg. MONIMIACEAE. Peumns boldns — Oil of boldo leaves. , Atlierosperma moschata — Atherosperma oil. Citriosma oligandra — Oil of leaves and bark. f'itriosma cujahana—OW of leaves and bark. Citriosma apiosyce—OW of leaves and bark. Unknown species — Oil of para coto bark. Lauraceae. Cinnamomum campliora — Camphor oil. Cinnamomuin zeylanicuin — Oil of ciunamoTi (Ceylon), oil of cinnamon leaves, oil ot roots. Cinnamomnm cassia — Cassia oil. Cmnamomnni lonreirii — .Japanese cinnamon oil. Cinnamomum kiamis— Oil of bark. Cinnamomum ciz/i/aira/j— Culilawau bark oil. Cinnamomum wightii — Oil of bark. Cinnamomum oliveri—0\\ of bark. Persea gratissima— Oil of leaves. Persea caryophyllata—0'd of clove bark. ISectandra puc/jurj— Pichurira oil. 216 General Part. Nectandra caparrapi — Caparrapi oil. Ocotea caudaia— Guayana lignaloe oil. Ocotea species? — Ocotea oil. Nectandra myriantha. Nectandra or Ocotea species?— Venezuela camphor wood oil. Sassafras officinafe— Sassafras oil (bark), oil of sassafras leaves. Cryptocaria moscliata—Crjptot:ana, oil. Cryptocaria pretiosa — Oil of bark. Laurus nobilis — Oil of laurel leaves, oil of fruit. Lindera sericea. — Kuromoji oil. Oreodaphne caUfornica — Oil of mountain laurel. Benzoin odoriferum — Spicewood oil. Tetranthera citrata — Tetrantliera oil. Dnknown species — Massoy bark oil. Cruciperab. Lepidinm sativum — Pepper-grass oil. Tlilaspi arvense— Oil of herb. Cochlearia officinalis — Oil of spoonwort. Coclilearia armoracia — Oil of horseradish. Ailiaria oiBcinalis—Oil of hedge garlic. FSrassica nigra, B. juncea — Oil of mustard. Sinnpis alba — Oil of white mustard. Nasturtium officinale — Oil of watercress. Raphanus sativus and B. nigei-—Oi\ of cominon radish. Resedaceae. Reseda odorata — Mignonette oil, oil of root. Hamamelidaceae. Liqnidambar orientale — Oil of liquid storax. Lii/tiidambar styracitinum — Oil of sweet gum, oil of leaves. Altingia excelsa — Rasamala oil (wood). Rosace AE. Sytiraea nlmaria -Spiraea oil. /I'o.sa damascena — Hose oil. ttosa centifolia—Uot^e oil. Frunus amygdalas, P. armeniaca, P. persica— Bitter alnv(jnd oil. f'runns laurocera,sus—C\\evvy laurel oil. Prunus virginiana— Oil of wild cherry bark. Leguminosae. Copaifera officinalis C. guajanensis, C. coriacea, C. langsdortfia, C. confertiflora, C. oblongifolia. C. rigida — Copaiba balsam oil. .¥Frocar/7u.s /a.s-fio'iatus—Cabriuva wood oil. •. List, of Plants, Arranged According to Fninilies, etc. 217 Genista, tridentata — Carqueja oil. Indigofera. galegoides—OW of leaves. Caesalpinia sappan —Sappau oil. Tolnitera halsamum — Tolu balsam oil. Myroxylon peruiferum — Oil of leaves. Glycyrrhiza glabra — Oil from root. Glycyrrhiza glanduUfera — Oil from root. Geraniaceae. Pelargonium odoratissimum, P. capitatum, P. rosenm— Oil of rose geranium. TROPAEOLACE.iE. Tropaeoliim majus — Oil of nasturtium. Erythroxyl.wjeae. Erythroxylon coca — Oil of coca leaves. Zygophyllaceae. Bulnesia sarmienti — Guaiac wood oil. EUTACEAE. Xanthoxylum piperitum — Japanese pepper oil. Xanthoxyhim liamiltonianiim— Oil of seeds. Huta graveolens — Oil of rue. Boronia polygalifolia — Boronia oil. Barosma hetulina, D. serratifhHa,—0\\ of bucliu leaves. Empleurum sernilatum — Oil of leaves. Pilocarpus jahorandi— J aborandi oil. Cusparia trifoliata, — Oil of angustura bark. Toddatia aculcata — Toddalia oil. Citrus limonum—OW of lemon. Citrus aurantium — Oil of sweet orange, oil of neroli (Portugal). Citrus higaradia— Oil of bitter orange,, oil of neroli, oil of petit grain. Citrus bergamia— Oil of bergamot. Citrus medica — Cedrus oil. Citrus medica var. acida — West Indian limette oil. Citrus limetta, — Italian limette oil, oil of leaves. Citrus nobilis — Oil of mandarins. Citrus decumana — Grape fruit oil. Schimmelia oleifera — We.st Indian sandalwood oil. Dacryodes bexandra—Oil from oleoresin. BURSERAOBAE. Commiphora abyssinica, C. schimperi— Oil of myrrh Balsamodendron A-a/a7— Opoponax oil. BosweWn carteri— Oil of frankincense. 218 Gi^riprnl Part. Canarinm Bpec? — Eleini oil. Icicn. IwptiiphyUa— Comma, resin oil. BuTsera atoe,vv/on— I Mexican ) iignaloe oil. Meliaceae. Cedrfln. orlonita and other S]iecies— Cedrelar wood oil. POLYGALACBAE. Polvfiahr senega — Oil of senega root. Polvft-ala variabilis, P. oleifera, P. ealairea, P. depressa, /'. Jwiiioriy;i,u;a — Metljyl salicylate. EirPHORBIACEAE. Croton eJnteria — Cascarilla oil. Stillingia si/ratica— Stillingia oil. Anacardiaceae. Pistaeia lentisens — Mastic oil. Pistacia terebinthus — Chios turpentine oil. Schinus mo//e— Schiuus oil. A'^ITACEAE. Vitis vinifera — Cognac oil. TiLIACEAE. Tilia Jilmifolia, T. jtlatyphyllos — Oil of linden flowei'S. Malvaceae. Hibiscus abelinoschus — Oil of ambrette seeds. Theaoeae. Thea cliinensis — Tea oil. DiPTEROCARPACEAE. Dryohalanops camphora — Borneo camphor oil. Dipterovarjais turhinatus and others — Gurjun balsam oil. ■ii' ^ ■ Oistac:eae. Cistus ereticiis, C. hulaniferiis — Labdanuni oil. (.'.ANELL.\CEAE. ('ajielhi alba, — ('anella oil. TURNEH.ICEAE. Turnera ajiliroilisiaca, T. ihlftisa — Damiana leaf oil. List of Plants, Arranfrrd Accordino; to F;iiiiilies, etc. 219 Lythraceae. Lawsonia inprinis — Henna oil. Myrtaceae. Mrrtus commnnis — Oil of myrtle. Myrtns cheken — C'heken leaf oil. Piiiifiita otRcinaUs — Oil of pimenta. Pinienta acris — Oil of ba.v. Eugenia caryopliyllata — Oil of cloves, oil of clove stems. Melaleuca leucadendron — Cajeput oil. Melaleuca viriditlora — Niaouli oil. Melaleuca leucadendron var. lancifolia, M. acuminata, M. decussata, M. ericifolia. M. genistifolia, M. linariifolia, M. squarrosa, M. uncinata, M. iFifeonii— contain in the leaves cajeput-like oils. Eucalyptus globulus, E. odorata, E. cneoriiolia, E. oleosa, E. dmnosa, E. amygdalina, E. rostrata, E. populifera, E. corynibosa, E. resinifera, E. baileyana, E. microcorys, E. risdonia, E. leucoxylon, E. hemipbloia, E. crehra, E. macrorrliyncba, E. capitellata,, E. eugenioides, E. obliqua, E. punctata, E. loxophleba, E. dextropinea, E. laevopinea, E. niaculata, E. citriodora, E. dealbata, E. planchoniana, E. staigeriana, E. haemastonia, E. piperita, E. diversicolor, E. Sssilis, E. goniocalyx, E. gracilis, E. lehmanni, E. longi- folia, E. occidentalis, E. paucifiora, E. stuartiana, E. terreticornis, E. tessellaris — yield the various eucalyptus oils. Backhousia citriodora — Backhousia oil. Araliaceae. Aralia nudicaulis — Oil of rhizome. U.MBELLrFER.AE. Coriandrnm sativum — Coriander oil. tuminum cyminum — Cumin oil. Apium graveolens — Oil of celery seed, oil of herb. Petroselinum .satii'uzc— Parsley oil, oil of root, oil of herb. Cicuta virosa — Cicuta oil. Cicuta maculata— Oil of fruit. Varum carvi — Caraway oil. Carum a/oi^an— Ajowan oil. Pimpinella anisum—kmae oil. Pimpinella saxifraga — Oil of root. Pimpinella nigra — Oil of root. Foeniculnm vulgare—F enniA oil. Mcnin atbamanticum—OW of root. Silaus pratensis— Oil of fruit. Oenanthe aijuatica— Oil of water fennel. Levisticum officinale— Oil of lovage (root), oil of seed, oil of herb. Archangelica officinalis— Oil of angelica (root), oil of seed, oil of hei'h. 220 General Fart. Angelica refracta (azjomflJa'-')— Japanese angelica root oil Ferula asa foetidn — (_)il of asafetida. Ferula rubricanlis — Galbanuin oil. Ferula fiumhul—0\\ of sumbul. Dorernn ammoniacum — Ammoniac oil. Peucedanum oreoselinum — Oil of fresh herb. Peucedamim ostruthiuni — Oil of root. Peucedanum graveolens — Dill oil. Anethnm .soiva— East Indian dill oil. Peucedanum sativum— Fastinaea oil. Peucedanum gvande — Oil of fj'uit. Peucedanum officinale — Oil of root. Heracleum sphnndrlium — (.)il of fi'uit. Heraclenm gigajiteum — Oil of fruit. Vaucus carota — Oil of carrots. Oninorrhiza longistxHs— Oil of root. PlHOLACEAE. Monotropa hypr>])ifys — Oil of stem. Ericaceae. Ledum palnntve — Oil of Labrador tea. Oaultheria procumbens — Oil of wintergreeii. Gaultheria punctata— 0\\ of leaves. Gaultheria leucncarpa — Oil of leaves. Primul.aceae. Primjila, reri.s— Oil of root. CONVOLVULACEAE. Convolvulus sco/iaria, C. tioridus — Oil of rhodium. Verbenaceae. Verbena triphylla — Verbena oil. Lantana, cainara — Oil of herb. Vitex trifolia — Oil of leaves. Labiat.ve. Rosmarinus officinalis — Oil of rosemary. Lavandula vera — Oil of lavender. Lavandula sjiica — Oil of spike. Lavandula, stoeclias—Oi\ of lierb. Lavandula, dentata — Oil of herb. Lavandula pedunculata — Oil of herb. Nepeta cataria — Oil of catnep. Nepeta. glecboma. — Oil of gill-over-the-ground. Salvia, officinalis— 0\\ of sage. List of Plants, Arranged According to Families, etc. 221 Salvia sclarea — Oil of herb. Monarda punctata — Horsemint oil. ■ i Monarda didyma — Oswego tea oil. Monarda fistulosa — Wild bergamot oil. Melissa officinalis — Balm oil. Hedeoma pulegioides — Pennyroyal oil. Myssopus officinalis — Hyssop oil. .Satureja hortensis — Oil of summer savory. .Satureja. montana — Oil of winter savory. ■Satureja thymbra — Oil of herb. ■Origannm vulgare — Oil of wild marjoram. ■Origanum majorana — Oil of sweet marjoram. Origanum hirtum, O. smyrnaeum and others — Oil of Cretian origanum. Thynms vulgaris— Oil of thyme. Thymus serpyllum — Oil of wild thyme. Thymus capitatus — Oil of herb. Lycopus virginicus — Oil of bugle weed. Mentha piperita, M. arvensis var. piperascens — Oil of peppermint. Mentha silvestris var. crispa, M. viridis — Oil of spearmint. Mentha aquatica — Oil of herb. Mentha arvensis — Oil of herb. Mentha canadensis — Oil of Canada mint. Mentha pulegium — Oil of European pennyroyal. Pogostemon patchouly — Patehouly oil. Pogostemon coniosus — Oil of leaves. Ocimum hasilicurn — Oil of sweet basil. Morula japonica — Oil of hei-b. ■ ■/Junila mariana — Oil of herb. Lophantus anisatus — Oil of herb. Pycnanthemum la.nceolatum — Oil of mountain mint. Pycnanthemum incanum — Oil of herb. vSOLANACEAE, Fahiana imhricata — Oil from leaves. Oaprifoliaceae. _ Samhucus nigra — Oil of flowers. Valebianaoeae. Valeriana officinalis— Oil of valerian. Valeriana officinalis var. angustifolia—Kasno oil. Valeriana celtica— Oil oi root. Nardostachys jatamansi —Oil of root. CoMPOSITAB. Eupatoriurn foeniculaceuni— Oil of entii-e plant. Ageratum convzo'ides — Oil of herb. 222 General Pnrt. Solidiif>-o of/o;vj— Golden rod oil. Solidngn nigosn — Oil of liei-b. Erigei-on canadensis— 0\\ of flea bane. Bluiiiea hnlsamiiera, Bl. /.■jeej-a— Bluniea camphor. Heliclirysuin stoechas — Oil of lierb. Inula, helenhirn — Oil of elecampane. Osmitopas asteriscoides—OW of herb. Ambrosia arteniisiaefolia — Oil of rag weed. Antheniis noliilis — Oil of Roman chamomile. Anthemis cotula — Oil of mayweed or dog fennel. Acliillen niillefohum — Oil of milfoil. Achillea nobilis — Oil of lierb. Achillea moschata< — Oil of floweiing herb. Achillea corono] nfolia—OW of hei-b. Achillea ageratum—OW of hei-b. Matricaria chamomilki — Oil of (iermaii chamomile. Matricaria partheninm — Oil of flowering jilant. Tanacetnni vulgare—OW of tansy. Tanacetum halsamita — Oil of herb. Pyrethrnm indicnm — Kiku oil. Artemisia vulgaris — Oil of mng-wort. Artemisia drarunr-ulus — Esdragon oil. Artemisia, cina — Worniseed oil. Artemisia absinthium — Oil of wormwood. Artemisia gallica — Oil of lierb. Ai-teniisia barrellieri — (_)il of herb. Artemisia glacialis — Oil of herb. Erechthites hieracifolia — Oil of tire weed. Arnica montaiia — Oil of arnica flowers, oil of arnica root. Saussurea lapjia — Oil of root. Carlina acaulis — Oil of root. Spaei'anthus indicus — Oil of root. SPECIAL PART. 1. Oil of Male Fern. Origin. The anthelmintir- properties of the rhizome of male fern, Aspidium fflix mas S\v., are .said to be due in part to small quantities of a volatile oil, which \yas first prepared by Bock' in 1S51 by distil- lation with water vapor. The yield varies according to the season in which the rhizome is collected. Ehrenberg^ in 1893 obttuned from air- dried rhizome freshly collected in June 0.025 p. c. ; from rhizome collected in the months from September to November he obtained 0.04 to ().04o p. c. of volatile oil respectively. Properties. The volatile oil of male fern is a light yellow licjuid, with an intense male fern odor, and an aromatic, afterwards burning- taste. It is readily soluble in ether and absolute alcohol. Its specific gravity lies between O.H.j and 0.8(). Most of the oil boils between 140 and 2.j(>°. Above this temperature decomposition takes ])lace and dark colored products distil over. Composition. 2 Besides free fatty acids (])rinci])ally butyrii- acid) oil of male fern contains the hexyl and octyl esters of the fatty acids from bntyi'ic acid upwards. ])robably up to pelargonic acid. The substances to which the peculiar physiological ac'tion is due have not yet been isolated. 3. Oil of Angiopteris Evecta. Tliis fern, Angiopteris evecta Hoffni., yields an aromatic oil, said to l)e u.sed in the South Sea Islands for perfuming cocoanut oil (Maiden-^). 3. Oil of Polypodium Phymatodes. I'olvpodium jihyiiintodes L. (Pleopeltis pliymatodes (i. Mciore) like the above fern yields an oil also said to l>e u.sed in the Sciutli Sea Islands for perfuming cocoanut oil.'^ 1) .Arch. il. Pharni., lir., j>. 262. 3) K.sefnl niitive plunts of Aiislr., p. ■2r,'A. 2| .\irh. a. Phai-m., 2.'!!, p. ?A7,. 226 S/in-inI Piirt. OILS OF THE ABIETINE.^. Turpentine Oil, Pine Tar Oil ("Kienol"), and the Pine Needle Oils ("Fichtennadelol"). Thp term turpentine oil is applied in a mure restricted sense to the product obtained by distillation of turpentine with water vapor. "Kienol" is the product obtained by the dry distillation of coniferous roots rich in resin. The name turpentine oil. in a more g-eneral sense, is sometimes applied to these oils also, but this use of the term should be avoided. The oils obtained liy the distillation with water vapor of the leaves or one year old cones of various conifers are grouped under the (.•ollective term of pine needle oils. As to chemical composition, the oily distillates of the turpentine, the wood, and the leaves have in common one characteristic constituent, viz. pinene. The turpentine oils proper consi.st almost exclusively, the l^ine tar oils very largelj^ of this hydrocarbon ; whereas in the pine needle oils the place of the pinene i.s frequently taken by limonene or o-xygenated substances, notably bornyl acetate. Turpentine Oils Proper. History. The oils obtained by the distillation of the oleoresins of various Abietineip were known to the ancients as cedar oil (ina-o-iXaiov)'^ and later became known as turpentine oil. The oil as well as the resin, the colophonium, were used by seafaring people. Taking into consider- ation the perfection early reached by the Chinese and Japanese in the preparation of varnishes and lacquers, it may be supposed that conifer- ous oils were distilled a.nd used hj them. However this may be. the oils of the Abietinea? obtained in a crude manner have evidently been the first volatile oils that found commercial use and technical application. The name turpentine oil seems to ha\'e been introduced during the period of Greek civilization. Like the older synonyms (cedar oil, etc.) it apparently was used as a collective term. It is of Persian origin, ^ and may have been derived from the Cyprian specie.s Pii^tacia tere- hiiithus L. As far as is known to history, the preparation of turpentine oil probably had its origin in the Caucausus and its south-western 1) Herodoti, Historlae, Lib. II, p. S3. — Dloacorides, De mat. meil.. Lib. I, p. 34. Editio Kiihn-Spi'enftel, 1829, 1. p. 93. — riinius, .N'aturalls historiae libi'i., Lib. 15, cap. i; — 7: and Lll), 16. cap. 22. ■■^1 Fliicliift'er, PliarniacoKnosie, p. 77. 0;7.s of the Ahiftine.-p. 2S7 8piirs. lu central. Europe it became known dni-ing tlie middle ag'es, womewhat later also in northern Europe. The North Americ-an industry had its origin in the dense and extensive pine forests (jf the >Soutli Atlantic States and developed in the beginning of the eighteenth eentury especially in Virginia and Carolina.' Inasmuch as the crude turpentine oil found little oi- no use in either household economy or in religious rites, it is but seldom mentioned in early literature. Attention has already been called on pp. 5, 20, 21, 22 and 51 to mentionings by the older writers. Since its introduction into medicine, the mediaeval works on distillation and materia medica make mention of the oil. In addition to the references by Villanovus and Lullus, who lived in the thirteenth century, to which attention has been called on pp. 20 and 21, mention is made of oil of turpentine by the following writers of the fifteenth century: Saladinus of Asculo^ and the canon .lohann of Santo Amando of Doornjrk.;^ during the sixteenth century by Walter Kyff,-"- Coni-ad Gesner.s Joh. Baptista Porta,^ Valerius Cordus'^ and Adolphus Occo.s Attention ha.s already been called to the synonymous usage during the seventeenth century of the designations of alcohol and turpentine as aqua ardens and spiritus. The name Spiritus tere- binthinae has maintained itself as a popular term up to this time. As hnile aetherfe it seems to have been first designated in the year 1700. The early observations made in connection with oil of turpentine concerned its behavior at low temperatui-es. hji early as 1794 Margueron" claims to have observed that the (jil. when reduced to a temperature of — 22° K. solidifies to a crystalline mass. Crystals had already been observed by Geoffroy in 1727 in the neck of the retort while distilling the oil. In conformity with the practice of designating- as camphor all solid substances separating from volatile oils, these needle-like crystals, presumably pinol hydrate, were called turpentine camphor. 1) Peter Kalm's Reise, etc., vol. a, pp. 418, 556; vol. 8, pp. 29.3, ,305, 52.3. Schiipf, Reise, etc., vol. 2, pp. 220, 22.3, 273. Michau.x, Histoire des arbrew, etc. 2 1 Saladini Asculanl, Compendium, etc. 3) E.xpositio .Janis de Santo Amando. *) Eyff, Neu sross DeHtillirbuch, etc., tol. 180. = ) Ein kostlicher tlieiirer .Schatz Kuonymi Philiatri, vol. 1, p. 2.38. ^) Gio. Batt. Portae, Magiae naturalis. 7) Dispensatorinm Noricuni. 1546. 8) Pharmacopoea pro Eepublica Augustana. 1.j64. 9) .Journ. de Chim. et de Phys., 2, p. 178: Crell's Chem. .\nnal., II, pp. 195, 310 and 4.30. 22H Special P.iH. While making the socalled Liquor antiirthrjticii.s Pottii. in the preparation of which hvdrogen cliloride is passed into turpentine oil, the apothecary Kind.i of Eutin, in IHO:! obtained a. solid crystalline mass- which he considered to be artificially prepared camphor. This compound was examined by Gelilen^ in 1819 and hj Dumas-* in 18;5>{. Tlie first elementary analysis of the oil was made by Houton- Labilliardiere^ in 1817. In the same year this oil served as the first volatile oil of whidi the angle of rotation was ascertained. OEiftiN. The various species of Pinus, Picea and Abies. (A the fannly Piiiacfae, growing in the tem])erate zones, contain in special ducts under the bark an oleoresin, which in some species collects in cavities. If the <-and)ium under the bark is wounded, (.>r if the cavities are tapped, the oleoresin exudes, sometimes turbid, sometimes clear. This cdeoresin, whidi since antiquity has been known a.s turpentine, is a solution of resin in volatile oil. This solution is mostly rendered turbid by the intimate admixture of aqueous sap. Even when exposed to the air it mostly rema,ins turbid and frequently congeals to a. granular or cr\'stal- line, honey-like maiSS. This turpentine, when distilled either by itself or with water vapor, yields the turpentine oil ; and there remains a residue which, when remolten and strained, constitutes rosin or colophony. In formei' centuries, oil of turpentine— most likely in pai-t also cedar oil — was distilled in the eastern countries bordering on the ilediter- ranean, e.speciidly in Asia Miiioi'. When, with the develoi)ment of the arts and industries as well as with that of navigation, it becjime more important arid found wider application, greater advantage was taken of the coniferous forests in the more northern European i-ountries. The prinei])al producers were, and are in part to-day, the central European mountainous sed-ions, rich in conifers, from Hungary and (ialicia to Spain and Portugal; also the large coniferous forests of Russia, of eastern (iermany, arid of the southern provinces of the Scandinavian counti-ies. In the course of the previous century. North America has been ailded with its api)arently inexhaustible coniferous forests, and with its turpentine industry that sm-passes that of all other c(_)untrie>^. In spite of the econ(nnic waste of two centui-ies, Americ-i still is .-iml, no doubt will continue to be the in-inci])al producer of these artiil(>s of commerce. 1) ^'rommMdorff's .roiini. iler Pharni., ll'i, p. 1;J2. 2) rineiie luoiiohydrochloride. (.'loHiyCl. ;'i Oehlen'H allgeni. .Junrn. f. d. ('Iiein.. (_1, ]>. 4(>2. •4) .^n^. de Chini. et Pliys., IT. ."iLJ, ji. 41)1); Liel>ig'.s Aniialeii, 9. p. .-,(•> -'■') .JoTlrn. de Phariiiacie, II. 4, ji. 't. Oils of the Ahietineir: 239 With reference to geographical origin, the Amei-ican and Frenrh oils only come into consideration in the world's commerce. The (jther commercial l:)rands have only local significance. Genekal Properties. Freshly distilled turpentine oil is ;\ colorless^ limpid liquid of a peculiar odor whi(_'h varies somewhat ai?cording to its source. The French oil, e. g. i-eminds somewliat of juniper ;i,nd has n, finer and milder odor than the American oil witli its decided terehin- thinate odor. The sharp odor of old oil is said to be due to an aldehyde,! C'loHKiOg, which is supposed to be formed by the exposure of the oil to the oxygen of the air. Turpentine oil is volatile at ordinary temperature. During eva|)o- ration, a part of the oil resinifies, taking up oxygen. The residue, whirh is .sticky at first, gradually takes on the consistency of rosin. Owing to the presence of traces of free formic and acetic acids, crude oil of turpentine has a faint acid reaction. For this reason it has to be rectified witli milk of lime for certain purposes. When air is not sufficiently excluded, oxidation products with an acid reaction are soon reformed. Of physiological interest is the fact that turpentine oil, when taken internally, or when the vapors are but inhaled, imparts to the urine a peculiar violet odor. This peculiarity is shared by all pinene-containing oils. Other terpenes do not possess this property. The inhalation of the vapors of turpentine oil for a. longer period produces an unpleasant affection of the kidneys known as painter's disease. Solubility. Turpentine oil is ditficultlj^ soluble in alcohol, especially in dilute alcohol. Owing to this property, it can often be readily recog- nized when added to other oils as an adulterant. In the course of time, however, the solubility of turpentine oil in alcohol undergoes (consider- able change. Whereas the solubility of most oils diminishes with age, that of turpentine oil increases. 2 To effect a clear solution of fi-eshly distilled oil, more alcohol is necessary, than for an old oil which ha,s been exposed to the air. The plausible explanation for this observation lies in the formation of more readilj' soluble oxygenated compounds. M If, according to Schiff (1896), the oil from which the aldehyde has been removed l)y shaking- with sodium acid sulphite solntion, be distilled in an atmosphere of carbon dioxide, an almost odorless product is obtained. The odor, however, is again rapidl.v developed when the oil is exposed to the air. Chem. Ztg., 20, p. 301. 2) A normal American tvirjientine oil which originall.y was soluble in not less than Ti p. of 90 ]>. c. alcohol, after standing seven weeks gave a clear solution with 3 ]>.; French oil, which had been standing for four years in a bottle that was not conipletel.v filled, gave a clear solution with but 1 p. of 90 p. c. alcohol. 2;!(t Sjipcial P;nt. Oil account of thi.s cliang-eabilit.y, little .stress is to be laid on the solubility as a. test. In general, a good turpentine oil will be soluble in from 5 to 12 parts of OO p. c. alcohol. Solubility of turpentine oil in alcohol of different strength according to Ledermann and Godeffroy.^ Variety of On.. Strength of alcohol in percentage by volume 70 80 85 90 95 parts requisite to effect solution: 1. Frencli, crude 6G 2. French, rectified | 80 8. American, crude i 56 4. American, rectified ^ 60—64 5. Austrian, crude — 6. Austrian, rectified , — 7. Pohsh ("Kienol") ' — 8. Russian ("KiiMK'il" ) : 4!) 18 16—17 20 17—19 16 14 12 12 12—14 i;i 11 6.5- ;— 6 G 8 5 5.6 2 2—2.4 2 2.2 3 2 Turpentine oil is soluble in almost any proportion in ether, chloro- form, carbon disulphide, benzene, petroleum ether, glacial acetic acid, also in the fatty oils. When mixed with other volatile oils, turbidity occasionally results. Turpentine oil is an excellent solvent for fats, resins and most varieties of caoutchouc. BoiLiNc; Point. By far the greater portion of turpentine oil. namely from 7-5— 80 p. c, boils between l.',.") and 1(52°. Above 1(52° the meivury rises rapidly a.nd there remains in the flask a. soft, colophony-like resin. Concerning the quantities that distill over at the vnrious temperatures, also the specific gravity and rotatory power of these fractions of rectified Americnn turpentine oil, Kremers2 has recently made a detailed report. (.)n account of the oxiilatiou and polymerization products formed, the boiling point of a resinified oil lies considerably higher. Of the pine tar oils also a, larger portion boils above 1G2°, because of the presence of dipentene and sylvestrene. Rotatory Powek. An important distinctive feature of the several oil varieties is their different rotatory power. French oil is always strongly laevogyrate, American o\\ mostly faintly dextrogyrate and but seldom laevogyrate. Austrian oils have been found to be dextro- as well as laevogyrate. Tlie angle of rotation is given in connection with the respective oils. 1) Zeitschr. <1. alig- ht Pharin. TtevuM\-. iist. .\iit.-\er., l.j, |>. .3S1: .Fahrt-Klier. f. Phai-i 1.-.. p. 7. 1877. p. ;ill4. Oils of the Ab'wtineii'. 281 Influence of Air and Lkiht. It is a well-known fact that turpen- tine oil when allowed to stand in open vessels undergoes rapid change, especially if water is present. The oil becomes viscid, the specific gravity increases and the boiling point rises, the solubility in 90 p. c. alcohol increases, the originally neutral oil becomes acid, resinifles, it becomes "rancid" as this change is technically designated. i Formerly such an oil was termed ozonized,' because it acted like a strong oxidizing agent. Most of these changes are referable to a slow oxidation caused by the oxygen of the air. Kchoenbein 2 had assumed that in this process the oil was charged with ozone, the oxygen of the air being activated by the turpentine oil. It was shown later, however, by Kingzett,* Bardsky,* and Papasogli-"" that the turpentine oil contained no ozone" liut hydrogen peroxide. 1) A normal American turpentine oil, Hp. ^v. <).807, which had been kept in a stop- pered but partly filled bottle, after standinfi' Ke\-en weeks had a sp. ^r. of 0.897. It wa.s now soluble in 8..') i>. by volume of 00 p. e. alcohol, whereas the original oil had required 6 p. to effect a clear .solution. Another sample of American (jil, after having stood for some time had acquired a sp. i^Y. of 0.91.^ and j?ave a clear solution with but 3 p. of 90 p. c. alcohol. A French oil, which had been kept for four years in a i>artly filled but well stojj- pered bottle, had undergone the following changes: Orifiiiiiil niiniiul oil. Ttie sjiiie after 4 yeai's. Specific gravity 0.871 1.009 Optical Rotation — 29°55' — 19°18' AA'hereas the original oil re(iuired 20 p. by volume of 80 p. c. alcohol to effect a clear solution, the oxidized oil was soluble in 1 p. of the same alcohol and was mis- oible In all propoi'tions in 90 p. c. alcohol. 2) Liebig's Annalen, 102, p. 183. 3) .Jonrn. Chem. Soc, 27, p. 511 ; Pharm. .Journ., Ill, ,'5, p. 84; ibidem, 6, p. 325; ibidem, 7, p. 201; ibidem, 9, pp. 772 and 811; ibidem, 20, p. 868; Ch. N., 69, p. 143; comp. also Robbins, Pharm. .lourn.. Ill, 9, pp. 748, 792, 872. According to Kingzett. tlie ultimate products of the slow o.xidation of turpentine oil, camphoric acid and hydrogen pero.xide. do not result directly Peroxide of camphor, C10H14O4, is first formed which, in the presence of \vater, breaks up into camphoric acid and hydrogen peroxide. C10H14O4 + 2H.,() = HjOj + CioHieOi CaiufilT'E- peroxide WatL-r Hy) An oil. sp. gr. n.sii+, after having been treated in this manner for 44 hours had a sp. gr. of 0.949. Kingzett also ob.sei'ved a considerable rise in the boiling point. Oils of the Abiethieiv. 233- By the action of direct sunlight on moist tm-pentine oil in the presence of air, or better still, of oxygen, pinol hydrate,CioHi80o, results. According to the solvent used, pinol hydrate crj^stallizes in laminae or needles. Its inactive modification melts at 131°. i Composition. The first elementary analysis, referred to on p. 41, revealed the fact that turpentine oil consistis of hydrocarbons CioHm. This was verified by later investigations, which also showed that different oils reveal physical differences in so far as some of them turn the plane of polarized light to the left, others to the right. Berthelot^ designated the laevogj'rate hydrocarbon terebenthene, the dextrogyrate one australene. Inasmuch as the two modifications are merely physical isomers, but chemicaly identical, Wallach^ introduced the terms 1- and d-pinene. Since pinene is one of the most labile terpenes, it is not surprising that some of its decomposition products are formed during the pro- duction of turpentine oil, and thus get into the oil. As alreadj^ stated, the oil c-ontains traces of formic and acetic acids, also resin acids. At liighej- temperatures, these act on the pinene so that dipentene and presumably polymeric terpenes result. At least both are found as constant companions of the pinene in the turpentine oil. Certain observations and indications render it probable that camphene and fenchene belong to the normal constituents of turpentine oil. Since the boiling point of both of these lies very close to that of pinene, a direct proof to which no objection can be raised is impossible. Nevertheless, it maj' be a.ssumed that the indirect proof for the presence of camphene has been furnished. Armstrong and Tilden* found camphene in the so-called terebene, the product resulting by the action of concentrated sulphuric acid on turpentine oil. The.y assumed that the camphene resulted ai-cording to a reaction analogous to the one by which it can be obtained from pinene hydrochloride, a possibility not to be denied off-hand. Power and Kleber," however, consider it more probable that the camphene is contained originally in the oil, anrl that its presence becomes notice- able only after the destruction and removal of the pinene. The results of the investigation by Bouchardat and Lafont" also seem to permit a similar conclusion. They heated French turpentine oil 1) Liebig''s Annalen, SO, p. 106: ihidem, 3) Liebig-'s .\nnaleii, 227, p. :iO0, •2~A^, p. .313; Joilrn. Chem. Soc, 59, p. 815. 4| Berichte, 12, p. 1758. 2) Conipt. rend., 55, pp. 496 and 544; •<) Pharm. Kundschau, 12, j). IC,. Lieljig'.s Annalen, Suppl. II, p. 226. 6) Compt. rend., 113, p. 5.~>1. 234 SjiMihd I'.irt. with benzoic acid auliydride for fifty hours. From tlie product of reaction tliey isolated eamplieue, also esters of isoborneol and fencliyl- alcohol, whose formation is probably due to the presence of camphene and fencheiie. The same investigators i obtained, by the action of sulphuric acid on French turpeiithie oil and the subsequent treatment witli alcoholic potassa, two potassium salts of the composition C111H17OSO2OK, which upon hydrolysis with acids yielded borueol and potassium hydrofien snljihate on the one hand, and 1-fenchyl alcohol and the same potassium salt on the other. The formation of these salts likewise indicates the presence of camphene and fenchene. The ])resence of 1-camphene in American turpentine oil was shown by Schimmel & Co.- in the followinji' manner. By treating fraction IGU— 1(51° of American turpentine oil (sp. gr. (X.S()9: [«]d = + 1° Ki') with glacial acetic acid and sulphuric acid according to Bertram's method/^ isobornyl acetate resulted which upon saponification yielded isoborneol (m. p. of the phenyl nrethane derivative 138°). Inasmuch as pure pinene, regenerated from the uitroso cldoride does not yield isoborneol when treated in the saiue manner, the formation of isoborneol is explained by assuming the presence of camphene in the American oil. Adulterations. On account of its cheapness, turpentine oil has been used largely as an adulterant. It itself has been subject to adulteration with petroleum and resin oils. Petroleum. Common ilhnnimiting oil, also the lighter as well as the heavier fractions of petroleum have been used. Illuminating oil and the lighter petroleum fractions are recognized by the lowering of the specific gravity; also by the lower flashing point, which lies at •■!:!— ;!4° for pui-e turpentine oil. The heavier fractions of petroleum are not volatile with water vapor and, therefore, remain behind, when the oil is rectified with watei- vajjor, as n fiuorescent residue which is not affected bv concentrated nitric and suluhuric acids. Kocalled patent turpentine oils are frecpiently nuxtures of ])etroleuni products with turpentine oil or camphor oil. Sometimes thev are nothing but petroleum hydi-ocarbons brought upon the market under various fanciful names. Such designations are:^ (.'anadian tur]ientiue oil, patent turpentine, tuiiientyne, turpeuteen, larixolin, paint oil, and others. According to Dunwody,-"" mixtures of turpentine oil and 1) Compt. rend., 1:35, p. 111. 4| Pharm. rontralh., .3:(, jp. 131. •J) Berielit V(.n S. & Co., Oct. ls>)7, p. r)S. si Anicr. .Joiirn. Phin-ni., (12, p. 2SS. 3) .Jourii. f. prakt. Chcm.. II, 49, p. 1. 0;/.v of tlie Ahietjueip. 235 petroleum differ from i^ure turpeutiTie oil by their different .solubilitj' in 99 p. c. acetic acid. Absolute acetic acid (99, ."i to 100 p. c.) is said to be miscible in all proportions with petroleum as well as with turpentine oil. An acetic acid prepared by mixin ;! 2 " Solution pffected with acetic ac, (9. c. or more of jjetroleuin was present, the mixture is turbid and separates into two layers upon standing. For the quantitative estimation of the petroleum, the turpentine oil is oxidized with fuming- nitric acid and the residue, not iicted upon by the acid, is weighed as mineral oil. According to Burton' TOO cc. of oil are carefull.v cooled in a spacious flask connected with a reflux conden.ser and 300 cc. of fundng nitric acid are slowl.v added from a dropping funnel. The residual oil is washed with hot water and weighed. Control experiments with known mixtures slif>wed that the determination is more accurate for the liiglier boiling fi-acfions of petroleum than for the lower ones, for the latter are somewhat attacked b,v nitric acid. A petroleum product boiling at 250° .vielded 81,1 p, c, in place of .85 p, c; 1) According to the former official (.lirecticjiis for testinft- for pur[»o.ses of re^'enue, an oil \va.s to be regarded as pure if an iricrea.^e in temperature of 2.'^ C. resulted ^vhen the oil wa.s shaken Avith an equal volume of fuming h,vdroehlorir acid, or witli one volume of hydrochloric acid (1.12) and % vol. of English sulphuric acid. As was to be expected, this process frequently yielded nnrelialde results and, as a conseriuenee, was frequently criticised. 3) Chem. Zeitung, 32, p. s;-!4. 3) Chem. Centralhl., 1897, II, p. 4-4!i. ^) Amer. Chem. .Journ., 12, ii. 1()2. :236 SjiPfinl Pnrt. a petroleum product boiling at 75° yiflded 17.9 p. c. in jilace of 20 p. c; and' 28 p. e. in place of 80 p. e. A similar method is described by Allen i who employs 400 ec. of fuming nitric acid instead of 800 cc. for the same quantity of oil. Tlie older method of Armstronut as l>ecomes apparent from the rotatory power of turpentine mentioned later, the .-niKle of rotation observed in a 2.^0 mm. tube! 6) Compt. rend., 124, p. IMCT. Oils of the Altktinen: 237 under 60 mm. pressure and the residue remaining above 100° is examined witli the polariseope. The resi(_lue from pure French turpentine oil is laevogyrate ; tliat of an oil adulterated with more than 5 p. e. resin t)il is dextrogyrate. Zunei employes the refract ometer as a means of detecting resin oil. The oil is .submitted to fractional distillation, three-fourths being distilled over: the index of refraction of the first fourth and of the residue being determined. The differen(.-e in the two indices for a pure oil amounts to from 0.00;i." to (.1.004; in the presence of resin oil, it is larger and amounts to 0.00() for 1 p. c. of adulterant. Productiom and Commerce. AYitli reference to importance and value of production of turpentine oil, the United States of North America occupy the first position as is shown by the total arrivals at the principal staple ports : From April 1. 1896, to March 31, 1897: 16.5, .578 banvls; From Ajiril 1, 1897, to Mai-ch 31, 1898: 139.301 barrels. The barrel contains ')() gallons or about 1.50 k. If an average ]jroduction of 4.5(), 000 barrels per year is assumed, the grand total ^ will be (57, .500, 000 bbls., with an approximate value of .f7,. 500, 000.00. The consum]ition of turpentine oil in the ITnited Btates amounted to: From April 1, 1896, to ilanli 31, 1897: 111, .560 barrets; From April 1, 1897, to March 31, 1,S9H: 130,722 banel.s. Total export from the United States : 1891: 12,618,407 gallons = abt. 252,000 barrels; 1895: 14,652,738 " = " 293,0(-H) 1896: 17,431,560 " = " 348,000 1897: 16,820,000 " = " 336, (JOO Thirty years ago. North and South Carolina only came into con- sideration in the production and export of turpentine oil. The forests in tliese states having been largely exhausted, the industry has gone farther south. Thus, e. g. Charleston, S. C formerly the important pc)rt has ceased to export turpentine oil. The business has lieen trans- ferred to tliF ports Savannah and Brunswick, l)oth in Georgia. Savannah is the most imiiortant port in the world's market for tur- pentine oil. It has expoi-ted moi-e than one-half of the total America-n output. From New York turpentine oil is exi)orted priuci]ially in cases to nf)n-Euroi)ean countries. < 1) Coilipt. rent!., 114, p. 4!l(l. 2) Fo]- 150 years. 2.3.S Spechil Flirt. During the last tliree years the turpentine oil industry has largely (leveloped in Florida and Alabama. It is feared that Pensacola will l;iecome a strong competitor of the present ports. The most important European markets for Ameriean turpentine oil are : London. Import 1H96: 2t,940 tons = abt. Ki.l.OOO bbls. 1807; 25,140 " - " 108,000 " Hamburg. Import 189(5: 7,974,700 kilo = abt. .'•3,200 bbls. 1897: 8,008,100 " - '• .57,400 " Antwerp. Import 1896: 7,170,000 kilo = abt. 47,800 bbls. 1897: 6, 144, .500 " = " 40,963 " The market price of American turpentine oil is not only affected by supply and demand, but is frequently influenced liy speculations and, therefore, subject to considerable variation. In January, 1897, the price per 100 k. f. o. b. Hamburg was M. 48.50. It rose to M. 47.00- in the beginning of June, and dropped again to M. 42.50 by the middle of July. It again rose to M. 54.00 by the beginning of October, but dropped to M. 5(j.50 by the end (jf Sejjtember. Still greater were the variations in price in 1898. Beginning with M. 52.00 in January, the price gradually rose to M. 72.00. Of much lesser importance is the production of turpentine oil in France. Nevertheless, it is suffi(>ient to supply the demand of that ■ country for the importation of American turpentine oil has been made prohibitive by a duty of Fi-. 24.00 ].)er look. The industry is confined to the Dep. des Landes. The principal commercial centers are Mont de Moreau, Bayonne and Boi-deaux. Under these conditions Init small quantities can be exported- According to official statistics, tlie export of turpentine oil from France amounted to : 1896: 1,937,990 Kilo; 1897: 1,411,500 " Of these amounts Haniliurg rec-eived : Antwerp 1 896 : 430,100 Kilo 1897: 992,500 " 1896: 970 Oolli; 1897 : 530 " Oils of tlw Aliietiiwn'. 389 Qualitatively the Fi-eucli oil holds the first position aiiioiig- all eoiii- inercial brands and in the arts is frequently preferred to the Ameriean. Its market value is, as a rule, from $2.00 to f2.50 higher per 100 kilo than the American. Among- the commercial varieties of turpentine oil, the Eussian ' comes next ui importance. According to the records published in ''Die Produetionskrafte Russlands" (1808), a work is.sued by the Imperial Russiiin Ministry of Finance the value of the oil of turpentine annually produced in Russia is Rb.2 1,.-)00,0()(). The greatest part of this is used by the country itself. The industiy has its .seat in the gouvernements to the north of the Volga and in Poland. It is conducted on a small scale and ls in the hiinds of the peasants. The export amounted to: 188.5 : 160,000 Pud,= value Kb. 498,000. 1890: 29.5,000 ' 811,000. 1892: 365,000 " " " 826,000. 1893: 300,000 ■' " " 853,000. 1891: 258,000 " " " 717,000. Corresponding to the qualitj^, the commercial value of the Russian turpentine oil is much less than that of the American and French. It is indeed the poorest of all the commewiial varieties. The Ru.ssian import duty on turpentine oil of (iO kopeken - gold per pud, or of nearly .13.00 per 100 k. has the object of a duty for revenue only. In the Antwerp lists of imports there appears regularly for several years a Spanish turpentine oil. The importation amounted to : 1896: 2,64-1 Colli: 1897: 7,520 " ■t. American Oil (Spirit) of Turpentine. Oleiini Terebiiithiiiae Ainericaiinin. — Aiiierikanisches Terpentiniil. — Essence de Terebeiithiiie Americalne. History a>'d Origin. The enormous areas which were at one time and in part are to-daj' densely covered with pine fore.sts acquire their maximum luxury and broadest expanse in the South Atlantic States, 1) The figureK enumerated, in all probability, refer pnniarily to tiie pine tar oil oI>tained by destructive distillation. Whether turpentine oil projicr, obtained from turpentine, is at all made on a commercial scale in Russia is not known. 2) Rubel "= 100 Kopeken = abt.. 80f ; Pud = 16.38 k. L'-iO Special Part. from Virginia to the Gulf States, in the eastern part of Canada, in British North America and on the western slopes of the Pacific States. The first mentioned area, which is also the largest, comprises the states North and South Carolina, Georgia, and Alabama and within it there has developed the principal turpentine industry. Up to the middle of the last century the products of this industry wei-e tar and pitch which were used principally in ship building and as naval supplies and hence were termed "naval stores. "i The preparation of turpentine oil seems to have begun as late as the middle of the eighteenth century in North Carolina and Virginia. Professor Kalm, the Swedish traveler, who is known as a careful observer, and who explored the Atlantic provinces of the then British colonies from Quebec to Virginia during the years 1749 and IT.")!), reports concerning the preparation of tar and pitch only. 2 Later travelers and reports, first make mention of the preparation of turpentine, turpentine oil and colophony in Carolina. Among these are Dr. Johann David Schoepf, who traversed the Atlantic States from Canadai to Florida ^ in 178H and 17H4; also Francois Andre Michaux, who about twenty years after the longer stay of his father, the well known botanist Andre Michaux, traveled in North America at the beginning of this (•entury.-'' Up to the year 1820 the consumption of turpentine, turpentine oil and colophony was restricted to the linuted demands of the home industries. The exportation of oil and rosin to England was un- important. Up to l."> of the i/ivil war. the period of industrial and commercial .stagnation. Up to the year 1837, the opinioTi prevailed in Carolina that the pine forests to the south were not adapted to the production of turpentine on account of differences in eliniate and soil. In the year mentioned, . 09; also Pharni. Itnndschaii. 2, p. 1S7. 16 242 S])ei-i:il Part. turpentine industry in the S(jutlieT-n states thus developed unimpeded. With the establishment of ehe;ip means of transportation by rail and by water, all the conditions were fiiven for a prosperous <;rowth to the enormous dimensions (in whicli this industry is being- eondueted at jiresent. At best, the larger pine trunks can be made to \'ield turpentine for from I'l to 20 years liefore they are exliausted. Of late years, the exhausted trees are mi longer ai)an(loiied to wind and Are. but are taken to thp mills to lie sawed into logs and lioards; to p;iper pulp fm/tories ; (ir are cdnverted into chareoal. It is ti-ne that wnste, tlie i-leariug of forests and temporary ilest]-ui-ti(jn liy hre has driven the turiientine industry away from the coast into the interior. A diminution or exliaustion of the American turpentine industry, liowever, need scai-cely lie feareil. Not only does there still exist an enormous wealtli of pine foT-ests, but tlie i-emoved ti-nnks are replaced liy ninv shoots from tlie roots and also by more rational metliods of cultivation. Former methods of waste have not been with- out their lessons. Manufacturers as well as the general iiopnlation have become alive to the necessity of displacing formei- irrational methods and waste by more rational ones wiiich insure a continuation of the industry. The ]iines whicli pi-incipally constitute the largest forests of the Soutliern states and which are used in the manufacture r^f turi)entine are four in nmnlier: Pimis p.-ilustiis ililler ( /-". rUz,sf7Vi/;'.s Michaux), long-leaved or Southern ])itcli pine, wliich is the most important in this industry; P. t;iefJ;i L., Loblolly or Rosemary pine; /'. hetPi'Ofiljylhi Klliot (P. cubf'u.'iis Griesebach), Cuban pine. Swamp pine. Slash pine; and /', echimita Miller (P. mitis Micheaux), short^leaved yellow ])ine. Preparation. The method of prodw-tion is in general the same every- where. On account of the extent and density of the jiine foi'ests. the size and diameter of the trees, the larger yield due to a favorable I'limate, the hack of foi-est cultivation and the ab.sence of control, the methods employed were those that insured the largest yield and quickest returns and had but little hee<:l of the permaneni'e of the forests. The operation, mostly by negroes, of the turpentine farms, beg'int> in the first dry days of spring, as a rule in April. The trees are "boxed" about 1 to 1% foot above the ground (diagonally across the trunk of the tree). The length of su(;h a box is about 14 inches, its greatest depth 6 to 7 inches, so that it has the capacity of more than a quart. Tf the trunk is very thick, a, similar "box" is sometimes cut on the other side of the tree. Oj7.s oI tlin Ahii'tiin':p. 243 As scioii as the sap bej;ins to tiow in spriiii;-. a strip of 1);h-1-; 2 iiiclics wide ami S inches h)ng is renioveil from the trunl< at either end of the Ikix ("cornering"). Then the surface above the box l»et\veen the two bare strii;)s is deprived of its bark down to the splint (■■hackinc-," ■'cliip- liinji"). The exudation of the sap soon begins and varies with the temperature and the formation and secretion of the saji ("bleeding"), the ex])osed surfaces above the lioxes are increased every one or two Bi:(HXXI\(; Tt) WoitK IN A \'lRliIN FcRKS weeks. In this manner the i-hipped surface above the Ijox is lengthened or widened or both (fig. -"iH) as long as warm weather lasts, mostly to the end of October. In the beginning and during very warm weather, tlie lioxes are filled every 2 to -i weeks and are emptied by means of a, tiat ladle into wooden pails (fig. ")9) and from these into barrels. With the advent of the cooler sea.son the exudation ceases. The exposed surfaces and boxes are tlien freed from adhering and dried oleoresin ("scrape") and allowed to heal or thev are again cut during the next spring. If allowed t(.) heal, 2+4 Sjifi-inl I'lirt. tliH operation of bleediiiji- is pHrforiiied on anotliPi- [lart of tlie tinmk dnriiig the following- or the third spring. The turpentine farms are usuallv laid out so as to supplj^ one copper still with a capacity of HOI) gallons or 20 blils. of turpentine. For the operation of this, 4000 acres of forest with good growth are neces.sary. This is divided into 20 lots, of whi(;h each contains about 10,000 boxes yielding olecresin. lna,sinuch as many trunks according to their SlllAr'INIi AMI DlCriNC l.\ a TUHr'KXTI.VIC OUCHAKI Trpe t(i the ris'lit .shinys scarirtefl Kiirl'ai.'t'. >eeu]:)yiug an dia,meter contain two, tliree, sometimes even foui- bo.xes. the above number is distributed over about 4— .")000 trees usuallv oo area of two acres. With a i-ational treatment the yield from 10.000 bo.xes for each collection amounts to about 40 to -"iO bbls. of turpentine of 2.S0 lbs. each. During the tirst years, and before the capacity of the trees ha-s beeu i-educed by excessive bleeding, the avei-ige yield of a turpentine fai-m is Oils of tlie AbietindP. 245 nboiit 270 bbls. of 280 Ills, each of dip tnrpentiiip ;iiid about 70 hl)ls. of scrapings at tlie end of tlie season. Eaeli barrel of dip turpentine yields about 7 gal. of oil upon distillation, the scrapings about H gals. The total yield of a farm, therefore, amounts to about 2,200 gals., or .")() bbls. ® 45 gals, of oil, and about 260 bbls. of rosin. During the first two or three months the collected turpentine is almost white and constitutes the best quality, •'virgin dip." This brsmd is brought into the market as "water white" and "wimlow glass." Inferior, more or less yellow brands are marked X. or M. K. Minor shades are indicated l)y the various letters of the alphabet, so that A indicates the poorest, and N the best grades of the varieties next to the W. G. During the second year of the operations, the yield of tlie dip is about 10 bbls. less than during the first, whereas the scrapings increase to about 120 bbls. The quantity of turpentine oil during the second year amounts to ab(jut 40 bbls. of 4-5 gals, each, and about 200 bbls. rosin. The quality of the oil is the same as that of the first; the rosin, however is mostly darker. During the third year the yield of turpentine diminishes. The continued use of the same cups and exposures, and the annual inc-rease of the latter bring about a deterioration of tlie oleoresin, due to evaporation and action of the air : a smaller yield of oil is obtained and the quality of the roshi is poorer. It is more advantageous, there- fore, to allow the trees to rest for several years and then to tap them at a <:liHerent place. As has already been stated, the distillation of the tuT-pentine has been conducted for years in coppei' stills on the larger tui-)ientine farms. In the course of the distilliition, and after the still has been hented, a thin but continous stream of water from the liigher placed condenser is allowed to flow into the bod.)^ of the still until the distillation is ended. The liquid rosin is allowed to flow off through iin exit tube at the bottom of the still. It is sti-ained through wire sieves anil filled into barrels for shipment. The total average output of a farm of the described size, wliicli is operated mostlj^ for four years only, is about 120,000 gals, fif tiirpentine oil, 52,000 bbls. of rosin of first cjualitj', 4,000 bbls. of i-osin of second .urade, and 2,400 bbls. of poor quality (Mohri). i| Pharm. ItunilKchiui. 2, pp. 16H. 1S7: 12, p. 211. 246 Spechil Part. With the wasteful methorls still larg'ely in vog-up, and in order to obtain the largest possilile iniinediate returns from such a venture, the timber, after four years' production of oleoresin, is cut either entirely or in part, provided a saw mill is located in the neighborhood or the wood can be disposed of to advantage in some other way. Each acre yields about 25, OdO— :!(),()()() ft. of lumber or riO— (id cords of fuel wood. According to the Forestry Division of the U. S. Department of Agriculture, the area involved in the turpentine industries of the Southern states during 1K!)(> amounted to 2. ;!()(), OOU arres of pine forests. Of late years, tlie distillati(.)n of the encjrmous wastes of the saw mills lias increased largely. For this purpose the stiw dust and other waste, esperiiilly of the older, dying trees are u.sed. While gradually drying, the lower jiortion of these trees accumulate a larger amount of oleoresin. This wood, permeated by dried oleoresin. is known as "light wood" and is used for underground constructions, such as rail- road ties and as fuel for boilers and locomotives, ['pon distillation, it yields about 2 to 2}{, p. c. of pine ta-r oil, also tar, pyroligneous acid, pitch and i-haT-coal. The yield from (iOO llis. of fairly dried wood rii-li in resin from Pinu.s iiui^triilis is about 21 to 22 lbs. of tar oil, '.».") lbs. of pvrolig- neous acid, ^~>0 lbs. of tar, and 127 llis. of charcoal (MohrM. Properties. The s]iei-ific gravity of crude Amerii;-an turpentine oil lies as a rule between O.ISGS and O.STO. However, lighter (sp. gr. O.S.'.S) as well as heavier (up to <»..S77, Kremers^) oils occur. Freshly distilled or rectified oil is mostly lighter than the crude or old oil. \Mien frjictionally distilled, abcmt S.") p. >•. !°. Inasmiich as the American species of pine vield dextro- gyrate-' MS weU as laevogyrate^ oils, the rotatory power of the com- mercial oils necessarily varies. Accoi'ding to the prevalence of the one oi- other species at the locality of proihiction it may be more or less strongly dexti-ogyrMte. or even laevog.vriite. Armsti'ong"' observed in 1) Pharm. Riindscluni, 2. ]>. lU'.i. -) Pharni. Iteview, 15, p. S. ■*) [''Ji' of the oleore.sin from I', pnlu.'^tris — l;!.(;r>.'i'^, [«]i. of the oil from P. iniliistris - + 2:!. '.13°, ['''-]i. of tlie oleorewiii of P. cnhfitsis ^ — .S2.428^. I'^-l*' of the oil fr(jni P. cuben^is -^ + 0.1)^. V, Kre nei-H, Pharm. Riind8chan, 13, pp. 1 ;{.*, 1.3f;, i> .icoording to Long (Journ. Amer. Cheiii. Soc, 16, p. S44 ; .\bstr. ('hem. Centrallil.. 1H05. I, p. lot!) the oil of Piniis glabra in ntvougl.v laevogyrate, a,, -= :i\.r,° to 35° .^ccoi-ding to the same author (C'hem. f'eiitrallil.. lSi)3. I, p. S3.5) the oil of Piniis imluxtris is also laevogyrate. This is i-ontrailiotor.v to the observations Tuade h.v Kremers (see footnote 3). 5) Pharm. .[ourn.. III. 13, p. 5,S4. Oils of the Alnetwfiv. 24T lHH;i that the rotatory power of 28 .saniples from Wilniiniitou varied from +iy°°-t()' to —2°.",', 5. French Oil of Turpentine. Olpiim Terebiiitliiiiae Uallioiiiiu — Fraiizosiselies Terpentiiiol. — Essence de Terebeiitliine Fraii(;aise. Origin and Preparation. The larger part of the turpentine oil pre- ])are(l in Europe is obtained from the turpentine from the Pin mnritime, Pinus pinnstfr Solander (Piniis mnvitinm Poiret) and is obtained by steam distillation. This tree, which attains a. height of -10 m., thrives best along the westei-n half of the southern shore of the Mediterra-nean as far as the Bay of Biscay. The pri)du(:tion takes place principally in the western French dune districts (Lundes) of the Departments de la Gironde and des Landes. The principal commercial centers are Bordeaux and Bayonne. In order to obtain the tur])entine. one or two narrow nrjtehes [variv) down to tlie splint are cut near the base of the trunk in spring when the sap begins tf) rise. The.se wounds are made -W to 40 cm. long and 10 cm. wide. Below the notch a tin or earthenware vessel is fastened so that the rjleoresin as it exudes flows into it. According to temperatui'e and duration of the flow, the incisions a,re extended upward from time to time (jiiii;igf). so that, in the course of 4 to •' years they constitute parallel stripes, 4 ni. in length, along the trunks of the trees. Only after the abandoned incision (fniTP) has liealed, is another made on the opposite side in the following spring. The vessels in which the turpentine collects are emptied whenever necessary. The soft turpentine (gfinme) is Tnostly distilled in the neighborhood of the ]ila.('e of col- lection. That which has dried along the carvfn is T-emoved in fall and brought as galipot {ba,rra,s) into the market. As a rule the trees are tapped (gt'inwrige) oidy after they have reached an age of 20 to 30 years. Under rational treatment, a normal tree can then be used for the production of turpeutuie for almost 100 years. Trees that show signs of exhaustion, after a final tapping made in such a manner as to produce the largest yield possible {geminagv a inorte] are cut down at the end of the season for the wood. The trees are reproduced by shoots from the roots. 100 Trunks of the Pin mnritime in western France, on an average, yield 360 k. of turpentine, which upon distillation yields 1.") to 18 p. c. 2i8 Sppr-inJ Part. of turpentine oil.i When the turpentine is to be distilled, it is first sufficiently heated in casks so that it i-an be strained through a wire sieve, whi(-h removes fragments of bark and leaves, into the (iopper stills of about 800 liters capacity. The distillation is conducted over direct fire while a current of steam is passed into the still. The residual resin {hnii) is transferred to barrels and brought as j^ellow c-olophonium into the market. Properties. The specific gravity of P^rench tui-pentine oil- varies from O.S.'if) to O..S72. as a rule from O.SG-o to 0.876. Formerly higher values were occasionally given. The optical rotation was first ascer- tained by Biot in 1818. Later the following angles were observed by different investigators: «□= — 20° to — 4()°;3 — 8.H° to 88° (Pereira.* 1845); —80° to — :iO°80' ( Armstrong.s 1888); and [a]D = — 89°.50' (Lafont," 1888). In its other properties as well as in its composition, the French turpentine oil agrees with the American oil. 6. Austrian Turpentine Oil. Oesterreichisches (Neustadter) Terpeiitiniil. Ohkiln and Preparation. The turpentine industry in Austria is confined principally to the "Wiener Wald." In the vicinity of Moedling' Voeslau and Neukirchen, Pinus laricio Poiret serves for the production of tui-pentine. The method pui'sued is the same as that in America, but trees at. least .50 years old only are tapped. Near the base, a <-avity is cut into the trunk, into which the exuding oleoresin flows. Above this cavity {GiH.nclel) the bark and splint are gradually removed by means of a bent hammer up to a height of about 1."") ini-hes. From time to time, when necessary, the turpentine is removed. During the following spring 1~> inc-hes more of bark are removed above the olil wound. Tn order tliat the oleoresin may not flow too slowly and get dry. n gutter is made from the newly exposed surface to the cavity below. 1) Comp. under BiblioftTrtjiliy : Petzlioklt, p. SS ; Curie; Mathieii, p]>. r,;-{7 — 540: DesnoyerK. 2) The Spaniwh turiientine oil mentioned on ]^. 239 can not be distingnislied from the French. A .sample of this oil exainined in the laboratory of Schimmel & Co. ]ios«eB.sed the following properties: sp. gr. 0.S478 ; [«Ji, = — 28°4:'; soluble in 7 parts of iK) p. e. alcohol. Upon distillation the following fractions were obtained : 1.57 — 1.590. -,0 p. c; 1.5!)— llil', 2S p. e.; 161—1015°, 10 p. c.; 16(5—170°, 2 p. c.; 170—190°. 5 p. c; residue r-, p. c. ■■') Bericht von S. & Co., April 1M!I7, 11. 47. , 4) I'harm. Journ., I. .j, p. 70. ' 5i Ibid.. Ill, IH, p. .584. «) Compt. rend., 106, p. 140. Oil.s oftlw Abiptinew. 249 The present annual prdduetion of turpentine oil in the "Wiener Wald'' is said to be about 4,000 ewt.i The principal romniercial center of this industry is Vienna (Neustadt). Properties. In the laboratory' of Schiminel & Co. a single sample of oil of unquestionable source was examined. 8p. gr. 0.866; angle of rotation +;-i°46': it was soluble in 6 — 8 parts of 90 p. c. alcohol. Upon distillation the following fractions were obtained : From 159—159°, 21 ]i. c. ao = + G°ln' " 159— 160°, 5(; " "- + ^°-2r/ " 160—167°, 18 " " = + 0°ls' Rf'sidut', 5 " Ledermann and Godeffroy- observed laevo-rotation in two Austrian turpentine oils. Taking into consideration the above, it would seem' doubtful as to whether they had Austria,n oil or not. 7. Galician Turpentine Oil. Of this oil, of which the botanical .source is unknown, but one sample appears to have been examined. It had a sp. gr. of 0.863; i/.u = + 17° 18'; and wa.s soluble in 4.."'> parts of 90 p. c. alcohol. Upon distillation in a Ladenbnrg fln.sk the following fractions were obtained : Up to 162°, 7 p. c, «D = +17° 15' fi-oiii 162—165°, IS ■' •' = +19°4' " 16.5—169°, 38 " " = +18°7' " 169—173°, l;! " " = +17° 28' '• 173-177°, 10 " " = +15°.T7' ■■ 177—210°, 12.5 " •• = +12°2' Residue, 1.5 " Judging from the relatively large amount of liigh ltf)iling fractions, the conclusion .seems justified tliat this oil must have a ilifferent com- jjosition from tliose previously enumerated. 8. Turpentine Oil from Venetian (Larch) Turpentine. History. -Larch tui-pentine was known to the Romans. It is men- tioned in the writings of Vitruvius,^ n contemporary of Caesar, also in those of Dioscorides, Pliny,* and Galen. During the middle ages, larch turpentine was one of the most highly prized balsams. The name 1) Accot'dinp: to a coiiiiminication by A. Ki-eniel of Vienna. 2) .lahresber. il. Pharin.. 1877, ]J. :-iit4. 3) Vitruvius, De architectnra, ^^ol. 2, j). \i ; DitjRCoriileK. l)e mat. meil., vol. 1. ii. O.'i. 4) Plinius, Historiae de jjlantiB, p. .'7.". '250 Special Part. Venetian turpentine was applied to it during tlie flfteentli I'entury. i because it was brought from Venice, at that time the center of the drug commerce, into the market. The first mention of larcli oil (Olfuiti bii-ici.s) in medi(.'al treatises is found in the works of Matthiolus- and (.'onrad Gesner.'"' Origin and Preparation. Venetian turpentine is prineipallv collected in southern Tyrol in tlie neighborhood of Meran, Mais, Bozen and Trient. also in vSteiermark from Lurix devkhm Miller {L. europnea D. C. Pinus hirix, L.), a larch that flourishes in the central European mountainous districts. According to experience, and as has been demonstrated liotanicidly by H. von Mohl* in IS.")!), the heart wood only contains numerous resin ducts, although they occur in limited nu7nl)ers in all l)arts of the outer wood and bark. The produi-tion of larch turpentine, thei-efore, is different from that described heretofore. By means of a wide auger, one or several holes are bored in spring to tlie center of the tree. These are (.-losed with a. wooden stopper and ojjened in fall in order to remove the oleoresin which has collected, witli an iron spoon. The liole is again closed for tlie further accumulation of ole(a-esin during the next summci-. If oidy one or two holes are drihed into tlie tree, the yield amounts to only several humlred grams, but remains the same for many years. [f a larger nunilicr of lioles Mre drilled into the tree, and the l.i,-ilsam is allowed to flow out. several pounds of balsam (■an be obtained in a single summer. In this case, however, the tree is exha-nsted after a imiiiber of years and the wood suffers considerable reducti(in in value. A more scientific maiiageinent of the forests, for the ]ir()(lnctioii of turpentiTie is. therefore, nioi-e remunerative (Wesseley.'"' 1S.";!|. In the French Dauphinc and about Briancon the oleoresin is i-epurted to be obtained in i\ similar manner. The holes, however, are drilled in ;i stiviight up and down line and e;ich h(.)le is provided with a short tin or wooden tube. After the exudation ceases, the openings ■■ire clo.sed and again opened atter 2 to '■\ weeks. After the first reopening the flow is said to be greater than when the holes are first drilled. The tapping gcH's on from Mai-cli to September. Large trees yield about ■"! — 4 k. of turjientine in a yeiir. .Vfter 40— .'>i> years the trees are exhausted." 1) I'liickiffer. I'hariiuicoji^iiosii.', |i. S(). 2) Mattliioli, Opera, 1, p. IIIM. 3) Pliiliatri, Ein kdHtllclier Schatz. ]>. 3S'.I. 4 1 licit. ZeituiiK, 17, pp. 329 aiul Hll . ■■') nie (isterreichisclien Alpenliinder unit ihre !-'or.ste. p. .-Iijll. runs\vick and west^'ard as far as Minnesota. 252 Special Part. The oleovesin exudes slowly into the cans, which are emptied daily and then thrust into a fresh pustule. One man collects little more than % Kal., or 2^ k., daily; with the aid of children he may collect double the amount. After every season the trees must be allowed to rest for from one to twfj .vears. bei^ause of the insufficiency of the accumu- lation of oleoresin. The principal place of export for Canada balsam is Quebec. The annual yiroduction has been given at g-reatly varying figures. It probably does not exceed 20,001 » k. during the best years. (Htearns.i i,s.")!); Saundei-s.^ 1.S77.) Upon distillation the balsam yields 1(> — 24 p. c. of oil. Propehties and Composition. The oil obtained from the dextro- gyrate balsam is laevogyrate. Its odor corresponds to that of the ordinary oil of turpentine. It liegins to distill at 160°, the major prjrtion coming over at 1()7°, a. smaller amount even above 170°. AVhen saturated with hydrogen chloride the oil does not yield a i-rystalline hydrochloride directlj'. A iM^mponnd of the formula CioHm.HCl was obtained by Fliickiger -^ only after treatment of the jiroduct of reaction with fuming nitric acid. The presence of ])ineue, rendered probable by this experiment, was proven by Einmerich-'^ (1M9.5) by means of the nitrosochloride, and the nitrolbenzylainine base melting at 122°. The pinene of Canada Vinlsam is l-pinene. lO. Turpentine Oil from Strassburg Turpentine. HisTOKY. Strassburg turpentine, which was known and used at the time of the Romans, has long disappeared from the market being dis- placed by cheaper varieties of tur])entine. The oil lias ])rolial)ly never been distilled on any other than a small scale ,iiid jiriiicip.ally for .scientific pui'jioses. OiiKriN ANii 1'repakatiox. The (.)leoresin of Abit^s nlba Miller [Allies pei-tiuntn. D. C.. Pinus jiicpn L. ) which is widely distributed in central Euroiie, is found in pustules like that of Allies linlsninen Miller. UpoiL raising the bark, the ])ustules are readil.v recognizable and arc opened. The exuding balsa.m is collei-ted in small tin cans. The yield is small and the collection of larger quantities tedious. Up to the middle of the seventies, Strassburg turjientinp was .still collected near Mutzig and Barr in the Vosges mountains. For local trade and use, the collection may still take jilace; in general, howevei-, this aromatic turpentine i.)OSsesses historic interest onlv. 1) .Xiiifi-k-. .Iimin. I'hanii.. :tl . |i. 2;i. 3| .TiilireKber. f. Pharni.. ISIl'.l, |). :1T 2 1 Prci'. Amei'. I'lmr)ii. .\s.sii.. 2.">. I'liariiiac9.° From fraction 28(1° a solid substance was also rjljtained, which, however, was not examined farther. 1) .Jahreyber. f. Phariu., ls(;j», jt. ;-i8 : I^harmacoftTaphi.-i. j'- 'ilo. = 1 Pharm. .loiirn.. HI, ■2^ . p. 1151; 56, ]>. 870. 3) In commerce the pine tar oil distiller! in Russian Poland i.s commonly de.sianaterl as RuHflian turpentine oil. *^ .Journ. d. rnss. phys.-chein. Ges., 20. p. 477: .lahresb^^r. f. I'harm., 188S, p. 10; Chem. Centralbl., 1889, I, p. 106. 5) .Journ. d. rnas. phys.-ehem. Oes., 20, j). 585; Clieni. Oentralbl., 1888, II, it. 1022. 6) Wiieti^er the oil "was obta.ined from the oleoresin does not become apparent from the abstract available. This, however, ma.v be assumed, since the oil from the needles of Finns sihirica, {Abies sibirica) does not contain canudiene. 254- Special Pnrt. 13. Turpentine Oil from Picea Excelsa. Rothtaniienterpentini')!. The tui'peiitine from Picen rxcelsa Lk. [Pinun pieen Duroi) col- It^rted ill thf iieif^'bhorliood of Naples, beinj;- distilled for experimental ])ur]ioses, yielded IS.:! p. c. of an oil of the sp. i^r. O.NdG. The optical rotation ao was + -'i" .">' at 1erties and roin|josition from the other tiir|ientini' oils. .Vcrurdin;:' to \\'elizell- (]!S7li) the ernde (iil hoils ])rinripall.\' between 101 — 10.')° and eonsists almost eiitirel.y of a h.yilroi-arlion. abii-'teiie, the s]i. i^'r. iif wliieli is ().(il)-l- at Ki.Ti". At the lieg'inniii.u' of the si^veiities it was sold in the San Fraiieiscn market nmler the names abietene. era sine, auraiitine and tlieoliiie as a substitute for petroleum benziii for the renioyal of stains. Abietene is not affected liy liydroehloric. sul]jhnrie, and nitric acids in the (/old and, accordinj;' to Tllorp^•3 i.s identical with heptane. The icxaminatioii b.v Schorlenimei-i (1SS3). Amenable'"' (ISSO). render it ])i-ol)able that this h.yilrocarlMin is mirnial heptane, identical with that from petrol('Uin. The souri;e of this oil has been a question of disptite. it ha.yine- been referred to P. iiondcvonn and to F. jetf'reyi as well; the oil has eyen been suspected of eonsistinji' merely of a. petroleum fraction. The classification and syuonom.y of the.se pines is in an unsatisfactory condition ami nmy well e-ive rise to misunderstaiidiues." Pine Tar Oils. Kienole. Besides pyrolij;-neous acid, pine tar oil is obtained in seyeral districts of p]urope rich in pine forests, as a by-product in the manufacture of charcoal and wood tar by the dry distillation of the resiniferous roots of the common pine, Pinus .sil vestri.s L. lii Scotland Pijms lede- i| BiTk-ht von S. * Co.. Oct. ISilli, p. 70. *) .\nnnlen, 217, p. 1+9. 2) AijLeric. .Tourn. I'harni.. 44, p. '.17: 5) Berlohte, 13, p. IIUU. I'hanii. .Tourn., II], 2, p. 7S1). O) pharm. Review. Is, p. lo,^. a) r>ieliiK'H Aiiiialen, IflS, p. aii4. Oils of the Abietinen'. 255 bourii Endl. is also used (Tilden,^ 1878). In continental Europe, most of the pine tar oil is made in eastern Germany, in Poland, in Finnland and in other parts of northern Russia, also in Sweden. The rrude pine tar oil contains tarrv, empyreumatic admixtures which are removed by rectification with milk of lime. Nevertheless, the oil retahis an empyreumatic odor. Though resemblino- turpentine oil, this odor renders it inferior. In a general way it can be said that all pine tiir oils ha^-e like properties and like composition. Their components are dextro-pinene, dextro-sylvestrene, and dipeutene.=^ From turpentine oil they differ principally liy their sylvestrene content. ■' 15. German Pine Tar Oil. Deiitsclies Kieuiil. The distillation of tar is conducted only in ;i few plai.es in tlie vicinity of Torgau ( Pi-ovince of Saxony); the produ(.-tion of (.'harcoal. tar and pitch have become the prime object. While the trunks of the pines are converted into lumber or fuel, tlie roots rich in i-esin are submitted to dry distillation after the splint has been removed to be u.sed as fuel. With the present rational method of iiroductioir^ the di.stillation of tar is conducted in a suirarloaf-like oven, Imilt of fire- brick, which is heated by a wood fire cii-i-ulatin;;- outside of these walls. The floor, which inclines toward the center, is provided with a large exit tube through which all of the liquid products of distillation escape into a pit of masonry. Through a lateral branch of the exit tube, the more A'olatile aqueous and ethereal products of distillation i)ass through a condenser and are collected in large Florentine flasks. In this manner the lighter oils are separated from the heavier pyi-oligneous acid. The crude pine tar oil is rectified over milk of lime and charcoal. It is used in the preparation of iron paints, for the cleaning of type and elec- tros, and in the preparation or dilution of the idieaper grades of paints. 1) Pharm. Journ., Ill, 8. p. .".S!). 2) In order to ascertain whether eyh-e.strene and dii^entene are to be regarded as original components or as decomposition products due to destructive distillation^ .\.schan and Hjeit (Chem. Zeit., 18 [1894], p. 1.566) distilled the trunk wood of the Scotch jiine (tir) ^^ith water vapor. They found pinene and sylvestrene, but no dipentene. It would appear, therefore, that sylvestrene is an original constituent of the pine oil, but that dipentene must be regarded as a product of inversion of the pinene due to heat. 3) So far, sylvestrene has been found in the roots, the wood and the needles of Pinufi silvestris L., also in the needles of Finns montami Duroi. Appai-entl.v it is found in pinus species only and not in other genera of the Ahietiiieae. *; According t — 171°. 10 ]). c. : between 171—172°, (v! p. c ; and between 172—185°, 24 p. c. Polish piiLe tar oil was exannned in 1877 by Tilden and in l.S,S7 by Flawitzky." Dextro-iiineue was found present; a terpene boiling between 1) Kdwak'U'ski. Die I'ro(lukti\'kr!iftc' RuHHlaiuLs. (xer man tran.slatiuii. Lei])zig: IHiJS, l)].. 2.^,4. 2.5.5. '-') According to a private coTuiiuiiucation (l.s'J6) friiiii Piv)!'. G. Wagner of Warschau there are in Ru.ssian Poland, particularly in tile S'onvernenients Lnblin, Loiiiza and .SiiwaIki nearly 100 tar (listiileries. each one of which produces on an averaj^e about l.r.OO- 2,500 kilo of ]iine tar oil. 3) Pharni. .fourn., Ill, 13, p. 58G. ■t| Liebig's Aunalen, 230, p. 245. 5) rharni. .Tourn., Ill, 8, \\. 447; .lonrn. ('hem. .Soc, 33, p. SO. <■>) Berichte, 20, p. 195G. Oife of tlie Ahietiue;p. tWt 171 — 172° wliidi Tilden supposerl to be sylvestreiie, though he did not .sueeeed in preparing the chlorhydrate, m. p. 72°; and cyraene, identified by niean.s of Ijromine and sulphuric aeid.i Wallaeli in 1885 suljstantiated the presence of pinene.- He also identified the sylvestrene in fraction 170 — l.S()° by means of the crystalline hydrochloride, m. p. 72°. In the fractions boiling about 18f)°, he also identified dipentene by means of its tetrabromide, and a terpene which yielded a li(piid addition prodm-t with bromine (ferpinene?). 17. Swedish Pine Tar Oil. Sclnvedisclies Kieiiiil. Swedish pine tar oil has a sp. gr. 0.871, and a. rotatory power «D^ + l-t°l''^'- According to the examination of AtterbergS (1877) it contains dextro-pinene, b. p. l."iG.5 — 1.''j7..")° (pinene chlorhydi-ate, m. p. 1;!1°|; and a. hitherto unknown terpene, b. p. 17:5 — 175°, winch After- berg characterized by a dichlorhydrate melting at 72 — 73° and which he termed sylvestrene. Wallach * (1885) also examined this oil. 18. Pine Tar Oil from Finnland. Finliiiidisclies Kieiiijl. Since closed ovens are used in the produi-tion of wood tar in Finn- land, a large quantity of fiine tar oil is obtained as by-product from the trunks of the pines," spruces and firs. Two varieties of pine tar oil from Finnland have been examined by Aschan and Hjelt" (1894). 1. From southern Finnland. After five repeated fractionations the following fi'a(;tions were obtaineil ; 1) 155 — 100°, 7.1 p. c. ; 2) KiO — 1()5°, :30.2 p. c. : 3) 165—170°. 22. (; p. c. ; 4) 170—175°, 20.1 ji. c. The first fr:iction consisted of pinene (hydrochhjride, m. ]i. 12;! — 124°; nitrosochloride, nitrosopinene). In fraction 170 — 174° sylvestrene (di- hydrochloride, m. p. 72°) and dipentene (dihydrochloride, m. p. 49 — 50°) were found. 2. An oil from northern Finnland differed fi-oni the former in the relatively larger amount of higher boiling fractions. Fractions l(i(.t — 165°, also 165 — 170° were insignificant, whereas fraction 1 70 — 174 i-epresented ■32.2 p. c, and fraction 174—178°, 21.2 p. c. In the lower fractions ij In the presence of terpenes tlii.s reaction cannot be conHidered a jiositive jiroof. 2) Liebiff's Annalen, 2.30, p. 24.'i. 3) Berichte, 10, p. 1202. + ) Liebig;'R Annalen, 2S0, p. 24(t. 3) The fore.HtH of Finnland consist approxiniatel.v of 77 p. c. jiines and 12 p. c. si)rnce. 0) Chem. Zeitniig, IK, pp. 1.560, XCV.), 1800. 17 258 Special Part. pinene was found, whereas the higher fractions consisted (/liiefly of eciflc gravity are not great and, therefore, of less importance than the examination of the rotatory power of the oils. Besides, the saponification number of the oils Oik of the Aliietiiie.-p. 2.10 adulteratt^d witli turpentiiip oil is much smaller than tha.t of the genuine oils and, therefoi-e, may serve in a general way as a good test foi- the purity of the pine needle oils. 19. Pine-Needle Oil from Abies Alba. Edeltauueiiiiadelol. This oil is distilled prhicipally in Switzerland and Tyrol (in the Puster valley) from the needles and twigs of Abies alha Miller (.Ifti^s pertinatn I). ('.. Abies exeelsa Lk. ) (Gferni. Edeltaniie. Weisstiuine or Silbertaniie). Properties.! This oil is a colorless liquid possessing a balsamic odor ; sp. gr. 0.869— CHT.") ; au — — 2()° to — .')9°. It is soluble in .5 parts of 90 ]). c. alcohol. It r-ontains 4..j to 10.9 p. c. of ester (bornyl acetate). Upon distillation, H p. c. come over lielow 170°, and 5.5 p. c. between 170 — 185°. Above this temperature partial decomposition results, the bornjd acetate splitting off acetic acid. Composition. Bertram and AValVjaumi- ascertained the presence of the following coii.stituents : 1-pineue (pinene nitrol benzylannne, m. p. 122 — 123°), 1-limoneiie (tetrabromide, m. p. 104°), 1-bornyl acetate. - and a sesquiterpene not yet identified. 20. Oil from Cones of Abies Alba. Edeltaiinenzapfenol. Teinpliiiol. This oil is obtained in several sections of Switzerland and the ThuringiaTi forest by distilling the one year old cones of Abies alba Miller, collected in August and September, with water vapor. Properties. This oil is colorless and possesses an agreeable balsamic odor reminding somewhat of lemon and orange. Its .sp. gr. is 0.853 to 0.870; its -/d — — <)0° to 76°. The amount of ester (calculated as bornyl acetate) is 0.5 to 4 p. c. With 6 parts of 90 p. c. alcohol, the oil gives a clear solution. It is characterized by a large percentage of 1-linionene. Inasmuch as this strongly optically active terpene is its most valuable constituent, the rotatory power of the oil is taken as a criterion of its value. The stronger the laevoi-(jtation and the lower the sp. gr., the more limoneiie the oil contains. i| P.ericht von S. & Co., C>ct. 18112. p. 21; .\pril lM!i:i, p. 2'.); .Vrchiv d. Phaiii]., 2.31, p. 291. 2) Hir.schH')hn, Pharin. Zeitschi-, f. Itiiw.sland, 81, ]>. .^'j:-!. •2(H) Sjiecia.l P;u-t. U])on distillation lip. c. came over between l.",()— 170°, and ;',7 p. r. between 170— 1H5°. Above this temperature partial decomposition ac(.'ompanied by splitting oH of acetic acid takes place. Composition. Of the older investigations of Templin oil those of Fliickig-er^ (1856) and of Berthelot^ (1856) should be mentioned. These investigators studied the action of strong acids on the oil and obtained terpin hydrate, a terpene monohydrochloride and a terpene dihj-dro- chloride. The formation of these compounds is to be attributed to the presence of pinene and limonene as shown later. In IHH,") Wallach'^ examined a "templin oil" designated •'Fichten- midelol' and found its principal constituents to be pinene and 1-limonene. Bertram and Walbaum 't (liS9:i) showed that the pinene also is laevo- gyrate and that '■Templinol" consists principally of 1-piiiene and 1-linioneue. They also found a trace of an ester, the nature of which coulil not be ascertained, but which in all probability is bornyl acetate, also found in tlie oil from the "needles. On account of the large per- centage of 1-limonene, this oil is the best source for this hydroearbf)n. 21. Pine Needle Oil from Picea Excelsa. Ficliten- or Rothtaiiiieiiiiadelol. The '■Fichtennadelol" proper is obtained Ijy steam distilhition from the fresh needles and twigs of the Norway spruce, tlie Picea. e.vec/.sv) Lk.. {J'icf;i vulgaris Lk.). The yield is about 0.15 p. c. (Bertram and Walbaum.-'') As far a,s is known, it is not a commercial article. The odor of the colorless ies alba Miller nnd Pinus montmifi Miller but is less delicate. Its si>. gr. is ().,S84— 0.8H6 and its ao = + 7° 3' to 10°. Upon fractional distillation 10 p. c. came over between KJO — 170°. 16 p. c. betw. 170 — 185°. With 10 p. of !)0 p. e. alcohol the oil gives a clear solution. The ester content, calculated as bornyl acetate, is 3.2 — 3.5 p. c. ('oM POSITION. The (jernian oil, like the pine needle oils previously mentioned, contains pinene, but the pinene differs from that fouml in the.se oils in lieing dextrogyrate i (nitrolbenzylamine, in. p. 122 — 123°). Tt also contains d-sylvestrene. Its dihydrochloride first melted lJ^■low 50° ,iiid only after repeated recry.stallization acquired a constant melt- ing point of 72°. Inasmuch as. according to Wallach. diiientene dihydrocliloride i-a.uses a material depression of the melting jxiint of sylvestrene dihydrochloride, the assumption that dipentene is present may be justified. T'poii saponiflc'ation, acetic acid was found vhii-h was evidently combined with an iilcohol (])rol)ably boi-ne(d or terpineol ) not yet identified. In the higliest frai/tions ca.dinene (dihydrochloride, m. p. 118°) Wiis f<_iuiid. Swedish "Kiefernadelol" is distilled in Sweden, more ])articularlv in the district Jfinkiiping, and is brouglit into the market as Scliwedisches Firlitenuadeldl. It is used for hygienic and medii-al purposes, in iiilialations for affections of tlie lungs, as admixture to baths, and in sprays for sick chamljers. Properties. The Swedish oil corresponds in its gvnei'al properties witli tlio.se of the German oil. Its sp. gr. is 0.,S72. its rotatory power -f 10° 10', ;ind u]ion distillation yields 11 p. c. distillate at 1<30— 170° I I .lirliiv (1. Phariii., 1131, p. 300. -) )liiclem: and Her. von S. i Cu., (let. ISCMI, p. 7C>. Oik o1 the Ahietine;i\ 2fiS and 4:(.) p. e. at 170—185°. It contains d-phipuf (iiitrolbenzylamiue, m. p. 122 — 128°). d-sylve.strene (dihydrochloride, m. p. 72°), and small amounts of an ester (3.5 p. c. calculated as borujd ester), the nature of which has not yet Tieen definitely a.scertained hut, jtidging from the odor, appears to be bornyl acetate (Bertram and Walbaum,^ 1898). English "Kiefernadelbl." From the German and Swedish oils, the English is rlistinguished by its laevorotation. Umney- (1895) di.stilled the needles of the Scotch hi-, Finns Nilvestri,<< L. at different times of the year and obtained 0.5 p. c. of oil in June, and 0.138 p. c. in December. Its sp. gr. varied from 0.885 — 0.889. and its r(jtatory power, ^d =; — 7.75° t(j — 19°. The ester content, calculated as bornyl acetate, ajiionnted to 2.9 — 3.5 p. c. Upon fractionation of the two oils, the followino- results were obtained : Oil di.stilled, In Tune In December l.-,7— 107° 8 p. c 13 ],. c. 167—177° 27 24 ■• 177—187° 20 " 9 •■ 187-197° 3 " ■' 197—240° 7 " 7 24(1—252° 6 4 " Kii-sidue 29 " 87 " Composition. The lowest fraction deviated the ray of polarized light 18° to the left (in a 100 mm. tube) and possessed all the properties of 1-pinene. Fraction 171 — 175° was slightly dextro rotatory (+0.75°), and corresponds in its propei-ties to dipentene-'' and gave with glacial acetir; and sulphuric acids the characteristic' violet syh'estreue reaction. With the exception of the opposite rotation, it may be assumed that the English oil has the same com]iosition as the (jerman and Swedish oils. . ■ 24. Hemlock or Spruce Needle Oil. Hemlock- or Spnice-Taiineimadeliil. The needles ahd yOung twigs used in the 'distillation of this oil seem to be contributed by three different species: 1) Abie.s ciinufleiisis M'u-hx.. (Tsugu Ccinadensis Carriere), the hemlock (Ger. .Sy^rure- Hemlock- oder Schierlings-Tanne) which occ'urs throughout North America from Gana.da to Alabama and westward as far as the Pacific ; 2 ) I'iceu alba IJc. or 1) .irchiv d. PharnV., 2.31, p. 299. ' - "■ ■' ■'■ ' ■ 2) Pharni. .IcJiiM].. 55,''pp. 161, .542. ' ' " ' •^ ' ' '' -' ■ ' ■ 3) DerivativeH of thift 'hydrocarbon were evidentl;<' not jirepared. NVither did iTn'ine.T succeed in obtaining' the dihydrootiloride of sylvestrene. ' - • . 2(>i S]iecUiI Part. white S])riicp (der. weisnf Tnniif): anil :!) Picen. nigrii Lk., the black spi-nee (Grer. si-hwiirze Tnuiie). The two latter are equally widely ilis- trihuted with the first. In the collection of the leaves and twigs it seems highly probable that no distinction is miide between these three species, so that a commercial oil ma,y cimtain variable amounts oi the oils from all three. In fact the oils of these three species, being regarded as identical, are brought into the market under the common name of hemlock or spruce oil. Inasmuch as the oils are alike in properties and composition, quantitatively, the confusion in this case may be regarded as being of little or- no consequence. Pkoperties and Composition. Hendock or spruce (jil is colorless. of a,n agreeable balsannc odor,'' s]j. gr. 0.907— 0.!)13, ay = — 20°54' ( Bertram and Walliaum 2 ) to — 2H° .").")' ( Power^ 1. Fractional distillation yielded II p. c. between 150—170°. and :-!7 p. c. betw. 170—18.5°. Above this temperature decomposition sets in with tlie formation of acetic acid. Hemlock oil contains l-])inene ( nitrolbenzylamine, m. p. 122 — 128°)' ;!() p. c. 1-bornyl ai-etate and sesquiterpenes not identified. HunkeH examined an oil distilled by himself from the fresh twigs of Abies canadensis Michx. Its sp. gr. at 20° was 0.92.S,S, [«]d = — 18.3!)9°- It contained 51.5 — 52 ]>. c. of 1-bornyl acetate. 1-Pinene w;is identified by means of the nitrolbenzylamine base. m. p. 122°. An oil distilled in September consisted principally of about e(]ual parts of 1-bornyl acetiite and 1-pinene. 35. Needle Oil from Picea Nigra. Scliwarzflchteiiniideliil. Tlie oil from Picea. nigra. Lk. already mentioned nnder the ]U"evious heading is almost identical with hendock oil. Its sp. gr. is 0.922 at 20°, ,.D = -30.867° at 20°. [a]D = — 89.45°. The oil distills between 1()0 — 280°, the principal fraction between 212—280°. It contains IS., s.5 p. c. l)0rnyl acetate ( Kremers,'"' I S95 ). 26. Needle Oil from Balsam Fir. Bal!samtaiiiieiina(tel(il. The fresh twigs and young cones of the North American lialm of Oilead fir yield upon distillation with water vapor an oil similar to the pi'eceding ones. 1) The oil with \\iiii-h Hiiiikol wni-keil -■ ) .^ic-liiv. d. I'hanii., 2H1, p. 2i)-t. AMIS b.v no means very usreealile as to '•'■) Dewi-. I'ataloffne of ess. oils, p. ."is. 4k1(M'. Kleber, however, rej»arris to the odor +) rhai-ni. Iteview, 14, j). 3.^. p. i;-. : 160—170°, 47.7 p. c. ; 170—18.')°. 20.2 p. c; lis.")- 210°, 1G,2 p. c. ; residue .').!: p. e. Tliis oil contains 17.(1 p. c. of bornyl acetate. Fraction IGO — 165°, which is laevogyrate, yielded a nitrosochloride melting at 101°. Although the yield was too small to make any of its derivatives it may be assumed that tlie frai-tion in (pie.stion contains 1-pinene (Hnnkel.i 1«9.")). 27. Siberian Pine Needle Oil. Siliirisclies Piclitennadelol. This oil is distilled from the needles and young- twigs of Abien sihi- riea,- (Ger. sjhiri.srhe Fiehte); on a large scale in the gouvernement Wjatka. in northern Russia. On account of its strong, balsamic odor, the oil is used in perfuming '"Fichtennadel" soaps and the cheaper "Tannenduft" preparations. Properties and Composition. The oil is colorless, has a sp. gr. of 0.905—0.020; «d = — 4:0 to —42°. The ester content (bornyl acetate) varies from 29 — ;i(; p. e. With equal parts of a 90 p. c. alcohol it makes a clear solution. Fraction 1(50 — 1(58° contains 1-pinene (uitrol- benzylamine, m. p. 122 — 128°). Camphene could not be identified. In the higher fractions 1-borneol was contained as a<.-etic ester (Hirsch- sohn,-i 1892). Besides bornyl acetate, it contains the ester of another terpene alcohol, possibly terpineol.-*^ 38. Needle Oil from Pinus Cembra. ZirbelkiefernadeliU. The needles (without the branr-hes) of the Siberian (/edar. I'iuun reinhiei L. (Ger. sibirisehe Cedev, Ai-ve) yield upon distillation with water vapor 0.88 p. c. of oil. Its rotatory power, '/d= + 29,1°. It con- sists chiefly of d-pinene (monohydrochloride, m. p. 125°). Fraction 15()° has a verj^ high specific rotatory power ['/]d = + 45.01°. On account of this liigh rotatory power, the oil is \-cvy servicealile in the preparation of a strongly dextrogyrate pinene ( Flawitzkj',-? 1892). 1) Amer. Journ. Phanii., fi7, p. 0. 2) According to a statement of the fii'm of R. Koehlei- & Co.. c)f .Mowoan : coinp. aLso Bericht von .Schinimel & Co., Ai>ril 1880, p. 1.5. AccoriUng tr) Prof, ilenthin of Warsau, however, this oil iw obtained from the needles of Larix sihirica Ledebour (Pinus ledebourii Endl.). 3) Pharm. Zeitsehr. f. Rvissl., 80, \i. 593. ■t) Ber. V. S. & Co., Oct. 1896, pjJ. 4a & 76. 5) .lourn. t. pralit. Chem., II, +.5, p. 11.5. :2(i() SpecinI Pnrt. ' 2d. Oil from the Cones of Abies Reginae Amaliae. The fruit of Ahien ivg-iii.-w arnaline Heldr.. which «:tows in the forests of Ai-i-adia, roiitains so laT^^e an amount of volatile oil that it exudes when the fruit is conipressed. Upon distillation of the crushed fruit more tluin K; p. c. of volatile oil has been obtained (Buchner and Thiel.i 18G4). rROPEHTiES AN'i) COMPOSITION. Tile sp. gT. of the oil is 0.868, its rotatory power — :20°. It begins to boil at l.")<)°. the l)oiling point remains constant for some time at 170° and finally rises to 192°. As shown by elementary analysis, the oil consists principally of hydrocarbons OiuHk;. A solid hydroi'hloride was not obtained. This is evidently due to the fact that besides pinene the oil probalily contains limonene and diyientene. A mixture of hydrochlorides is thus obtained from which it is ilifHcult to separate the individual compounds. 30. Larch Needle Oil. Liirclieniiadeliil. The needles of the larch, Larix dei-idua Mill, upon distillation yield but 0.22 p. c. of oil of the sp. gr. O.STS; an = + 0° 22'. 2 It forms a clear solution with 5 and more parts of !)0 p. c. alcohol. 8aponiflcatiou number 23.3, 8. Z. after acetylization 4:(). If it is assumed tha,t the ester of this oil is bcu'uyl acetate, as is the case in most coniferous oils, and that the alcohol is borneol, the above figures indicate a percentage of 8.1 p. c. of bornyl acetate in the original oil and Ki.l p. c. in the a.cetylized oil. With reference to the alcohol, the same figures indicate ('>Xi-.\ p. c. of horneol as ester, and ().14 p. c. of free borneol, a total of 12. (JT p. (•. U)ion distillation the following fractions were obtained: KiO — K)."!", ;{() p. ,;. (an = + 1° 1-')'); Ki.")— 170°, 24 p. r.; 170—180°. l(i p. c; IcSO— 10(.)°, H ]). c; 1!)0— 200°, 4 p. c; 200— 230°, <) p. c; residue 1) ]>. c. Larch needle oil has fi pleasant, refreshing pine needle odor. The small yield and liigh price, as well as the ditficulty of obtaining larsi'er quantities ju'event its ])ractical aitplication. 31. Sequoia Oil. r])on distillation of tlie needles of the Ca.lifornian giant. Sequoin gi. . • . . Oils of the Ahietiiip;!'. 267 The g'reatei- i)ortiou of the distillate consisted of a hydrocarbon OinHie, boiling- at l-~)5°, which possessed a pleasant teivbinthinate odor, had a sp. gv. of 0,S.''i22 and a rotatory power [«]i = + 2:i.H°, With hydrogen chloride, a white, camphoi'-like hydrochloride crystallizing in needles was obtained. Althongh these facts indicate ]:)inene, Lunge and Steiukanlei' regard it as a new tei'penf on account of its high rotatory power. 1 Fraction 227—2:10° had a sp. gr. l.Oi.'). angle of rotation + 0°, and its odor reminded of peppermint oil. From the elementary analysis the formula CisHooOa was calculated. Between 2H(I and 290° a small amount of a heavy yellow oil of enipyreumatic odor was obtained. Further there is contained in the oil a colorless hydrocarbon, which crystallizes in laminae melting at 10.")° ami boiling between 290 — 300° (uncorr. ). It is called sequojene and probably has the formula CisHki IjMng isomeric with fluf)rene. 32. Sandarac Resin Oil. According to Balzer- (189()) African sandarac from Cnllitris ijunil- 7-;ivi/ri,s' Yent. contains about 1 p. c. of volatile oil which can be obtained by steam distillation. The oil has a brownish color, a pleasant, strongly aromatic odor reminding of the odor of pines. In the cold it becomes viscid and apparently separates a stearoptene-like substance. 33. Thuja Oil. Oleum Thiijae. — Thnjadl. — Essence de Thuya. Origix and Production. Thuja oil obtahied by distillation with water vajior of the leaves and twigs of the avhov vitue, Thuja occi- dentnlis L. (Ger. L(^hriishuuin). The yield varies according to the season from 0.4- to ().()•' ]). c. It is largest in spring (March) and decreases toward summer (June. Jahns,^ l.S,s;i). The small amount necessary to supply the demand, is distilled principally in North Amerii-a. Properties. Tlnija oil is a limpid, C(jlorless liquid or of a yelloAvish or greenish-yellow color. It has a characteristic strong, camphor-like odor of tansy, and a bittei- taste. Sp. gr. 0.91." — 0.9;!.''i ; '/.£, = — ."> to — 1-1-°. Witli •"!— I- parts of 70 ]i. c. alcohol it foi-ms a clear solution. It boils between 100 and 2.")0°. The first runnings contain an acid liquid consisting principally of acetic acid with a little formic acid (JahnsS). 1) Since then Flawitzk.y (18i)2) (.lourn. f. jirMkt. Cheiii.. II. 4."i, p. 115) has isolateil a ])inene with much hift'ht^ flextro-rotation. See needle oil frnin Finns cemhra on p. 2G.'>. 2) Archiv il. Phariii , 2.34, p. 311. ' 3) Archiv il. PhniMn,, 221, p: 74S. ' .: 268 SpeeinI Part. (JoMPOsiTiox. Thuja, oil was first examined by Si/hwelzei-i in 1H48 without definite results. Jahns sucreeded in separating three sub- stanees liy fractional distillation. He obtained a, dextrogyrate terpene fraetion between l.">()— l(il°, a dextrogyrate oxj'genated fraction lietween l!).'i— 107°, and a laevogyrate oxyuenated fraction between 107—1!)!)°. The two latter fractions had the formula CioHieO and inasmuch as they appeared to be optical isomers, he named them il- and 1-thujol. A few years later ( l.S!)2j Wallach's- investigation cleailj' revealed the composition of thuja oil. By means of the nitrosochloride the identity of fraction KiO"^ with d-]}inene was established. The fractions up to 190° also contain a substance that is acted upon by potassa with the formation of potassium acetate and probalily contains an acetic acid ester. Fraction 190 — 200° contains two chemically different ketones of the formula (hoHieO, 1-fenchone, and d-thujone. The purification of 1-feuchone, Wallai-h accomplished by ac-ting on ti-action 190 — 1!).">° with potassium permani;anate and nitric acid, thereby completely destroying- the thujone whereas the very stable fenchone remained almost un- affected. The fenchone thus obtained corresponds in all its properties, with the exception of opjiosite optical rotation, with the ketone obtained from fennel oil (comp. p. l(i(;). To the second ketone ('loHieO, wliich boils slightl^y higher, Wallach applied the name thujone. Properties and derivatives of this sub.stance are desc-ribed on p. 167. From fraction 220° of the oil, Wallach'^ (l.S!)4) obtained an inactive oxime melting at !)H — 94° which corresjionded with optically inactive (■arvoxime. Upon hydrolysis with sulphuric acid it yielded an oil volatile with watei- vapor, which had tlie odc^r of carvone and which boiled between 220— 2;!0°. The jiroperties of the hydro-sulphide addition ]iroduct. however, did not agree with those of the corresponding com- jjound obtained with inactive synthetic carvone. Later on it was shown by analysis that the oxime is not a derivative of i-carvone, as Wallach first supposed, but of hydrocarvone. (Ji,)HinO^ (1S94). inasmuch as Semmler'' has shown (1H94) that thujone, when heated to higher tem- peratures, is converted into <-arvotanacetone= hydrocarvone, it .spcnis probable that hydrocarvone is not contained iu tlie original oil but is foi-med by fractional distillation from thujone. 1) .)iiurn. f. prakt. Oheiii.. :iii, p. ;.!7(j; 3) Liebig's .^nnnk'ii, L>7.">, p. 1S2. Llibig'H Annalen, .">2, ]). 3'.)S. i) l.iebiR's Aiiniilen, 27:>. r.) Berifhte, 27, p. s',!.",. Oils of the AhietwfiT. 269 34. Thuja Root Oil. The oil from the root of Thujn oceidentnlin L. has a deep-brown <;olor, an odor reminding of tiiat of thymoquinone, and a sp. g-r. 0.979. The yield is about 2.75 p. e.i 35. Oil of Cypress. OleuiiL Ciii)ressi. — Cypressenol. — Essence de Cypres. Ori&in and Hihtoky. Cypress oil whii-h was reciommended by Bravo in 1892 against whooping-cough, was introduced into commerce by Schimmel & Co. in 1894.2 It is distilled from the leaves and young- branches of Cupre.s.sus spmpei-virens L. According to the season and the freshness of the material the yieM varies from 0,6 to 1.2 p. c. Properties. Cypress oil is a yellowish liquid, the odor of which is pleasant and reminds of cypress, but which after evaporation leaves an odor that reminds distinctly of labdanum and is ambra-like. Sp. gr. 0,88—0.89, «D = + 4 to + 14°. The oil is soluble in 4— .5 parts of 90 p. c. alcohol. Composition. Cypress oil consists chiefl,y of terpenes, principally of d-pinene (nitrolbenzylamine, m. p. 124°). Sylvestrene and sesquiterpenes appear also to be present. Fr(im the last runnings a crystalline substance occasionally separates, which crystallizes from alcohol in fine needles, from petroleum ether in compact crysta,lline masses. In its behavior, "cypress camjjhor" resembles cedar camphor or cedrol, from which it differs, however, bv being optically inactive. Probably it is the opticall.y inactive modification of cedrol. In addition, cypress oil con- tains small aTuounts of esters. * 36. Hinoki Oil. The white wood of the hinoki tree, (.'hnmtwcypm-in obtusa, Endl. ( lletmospoi-i ohtuna. Sieb. et Zucc). -(vhich is cultivated in Japan, is used in the construction of the Shintd temples and the manufacture of lacquered goods. -^ The odor of the oil distilled from the leaves resembles that of the oil from the savin or thuja. It ha,s a remarkably low boiling point. About half of the oil distills between 110 and 100°, the other half between 160 and 210°.* 1) Bericht ron S. & Co., Apr. 1892, p. 43. 2) Ibidem, Oct. 1894, p. 70; and Apr. 189.5. p. 22 3) Rein, .Japan, Leipzig, 1886, voi. 2, p. 277. i) Bericht von S. & Co., .4pril 1889. p. 44. 270 Sjwci;}! Part. 37. Oil of Juniper Berries. Oleum Jmiiperi. — W. cliolderbeeriil. — Essence i8), and Spiehnann.s Production. The distillation of the berries and the pvepaiaticin of the extract go hand in hand. After the mashed berries have l)een distilled with water, the residue in the still is extracted with hot water. The aqueous liquid is evaporated in vacuum pans to the consistency of a soft extract and is In-ought into the nm.rket as Succus^ or Itooli Jimijipi-i. The yield of both oil and extract varies considerably in different years. The (piality of the juice likewise varies consideral.ily. In some years it is so rich in sugar that it congeals to a, fairlv solid mass. 1) See p. IS. 2) Fiindamenta iiialeria nieflicae, vol. li. p. 84-t». 3) Ibid., vol. 2, p. 272. 1) The extract obtained in this manner doe.s not correspond to tiie Succiis Juniperi of the (jernian I'harniacopoeia since according to the method of in-eparation of the latter a part of tlie oil i-eniains in the extract. Oils of the Abietinex. 371 Oii an average Italian bei-rie.s yield 1—1.5 p. i:-., Baviirian 1—1.2 p. i-., Hung-arian 0.8 — 1 p. r. of oil. A smaller yield of oil, O.G— 0.0 p. c is obtained from East Prussian, Polish, Thuringian and Prankish juniper berries. A distillaticju of Swedish Ijerries yielded l;iut O..^ p. c. of oil. These data contradict the opinion expressed by Maieri (1867) that the oil content of juniper berries grown in northern countries is greater than that of berries grown in southern countries. The above data indicate the opposite to be true. However, the collected data, are not sufticient to settle this question finally. Fairly considerable quantities of oil of juniper berries are brought into the market from the Hungarian ''Komitat" Trencsin. Judging from experience, this Hungarian oil is of minor quality and not normal in composition. It is probabh^ obtained as a by-product in the manu- facture of gin. Oil of juniper bei-ries is used principally in the preparation of gin (Steinhager, Gpnipvre) and liquors, also to a limited extent medicinally, particularlj^ in veterinary practice. Properties. Juniper berry oil is a limpid liquid, colorless or slightly greenish. Old oil is more viscid, reacts acid and smells more or less rancid. Fresh oil possesses a peculiar terebinthinate odor, and a balsamic, burning, somewhat bitter taste. In regard to its physical constants, it shows considerable variation according to origin and method of preparation. The sp. gr. lies between 0.865 — (_).882, and in a normal oil between the narrower limits of 0.867—0.875. The oil is mostly laevogyrate up to — 11°, seldom inactive, now and then slightly dextrogyrate. In alcohol, particularly in dilute alcohol, it is but slightly soluble. To effec-t solution 8 — 10 parts of 90 p. c. alcohol are requisite. With some oils a clear solution cannot be effected with 90 p. c. alcohol in any proportion. The solubility further diminishes with increasing- age. With chloroform, carbon disulphide, benzene and amyl alcohol, juniper berry oil is miscible in all proportions. The previousl,y mentioned Hungarian oil has a sp. gr. 0.862— 0.S6.S, and is optically active up to —18° 48'. In its solubility in alcohfil it behaves like the German. So-called exti-a strong juniper oil, which is obtained either by fractiormi distillation or by shaking out with alcohol of varying strength, loses its original greater solubility witliin a short period. 1) Die athei-lHChen Ot*le. p. 102. 272 Sjipcial Part. f'oiiPOsiTiox. Frnr-tion l.").'}— 162° contains pinene i (AVallach, lH8o|; fraction 2V>()—27'>° cadinene, as whown by the preparation of tlie dihydrochloride melting at 118°.- Tlie fractions between 162 and 2(i()° have not j'et been speciaU^y examined, although they probably contain the charai:teristic constituents of the oil. The supposition that the pec-nliar oilor of the oil is due to esters- had to be dropped since the oil retains its odor after saponitication. The amount of sa.poniflable substances is small, for the saponification figures are very low: e. g. 3.8. 3.4, 3.5, 3.7. Kremel3 (1H8H), however, lias found figures as high as 7.1 and 16.4. Ali.-oholic constituents which can be converted into esters by boiling with acetic acid anhydride, are present in small quantity only. In three normal oils the following saponification numbers were found after esteri- tication: 18.3, 22.5, 22.!). Substances containing a methoxyl group are likewise not present. A further constituent is a. substance olitained from the last runnings of an oil that had been standing in a cool place for a long time. It separa.ted in the form of fine needles. After several rei'rystallizations from alcohol, fine needle-shaped crj^stals were obtained which melted at 165 — 16()°.* Similar crystallizations have been formerly observed and have been described in oldei' literatui-e ■"> as juniper camphor, juniper berry stearoptene, juniper berry hydrate." Adulterations of juniper Ijerry oil have seldom ))een definitely proven, because a moderate addition of turpentine oil cannot be readily established, since pinene is a regular constituent of the oil and since the addition of tui'pentine oil but slightly changes the physical constants of the oil. The addition of alcohol is ascertained according to the method descril)ed on p. 2(10. 38. Oil from Juniper Wood. The so-calleil juni])er wood oil is nothing but tui-])entine oil distilled from juniper wood or bronches, ov turpentine oil to which some juniper berry oil has been added. The juniper wood oils of commerce correspond in their properties with such products. They are used externally as domestic remedies or in veterinai'y pi"ictice. 1) Liebig's Aniialen, 227, p. 2S.S. = ) Bericlit Mill S. & Co., Aiiril, IS'.io, p. 4:'.. :■) Pharni. I'o.sl, 21, |i. S2y. *1 Bericht von S. & Co., Oft. 189.'i, p. 4r,. 5) Of the older contribution.s on juniper lierrv oil the lollmvins iiiiiy here be men- tioneil: Blanehet (18.3.SI, T,iebig'.s Annalen, 7, p, tC7; Dnnias (1 8:!."D, Uebis'.s .\niialen, 15, p. 1.59: Siiubeiran and Capitaine (18411), T,iebis"s .Annalen, 84, |i, 324. 6,1 lilanchet. loc. clt.; Buchner (1S25|, Uepert. d. riiarm,, 22, p. 425. From the inHufflcieiit data of the idder authors it does not become apparent whether thev had the same substance as Schimniel & Co. ro- pos.sibly terpin hydrate. Oils nf the Abietinf:e. 273 39. Oil from the Berries of Juniperus Phoenicea. A commercial variety of red juniper berries obtained from Smyrna and probably the fruit of Juniperufi phoenicea L., yielded upon distil- lation 1 p. c. of oil. Its sp. g-r. was 0.859, «d = — 4°r)5' at 16°. The oil corresponds in all of its properties with those of the oil from Junipei'us communing 40. Juniper Oil from Juniperus Oxycedrus. The reddish-bro^^^l berries of Juniperus oxycedrus L., growing in Dalniatia and Istria, yield about \.'■^- to 1.5 i p. c. of oil which is quite terebinthinate in odor, reminding but faintly of juniper-. The sp. gr. of the oil is O.SSl^ to 0.854;; «d = — 4:°4:0'i to — 8°30'.2 It does not produce a clear solution with 10 p. of 95 p. c. alcohol. The odor of the oil distilled from the fresh twigs in Spain reminds of that of the finer pine needle oils.s 41. Oil of Savin. Oleaiii Sabinae. — Sadebaiimol. — Essence de Sabine. Origin and History. Savin, Juniperus sabina, L. is indigenous to the temperate zones of tlie old world, but is not widely distributed. Savin was used medicinally and in veterinary practice by the Romans. It seems probable that the name Sahina has been derived from the mountainous country of the Sabines l.ying to the north-east of Eome. Dioscorides and Pliny mention the plant among those being used medicinally, but distinguisli between two varieties. The differences, however, were probably those of source only and slight morphological variations. Charlemagne in the ninth century mentioned it in his Capitulare and thus caused its cultivation in the northern Alps. The a,bbess Hildegard of Bingen mentions savin as a remedy in her writings ; it is also one of the 77 remedies praised bj^ Otto of Meudon (Macer Floridus). In England the tree seems to have been cultivated and used before the Norman conquest. 1) Berleht von S. & Co., Oct. 1895, p. 45. 2) Observation in the factory of Schimmel & Co. 3) Bericht von S. & Co., October 1889, p. 54. Cade oil, which is obtained in HOnthern France by the dr,v 5 et seq. The distilled oil is first mentioned in the prii.-e ordinance of Frankfurtr- on-the-Main for 1587 and wa.s described by Begxiinus at the close of the seventeenth centur^^.i Concerning the yield of the oil Hoffmann seems to have ma,de the first experiments about 171 -"i.-' Wedel examined the oil in 1707 according to the methods in vogue at his time.^ The first chemical examination was made by Dumas in 1H;!5.-i Preparation. Oil of savin is prej)ared by distillation with steam of the leaves and twigs (Sumniitates sahinae). The .yield varies between 4 and 5 p. c. accorrling to the tiine of collection and the freshness of tlie material. The leaves used for this purpose come prin(.-ipally from Tyrol. In sontherii France the oil is also distilled, but apparenth' the Frendi oil of the mai'ket is invariably adulterated with large quantities of turpentine oil. Properties. Oil of savin is a colorless or yellowish liquid of an unpleasant naTcotic odor and a bitter, pungent, camphor-like taste. Sjj.gr. 0.910— 0.980; ao= + 42 to + 60°; saponification number 11.")— 12.5. It is soluble in % part or more of 90 p. c. alcohol. Of 80 p. c. alcohol. 1')— 20 volumes are requisite, but a. perfectly clear solution is not always effei-ted. The oil distills between 17.") and 2.")0° leaving con- sideralile residue. Below 200° at most 2.") p. c. distill over." Composition. The principal constituent is an alcohol, •■sabinol", which oci'urs partly free, partly combined with ai-etie acid as ester. '> 8abinr)l, which can be obtained by fractionation of the saponified oil. boils at 210—218° (under 20 mm. pressure between 10.")— 107°). Its. odor reminds of thujone; the odor of the ai-etate reminds, of savin. Inasmuch as oil of savin yields a higher saponifi(^ation number after acetylization tlian before, a. part of the alcohol possilily exists in the free state. The acid combined with sabinol was sliown to be aretic acid by the analysis of the silver salt. If the formula assumed for sal)inol, CioHisO. is correct, the saponi- fii'atit)n numbers 11.")— 12.') correspond to a content of 40—44 p. c. of acetate. The amount of free alcohol in an oil examined was about 10 p. c. 1) Tyroceynium chyDiicuiii, vol. Ill, p. 27. ^^ l.iebis's Annalen. l.T, j). ir>9. - 2) Opera omnia, Uber e.""). Obsi'i-vatio 1. s) Phai-ni. .Joiirn., Ill, 25 (189.'">),p. 104.">. 3) Dissertatio cle Snljina. Jeiiae 1707. e) IJericht von S. & <'o., Oct. 1SH5, p. 3',). Oils of the AhiPtine;v. 276 Aecordiug to a more reeent investigation by From in, i (1H!)8) the formula of the alcohol is not CioHisO, but (JioHieO. When juire it boils at 208—209°, its acetic ester C10H15OCOOH3 at 222—224°. In small part the sabinol of the savin t)il is combined with an acid that boils at 24-7°. Oxidized with potassium permanganate, sabinol yields quantitatively tanacetogen dicarbonic acid. f'uHiiO^. which melts at 14-0°. In the highest fractions of savin oil, Wallach^ (1887) found cadinene, 0i-,H24. In addition, it is probable that terpenes are present, but nothing reliable as to their nature is known. From the results published by Dumas 3 in 1835 the conclusion that either pinene or camphene is pre.sent might seem warranted. Dumas isolated a fraction 1.1.5 — 161° which had the composition CioHie. Gruenling* (1878) obtained terephthalic and terebinic acids upon oxidation of fraction l(il°. This also indicates pinene. Inasnmch, however, as savin oil does not contain any consideraljle quantities boiling below 175°, and since it is frequently adulterated with turpentine oil, these statements should be accepted cautiously. According to IJmney'' oil of savin is said to contain a considerable amount of polyterpenes of the b. p. 220°. This, however, does not seem very probaljle since the boiling point of the polyterpenes lies in the neighborhood of about 800°. The chemists of Schimmel k Go." have isolated an aldehyde or ketone from fraction 220 — 250° which, when regenerated from the sodium acid sulphite ad Hroo. Chem. Soc. 1896, p- 1-10. -^) Observation made in the Laboratory 2) Bull. Soc. ehim., II., .37, p. 30.?. of Schimmel & Co. ■■)| Bull. Soc. chim.. III.. 17, p. 48.5. •27H Special Piirt. Examination. Adulterations of cedarwood oil have not yet been observed. Tliis cheap oil, however, is frequently used for the adulteration of other oils, for which purpcwe it is well adapted on account of its feeble odor. It can be recognized by its high sp. gr., its high boihng point, its strong laevorotation, and l)y its slight solubility in alcohol. 43. Oil of Cedar Leaves. Oleum Folioruiii Cedii. — Cedernblatteriil. — Essence des Feiiilles de Cedre. Ai-cording to the observations made in the laboratorj- of Fritzsche Bros..i the oil of cedar leaves of American commerce is never what it ought to be, Tiamely the oil from the leaves of Juniperus vivginhina L. This is partly due to the fact tha,t the name cedar is applied in this (country to two totally different trees, viz. Juniperus virginiana and Thuja occidentalis. It is true, a distinction between them as red and white cedar is generally made, but the distillers of the oil evidently pay little ov no attention to it. They not only use the leaves of lioth species indiscriminately, but also those of other conifers. It is not surprising, therefore, that the cedar leaf nils of commerce vary considerably in their projierties. The spe(.-ific gravities of a numl)er of commercial oils varied from 0,8G.s to ().!)2(), the optical rotation from —3° 40' to — 24°1()'. Some of these oils were soluble in 4 or 5 vols, of TO p. c. alcohol, others not. All of tliese oils had a more ov less thuja-like odor. Geiuhne cedar leaf oil seems to have been distilled but once. 2 The yield was 0.2 ]>. c. This oil had the following properties:-' sp. gr. 0.887; "u = + 59°25'; insoluble in 10 parts of 80 p. c. alcohol. The odor was pleasant, somewhat sweetish. Upon fi-actional distillation most of the oil distilled below 180°, of this the greater part between 178° — 176°. The sp. gr. of this fraction was 0.847; optical rotation +8i)° (at 20° in ii loo mm. tube). Upon bromination it yielded a. tetrabromide melt- ing at 104— 10.j°. This fraction, therefore, consisterl almost entirely of ddinionene. Of the lower fractions but small quantities su]iposed to contain pinene were obtained. Although a nitrosochloride was success- fully prepared, no ciystalline piperidine and benzylamine bases could be obtained. Possibly, as seems to be the case with lemon oil, there are liere tprpenes, closely related to tho.se already known, liut which have not yet been definitely characterized. i| Beiicht von S. & f:ii.. April IS'.IS, |i, 1.-!. 2| In the factory of Fritzsche Bro.s. Cnnip. Bericlit von S. ^^c Co., .\pi-, ls'.i4, p. .j(> ■■') Bericht von S. & Co., Apr. 1898, ji. 1.^. OiI.s of the T'anihinaceiie. 379 The fi'actions boiling hig-liei' than limoneiie wei'e treated with alcohohe potassa because they contained mnall amounts of saponifiaV)le substances (saponification number of the original oil 10.9, of the acetylized 39.1). The acids thus obtained yielded a silver salt corresjionding with silvei- valerianate upon analysis. The acid-free oil then yielded upon distilla- tion under diminished pressui'e a fraction which under ordinary pressure boiled at 210 — 21.")°. Upon cooling, tliis congealed to a (/rystalline mass which upon expression and sublimation revealed itself as borneol melting at 203— 204". In the highest fractions cadinene could be readily identi- fied by means of its charactertstic hj'drocliloride. Genuine cedar leaf oil, therefore, consists principally of hmonene with cadinene, and some borneol, also small amounts of bornyl estei-s. 4.4.. Lebanon Cedar Oil. Origin and History. Whether cedar wood was distilled in antiquity or not does not become apparent from the statements by Dioscorides and other writers. Dioscorides i mentions as medicinal plants a number of pinus species, among them apparently also the cedar of Lebanoji. The Cednis lihani Ban'. (Pinus cedrim L.. Ahifs cedrus Poir, Larix eedrihs Mill.) was considered during antiquity as one of the noblest trees. As such, and on account of its durable wood, it is often mentioned in the books of the Old Testiiment. Upon distillation, the comminuted wood yields 2.9 p. c. of oil. 2 Properties. The yellowish-bi-own oil has a verj^ pleasant cedar odor and might find practical application if a sufficient quantity of the wood were to be had cheap. Sp. gr. 0.985; ^n = — 10°48'.- 45. Pandanus Oil. In India. Arabia and Persia, the flowers of Pandnmis odoratissimus L. (Fam. Pandannreiw) are highly esteemed on account of their fragrance and their supposed medical virtue. ^ The Mohammeda,n physicians use the aqueous decrjction r>f the bruised stems against various di.seases. Among the Hindoos, the aqueous distillate of the flowers is used as a preventive against small-jjox. If the distilled water is to be used as a perfume, it is sometimes prepared with rose water- and the addition of sandal wood oil. An odoriferous fatty oil, made by maceration of 1) De mat. med. Editio Klihn-Mprengel, Vol. 1, pp. '.)n, 140, «80. 2) Bericht von S. & Co., Apr. 1892, p. 41. .">) Dyniock, Warden and Hooper, Pharmaco(;raphia iadica. Part. VI, p. 280 Special Part. the flowers with sesame oil, is also much used. According to Holmes i (1880) the volatile oil has a very pleasant, decidedly honey-like odor. Concerning the other properties of the oil nothing is known. Andropogoii Oils. Origin and History. The genus Andropogon of the family Gra- mineae is distributed well-nigh over all parts of the globe. A number of species, which are indigenous particularly to the East Indies, the islands of the Indian Archipelago and northern Africa, are odoriferous on account of the volatile oil they contain. The oils distilled within recent periods from these grasses, some of which are being cultivated, are: palmarosa or rusa oil, also known as Indian geranium oil; citronella oil; lemon-grass or Indian verbena oil; and vetiver oil. These aromatic grasses have been used on account of their fragrance for various purposes during antiquity : for the aromatization of wine ; also of earthenware wine cups, the so-called Rhodian cups; in the preparation of ointments and oils ; a,n incense in i-eligious rites ; and ■Aff couciies during festivities. In Sanskrit writings, in the Old Testament, and in other documents of antiquity, these grasses are referred to under various names. The spices and annointing oils mentioned in the biblical translations and other ancient writings as imrde, stakte, schonus, etc.. apparently have been used synonomously for the fragrant andropogon grasses and their roots. Of these, it may be supposed that Andropogon laiiiger Desf. was the best known and most used during antiquity, inasmuch as it was more widely distributed throughout northern India, Thibet, Persia and Arabia as far as Egypt, Nubia and Ethiopia than the other species. Originally, however, and again in more modern times, the term uarde wa,s applied onlj^ to the aromatic root of the valerianaceous Nardostachys JB.tamansi D. C, indigenous to the Hima- layas of northern India, perhaps also to Valeriana eeltica L. indigenous to the European Alps. The Greek and Koma.n writers possibly referred to the same aromatic andr.opogon species when they used the woi-ds ^oivo^i or riK; foiiip. .\iTiiiv il. I'harni.. 2:t4. p. :)21. -) P.nnibay jd'esidt'nc.v. 31 StenhoUKt' (Litbig's Annalen. ."II, p. 1,o7) in 1.S44 reports on an inyestigation of East Indian gra.ss oil from Anilropuson ivaraacima, the odor of wliicli resembled tliat of rose oil, the taste that of oil of lei i. Upon di.stillation it yielded a hydroearbon, I'liiHiii, boiling at 170°. It may be assumed with some degree of eertainty that this grass oil was not iialmarosa oil, lint citronella oil from Anrlropoffon ii.-irdiix L., some- times also designated Andvopogoii ivnrilncusa Roxb. ; for citronella oil contains a teriiene boiling at 160°, viz. camjihcne, whereas palmarosa oil does not contain snch lo^\■ iKjiling constituents. (iladstone (.lonrn. Chem. Soc, 17, p. 1; .lahresb. f. ('hem., ISO:!, p. .l-IS) describes Oih of the Gnrininene. 283 The first exaiuination with unobjectionable material was carried out by Jaeobseni in 1871. He establislied the fact that the principal con- stituent of the oil is an alcohol, OioHigO, boilin.<>' at 282 — 288°. to which he gave the name geraniol. He further discovered the calcium chloride compound of geraniol, which is readily decomposed into its components b.v water, and which lias become of such great importance in tlie purification of this alcohol. Semmler^ later (1890) verified the correctness of the formula CioH^gO and recognized geraniol as belonging to the unsaturated chain compounds. G-eraniol tlms became the first repi-esentative of a new and important (dass of coTistituents of volatile oils designated as aliphatic terpene alcohols. The amount of geraniol in palmarosa oil varies from 76 — 98 p. c. Of this the greater portion exists in the free state, and about 5.5 — 11 p. c. are present a»s ester. The acids of tlie ester content of the oil are, as was shown by Gildemeister and Stephan-' (1890), approximatel.v like parts of acetic and normal capronic acids. Acetic acid was identified by means of its silver salt (calculated: Gl:.69 p. c. Ag. : found; 64.54 p. c. and 64.87 p. c. Ag. ). Tlie capronic acid isolated from palmarosa oil boils at 205—206°, has a sp. gr. of 0.985 at 15°, is opticall.v inactive and, therefore, identical with normal capronic acid. (Analysis of silver salt: calculated: 48.48 p. c. Ag. ; found: 48.24—48.55 p. c. Ag. ) Of terpenes but a small amount is present in palmarosa. oil, viz. about 1 p. c. of dipentene (tetrabromide, m. p. 125°; nitrolljenzvla.mine, m. p. 109— 11(.)°). Judging from the odor of tlie oil, traces of methvl heptenone are also piresent. Besides geraniol, Flatau and Labbe''' claim to liave found a second alcohol, viz. citronellol. Their method of separation of tliese two alcohols is as follows : The oil is first saponified and the saponified prodnct distilled under diniinishpd pressure. Fraction 120— 140°, under 30 nini. pressure, is boiled with an equal weight of phthalic acid anhydride and an ecjual volume of ben- zene for au hour in a flask connected with a reflux condenser. Soda, is then added, the product of reaction dissolved in water, and the solution extracted wdtli ether. H.vdrochloric acid is finally added whereby the acid phthalic acid esters of g-erauiol and citronellol are liberated. an Indian geranium oil. sp. gr. O.'.Ha at 21°. wliich he considers identical \vith the East Indian grass oil from Andropoffoii ivar:inijuii». Wliich oil if was i:i realit.v does not liecome apparent from the statements of the author. 1) Liehig'H Annalen, 1.^57, p. 232. 2) Berichte, 23. p. lOdS. 3| Archiv der Fhar., 234, p. 321. t) Oompt. rend., 126. p. 172.".; Bull. Sue. clnni., Ill, 19. p. (133. 284 Specml Part. These esters are now dissolverl in lig-roin and the solution cooled down to — 5°. At this temperature it is said that the g-eranyl ester crystallizes out quantitatively whereas the citronellyl estei- remains in solution. The isolated acid esters are sayjoiiified with alcoholic potassa and the free alcohols purified by i-ectification. In this maimer Flatan and Lablte claim to liave demonstrated the presence of 6:] p. e. of geraniol and ] 7 p. e. of citronellol in pahnarosa oil. A repetition of this experiment in the Laboratory of Sehimmel & Co.i has i-evealed the fact that tlie liquid ester reji'arded as tlie acid citronellyl phthalie acid ester was also fairly pure geranyl ester as was shown by the calcium chloride compound of the alcolnjl obtaineil by saponification. If citronellol is contained in palmarosa oil, the proof for ^vhich may be considered to be still wanting', it can be present in traces only. A second statement by the same chemi.sts appears to be based on a similar weak foundation. Flatan and Labbe^ have claimed tliat palmarosa oil contains a saturated fatty acid GnHosOs. m. p. 28°. According- to the investigations of [-ichimmel & Co.,-' pure palmarosa oil does not contain such an acid. The observation of the French chemists may possibly be referred to the presence of cocoa nut oil or some other fatty oil which had been added as a-dulterant. Properties. Palmarosa oil is colorless or light yellow, and has a pleasant odor reminding- of roses. The optical rotation ^-aries, some oils being- slightly dextrogyrate, others slightly laevogyrate, still others inactive. Angles of rotation varying- from +1°41' to — l".").-)' have been observed. It is solulile in 8 or more parts of 70 ]i. i-. alcohol. The saponifi- cation number lies between 2(1 and 4(». Aftei- acetylization the saponifi- cation number lies between 280 and 270. Jeancard and Satict have recently observed that the ainount of free acid in(/reases if the oil is kept in partly filled containers. Examination. Palmarosa oil is frequently adulterated. The follow- ing adulterants have been found: gurjun balsa-m oil, cedar wood oil, turi)en- tine oil, petroleum (kerosene, paraffin oil) and cocoa nut oil.-'"' They are all indicated by their solubility in 70 p. c. alcohol. Oils adulterated with cocoa nut oil solidify when exposed to the tempei-ature of a. freezing mixture. Petroleum and turpentine oil lower the s]). o-r., whereas fattv 1) Bericht von S. & Co., Oct. 1S9S, p. (iT. i 2) Compt. vend., 126, p. 1726. 3) Bericht von S. & Co., Oct. 189H, p. 2<.l. 'I Bull. .Soc. Chlm., Ill, 23, p. :!7. Ooni[i. also Bericht von S. * Co., Apr. 190U. p. 26. S) Bericht von S. & Co., Apr. l.s.SH, p. 22: Apr. 1SS9. p. 20; Oct. ISiiO, p. '^H. ~ Oils (if the Oraniinene. 285 oils raise it. "In donlitful cases it is well to resort to an acetylization. Oils with less than 75 p. f. total geraniol content are to be rejected. Prodtjction and Commerce. For the last 20 years Borabaj- has been the principal center and port of exportation, whereas formerly almost the entire output was taken by caravans over land from East India to Cairo and Constantinople. From these places it was distributed to the brokers. The oil is distilled in the Khandesli district noi-theast of Bombay. Pimpalner, Akrani, Nandurbar, Shahada and Taloda are the principal places of production. In skins it is conveyed on the bullock's back over the Kundaibari pass to Surat. and by Dhulia and Manmad to Bombay. Here it is transferred to large tinned copper vessels of lOO to 200 lbs. capacitj-. These are not boxed, but surrounded by a network of ropes for the purpose of more ea.sy handling. In 1879 the total production was estimated at 3,600 k. Since then it has risen enormously and may amount to about 20,000 k. at present. 47. Ginger-grass Oil. ttinger-grass oil is an inferior quality of palmarosa, oil, or a mixture of the latter with much (up to 90 p. c.) turpentine oil or mineral oils. Oct;asionally other grasses are also used in the distillation (Andro- pogon laniger?), for some ginger-grass oils possess a phellandrene-like odor which is entirely wanting in the palmarosa oil. Such an oil had the sp. gr. 0.897, «d = — 2°8' and was soluble in 70 p. c. alcohol. Its petroleum ether solution gave a faint phellandrene reaction with sodium nitrite and glacial acetic acid ( Gildemeister & Stephan.i 189(5 ). 48. Lemon-grass Oil. Oleum Andropoffonis Citrati.—Leiiioiigrasol.— Essence de Lemonjrrass. Essence de Verveiiie des Indes. Origin and Preparation. Lemon-grass, Andropogon fitnitus D. C, which is cultivated all over India, is used, in the form of an infusion, both internally and externally against all possible diseases. The oil, which is officinal in the Pharmacopoeia of India, is especia^lly esteemed by the Hindoos as a remedy against cholera. For the i)roduction of the oil, the grass is cultivated on a large scale only on the Malabar coast in Travancore on the western slope of the mountains, north of Ajengo. The distillation is conducted in a primitive manner in plain stills. 2 1) Archiv il. I'harin.. 23+, p. H2(i. =) Pharmacosraphia Indica, Part VI. p. 5B4. 2m Sppcial Part. Lpraou-gTnss oil is also distillpil iipar Singaporf anil in (Vvlon. Andro- pogou fitratuH is also (•ultivatfd in S. Thonie, where oil has l:)een distilled experimentally i (1897). In Brazil (Porto Alejire) an attempt to produce the oil has also been niade.^ Composition. Nothing- about the ehemicaJ composition of lemon- grass oil was known until 18H,S when citral, an aldehyde CioHioO possessing a strong lemon-like odor, was re(/ognized a.s the principal constituent in the laboratory of Schiminel & Co.'* Two years later Dodge-i ilescribed this sub.stance as citriodoric aldehyde. He, however, did not have the aldehyde in a, pure state inasmuch as he describes it as slightly dextrogyrate, boiling at 22.5°. Pure citral is inactive and boils between 228° and 229°. Inasnmcli as Barbier and Bouveault'' obtained three semicarbaz(nies'* by the action of semicarbazide on lemon-gi-ass oil, melting resp. at 171°, 160° and 1;?5°, they propounded the hypothesis that the citral from lemon-grass consists of three isomeric aldehydes. Since semicarba- zones of the same substance frequently oci-ur in different modifications, which are distinguished by their melting points, solubility, and behaAnor towaril acids, it nmst be i-onsidered in this case — as was, in fact, proven by Tiema.nn'^ — that there are no isomeric aldehj^des but isomeric .semi- carbazones. Flat;iu8 arrived at a like conclusion. W. Stiehl" also assumes the presence of three isomeric aldehydes CioHuiO in lemon-grass oil: (jf citral (geranial), 10 p. c; citriodoric aldehyde, -tO — 50 p. c; and of allolemonal 25 — 30 p. c. Judging from the method of preparation this citriodoric aldehyde, according to Schimmel & Co.,i" corresponds to the citral of commerce. Inasmuch as Semmlerii (1891) has shown that this is identical with the geranial from geraniol, citral and the citriodoric aldehyde of Stiehl may be reaarded as identical. 1) Ber. (1. pliarni. (ie.s., 7. )ip- 3.~i.-3, .~»01 ; s, p. 2a. 2) lifi-irht vein S. * Co.. .ijir. IsllO, jj. i;S. 3) Berirht von S. & Co., Oct. IS.SS, ii. IT. + 1 Aiiier. (.'hem. .J. 21M:t and Tiomann, Berichte. 81. p. S21. 7) Berichte, :t2, i>. ll.T. 8) Bull. Soc. ('him.. III. 21, p l.-.H. 0| .lourn. f. prakt. Chem., II, 58, p. ol. lu) Bericht von ,S. & Co., Oct. 1808, p. (ifS. li| Berichte, 24, p. 203: 81, p. 80(11. Oils of the Gniinineae. 287 Xeitlier has Stielil's third aldehyde stood the test oF eritirisin. Doebneri (1898) found that i^tiehl's alloleiiioua-l {-(insists of about eqiial parts of citral and a. non-aldehyde sul)stanee. From the exhaustive investigations of Tienuvnii^ (iSDiS) which can merely be referred to here, it becomes well ni<;h certain that, the bulk of lemon-grass oil consists of citral. Besides citral, it contains traces of citrouellal and possibly also of an isomer of citnd (Doebner,-' 1898). In the lii-st fracticm of lemon-grass oil Barbier and Bouveault-'' (1894:) found methyl heptenone. Inasmuch as they could not obtain hydro-m-xylene by means of zinc c-hloride, nor a solid bromide upon the addition of bromine, thej^ declared this methyl heptenone different from the one obtained by Wallach-"' from cineolii' acid. However, according to Schimmel & Co." the methyl heptenone obtained from lemon-grass oil is identical with that obtained bj^ Wallach. The methyl heptenone regenerated from the bisulphite com- pound from lemon-grass oil boils at 178 — 174°, sp. gr. (t.8.j;5 at 20°, index of refraction, nD = 1.^=8996. Wallach records the following physical constants for methyl heptenone from cineolic acid: b. p. 178 — 174°, sp. gr. 0.8.'):! at 20°. no 1.44008 at 20°. If the ketone from lemon- grass oil is heated with zinc chloride, hydro-m-xylene, CgHia (b. p. 182 — 18.")°) results in considerable quantity. Upon nitration this yields dinitrom-xylene (m. p. 92°) and the very characteristic trinitro-m- xylene which melts at 181 — 182° and is difficultly soluble in alcohol. The same substances have been obtained from the methyl heptenone from cineolic acid so that a doulit as to the identity of the methyl heptenone from lemon-grass oil and of the com])ounds of like composition obtained by Wallach and by Tieniann and Semmler' can no longer exist. Geraniol,* the alcohol corresponding to tlie aldehyde citral, is con- tained in the highest fra.etions of the oil and has been isolated by means of its calcium cliloride compound. The presence of linalool* in fraction 198 — 200° is also rendered probable. To furnish direct proof that the alcohol in this fraction is linalool is a difficult matter in the presence of citral and geraniol. Labbe» has found capronic and caprinie acids, which he supposes are present in form of the geraniol ester. 1) Berichte, .31, 7). 81!l.">. «) Bei-icht von S. & Cti. Ilct. 1894, p. .32. 2) Berichte, 31, pp. 327S, 321)7, .3;!24: Cump. also Tieiiiann & Senimler, Berichte, .32, lip. 107, 11.'. 28, p. 212(5. footnote. 3) Bericlite. 31, p. 1891. ?) Berichte, 2tj, p. 2721. i) fonipt. rend., 118, 11. 983. sj Bericht von S. & Co., Oct. 1894, p. 32. s) Liebig'K Annalen, 2.''iS. p. 319. n) Bull. Soc. (.'him.. Ill, 21, p. 159. 288 Special Part. The presence of a terpeiie, b. p. 175°, aD= — ^"iS', has been ob- served by Barbier and Bouveault in several oils. It yielded a liquid bromide from which small amounts of solid substance separated which melted at 8.")°. In other oils this terpene could not be found and possibly must be regarded as an adulteration. According to StiehP lemon-grass oil contains dipentene and possibly limonene. Properties. As the name indicates, lemon-grass oil has an intense lemon-like odor and taste. It is a reddish-yellow or brownish-red, mobile liquid of .sp. gr. 0.899— 0.!)0;?. On account of the dark color, the rotatory power mostly cannot be determined. In a few instances in which it was possible, an angle of from + 1° ^•")' to — 8° 5' was observed. The oil is readily soluble in alcohol, even in dilute alcohol, for it gives a clear solution with 2 and more parts of 70 p. c. alcohol. ^ The citral content amounts to 70—75 p. c. Examination. Adulterations with fatty oil or petroleum are recog- nized by the incomplete soluliility in 70 p. c. alcohol. The citral assay, which .should not yield less than 70 p. c. aldehyde, .supphes a further clue as to the quality of the oil. The method of assay is the same as tlie assay of cinnamic aldehyde in cassia oil: 10 cc. of oil are sliaken witli bi.suljibite solution, the number of cc. of oil going into solution being regarded as citral. Tbe necessary apparatus and the details of procedure are described under cassia oil. [nasmucb as methyl heptenone likewise reacts with bisuljibite, one might suspect that the aqueous solution not only contains the citral, but also the methyl heptenone so that the ai:)parent citral content was in reality that of citral -|- methyl heptenone. However, since the bisulphite compound of methyl heptenone is broken up into its components when heated in the waterbath, this ketone is contained in the oily layer, citral in the aqueous solution. The assa.y, therefore, shows the correct citral content. ^ Production and Commerce. Lemon-grass oil is principally produced in East India, more particnhirly in the province Travancore south of Cochin. The principal commercial center is Trivandrum. The total exports from the Malabar coast wei'e: 1) Loc. cit. 2) An oil distiJIerl In I'oito .^legre. Brazil, showeil a peculiar behavior in repfard to soliiblUty since it did not give a clear solution e\-en .with 98 p. c. alcohol. Its sp. gr. was 0.89.5. anfflo nf rotation — 0°8'. citral content 77 p. c. The oil, which has not yet become an article of commerce, is obtained from cultivated plants. In rainy years, four crops of this grass can be harvested; in dry years only three. The yield ot oil from the fresh grass varies from 0.2+ to 0.4 p. c. according to (he season (Bericht von S. & Co.. April 1896, |i, OS.) :') C!omp. Tiemann. Berichte, :!1, p. 3.324. Oils of the Grnmweaf. 289 Season 1891—92 l,-t5() Cases Season 1894—95 2,370 Cases 1892—93 l,8G;t " " 189C— 90 3,070 ■■ 1893—91: 2,332 " " 1896—97 3,000 ■' Each ca.se contains 12 wine bottles witli a total net (-(jntent of about ~Yi k. Some oil is also distilled in Ceylon, but only liere and there and then only in small quantities. Statistics of production are wanting. In the Straits Settlements the distillation is no longer i-onducted on as large a scale as formerly. The output is at most 2, Odd— 3, (>()() lbs., for the total export of volatile oils from Singarpore to England in 1896 amounted to only li.lS.j lbs. Engl., of which at least twothirds was citronella oil. 49. Oil of Yetiver. Oleum Andropogonis Mnricati. — Vetiver51. — Essence de Vetiver, Oeicjin and Prepahation. Andropogon nmricatus Eetz., known in India as Vetiver or Cus-Cus, is a perennial grass the leaves of which are odorless, but the long fibrous roots of which possess a peculiar strong odor reminding somewhat of m,yrrh. The plant is found all along the Coromandel coast, in Mysore, in Bengal and in Burma in moist, heavy soil particularly along the shores of rivers. It grows also in Reunion, Mauritius and the Philippines, further in Porto Eico and Jamaica 1 and in Brazil (Peckolt^). In India the root is used in the manufacture of artistic mats and wicker baskets. Inasmuch as the distillation of the oil is difficult on account of its sparing volatility and viscid consistency, it is usually cmiducted with sandal wood or sandal w(.)od oil. This oil is seldom exported, whereas the root constitutes a regular article of commerce. Tuticorin (south Coromandel coast) is the principal place of export. The root is of a reddish cohjr ;ind often contaminated witli i-ed sand. A half distilled root is frequently found in commerce and can be recognized by its light color. The yield obtained in Europe from the Indian root varies from 0.4 to 0.9 p. c. In Reunion larger quantities of oil are distilled, but the root is not exported. Properties. Vetiver oil is the most viscid of all volatile oils. Its color is a dark yellow to dark brown. It has an intensive and very per.sistent odor which is not pleasant to some persons. On account 1) Pharmacograiihia indica, part VI, p. 571; Odoroffraphia, vol. 1. p. 809. 2) Catalogue of the National Exposition in Eio 1866, p. 22 and IS. — Pharm. Rundschau. 12, p. 110. 19 290 Special Part. of its .sparing volatility it is used in finer perfumery primarily for fixing the more volatile odors. At Uj° vetiver oil is heavier than water. Oils distilled in Germany had a sp. gr. of 1.015—1.080 at this temperature. On account of the tough consistency of the oil no claim for great accuracy can be made for these figures. At higher temperatures the oil is lighter than water. One sample had a sp. gr. of 0.994 at 44°. On account of the dark color, the angle of rotation cannot be ascer- tained in most instances. In one instance an = + 27° 40' was observed, iu another +25 to 26°. "^ Vetiver oil forms a clear solution with 1% to 2 p. of SO p. c. alcohol. Upon the further addition of alcohol the solution becomes turbid. A vetiver oil distilled in Germany boiled between 144 — 200" under 28 mm. pressure. Between 144—164°, 8 p. c. were obtained; from 164— 170°, 10 p. c; 170—180°, 24 p. c. ; 180—185°, 80 p. c. ; 185—200°, 20 ]). c. : residue, 8 p. c. The saponification number lies between 60 and 80. The oils distilled in Reunion are less viscid and speciflcall.y lighter. In a. number of samples the sp. gr. varied from 0.982 — 0.998 at 30°. Being light in color the angle of rotation could be readily determined : w-D ^= -\- 29° and + 86° being observed in two cases. These oils possessed the same solubilit.y as those described above. Their faint odor and the difference in physical properties would lead one to suspect adulteration, but, owing to the want of knowledge of chemical composition, this cannot be decided. It is by no means excluded, however, that these differences are attributable to differences in the material distilled, for it seems but reasonable to assume that the Reunion oils are distilled fi'om fresh roots. Peckolt-' found the sp. gr. 0.996 at 15° and 0.972 at 18° respectively for two oils distilled from fresh Brazilian root. It should be noted, however, that only 10 kilo of root were used and that it would be ditticult to obtain the less volatile constituents from such small amounts. ExAMixATioN. The examination is restricted to the determination of the sp. gr., solubility and, if possible, of the rotatory power. Under all circumstances it should yield a clear solution with two parts of 80 p. c. alcohol. This permits of the recognition of fatty oils which are frequently used as adulterants.'* The admixture of sandal wood oil would not be recognized by the solubility test, but by the lower sp. gr., also bv the change in the 1 1 Berlclit von S. & Co.. Oct. 1897, p. (i2. •■!) Herlcht von S. & Co., A])r. 1893, p. ■) Footnote 2, p. 289. Oils of the Oramweae. 291 rotatory power. Inasmuch as sandal wood oil is laevogyrate, a vetiver oil adulterated with it will possess a lower rotatory power than a pure oil. 50. Cltronella Oil. Oleiiiu Citrouellae. — Citroiiellol. — Essence de €itroiielle. Origin. Gitronella oil is distilled from the grass Andropogon nnrduii L. This plant grows principally in Ceylon, the Malaccan penin- sula, also in India proper, and occurs frequently in tropical East Africa, i Ac(/ordiug' to Winter, ^ one of the largest distillers of citi-onella oil in Ceylon, two varieties of Andropogon nardui^ a-re used in the preparation of the oil. In Ceylon, whic-h produces most of the oil, Luna Batu is the most widely distributed variety. It is said to have first been found in Ma-tara, a city in the district of like name in southern Ceylon (comp. map). As will be shown later, this variety yields an oil relativelj^ poor in geraniol, and contains methyl eugenol, has a high specific gravity and constitutes the bulk of the oil of commerce. The second grass variety, which is cultivated in Ceylon only in the neighborhood of Baddagama, comes fi-om Malacca and grows on good soil only. Apparently this variety is generally cultivated in the Straits Settle- ments, also in Java ^ and is known as Maha pjangiri. The oil from this variety has a lower specific gravity. At least the oil from Java has a lighter color and may in general be pronounced the finer oil.-^ Preparation.-'' The cultivation of citronella grass in Ceylon is con- fined to the Southern Province, mainly between the Gin Ganga in the northwest and the Walawi Ganga in the east. It is found growing on the slopes of the hills. The individual tufts of grass grow at small, irreg-ular intervals, attaining a height of 1 meter. According to the statement of competent dealers, as much as 40,000 to .50,000 acres are at present under cultivation. The plants require little or no care, provided the formation of seeds is prevented by regular harvests. Otherwise the tufts become too dense, become yellow within, and spoil. In general a distinction is made between two harvesting periods. The first and principal season is in July and August, the second lasts from December until February. The yield averages from 1(3 — 20 bottles (of 22 oz. each) per acre for the summer. 1) Ber. (1. pharm. Ges., 7, p. .501. i) Beiicht v. S. & Co., Apr. 1000, p. 11. 2) CheiiiiHt and DruggiBt, .52, p. 646. 5) According to the Berlcht von S. & 3) Bericht v. S. & Oo., Oct. 1899, p. 13. Co., Oct. 1898, p. 11. 292 Special Part. and from 5— 1(.) bottles for tlie winter season. Exact data cannot be o-iven, for tlie yield naturally varies with the weather, and the age and location of the plantation. Thus e. g. a plantation yields less and less oil with increasing age, though climate and soil conditions are favorable. When the plantation has reached the age of 15 years new plants have to be raised if the industry is t(j be ])r()fltable. The distilleries are mostly located at the l):ise of riilges where cool water is to be had in sutBcient (quantity. The construction of the ilistilleries is not at all primitive, as is shown in the following sketch. The success of the natives, who constitute the majority of the proilucers, is really remarkable. The mai-hinery is housed under ;i long roof which serves as a protection against the sun. The Elevation. Fig. GO. 1. ('hiinni.'y. 2. Boiler. '•\. Stills. 4. Condeiispr. n. Condensing? I)asin. r,. I^oeked cellar for storage of the distillate. 7. Uoof itiff. rd). S. A\'ater supidy ijipe (tig. 61). 9. Basin for storage of distill,ate. regulation .steam l)()iler, provided witli safety valve and water gauge, rests on a. solid foundation. The cylindrical iron .stills, mostly 6 — 7 ft, high and 8 — 4 ft. in dia.metei-, rest on a base and are provided with a connnon, interchanoeable a.lemliic. Tliis connects with a spiral cooler in a lai-ge wooden barrel resting on a lowered water basin. The conden- sation products of the cooler empty into a, basin still lower tlian the one con.stituting part of the cooler, ntnl in a locked compartment. The complete arrangement is shown by the accompanying sketches. (Fig. 60; anil fig. (il, p. 293.) Oilfi of the Graniineae. 293 The distillation is <:-oiidneted with direct steam without the addition of water to the i^rass. The water in the barrel condenser, when wai-iu, is used for feeding- the boiler; whereas the water in the lower basin serves to effect eoinjilete condensation. The distillate is stored without effecting' a separation of the oil. After a definite period, the proprietor visits his distilleries to remove the oil. The aqueous distillate is p(jured away. A cliarge of dry gra.ss, for only such is used, is distilled in aljout 6 hours. The exhausted grass, after being dried in the sun, is used as fuel. The Southern Province is extremeh' poor iu wood. For this reason the distillation must be discontiiuied during the rainy season when the exhausted grass can no longer be dried. Ground-plan. Fig. 61. A still 7 ft. high and 4^ ft. in diameter yields about IG— 20 bottles of 22 oz. each per daj', or about 360 — 440 oz. The work never being controlled no accurate figures as to yield ai'e obtninalile. Besides the apparatus described above, such with direct Are are said to be ill use in some districts. However, most of the citronella oil is to-day obtained by steam distillation. If the ili.stillation is conducted over direct fire, water is added to the grass. It should t)e stated the o-rass is not dried l)ef(^re distillation. Nevertheless it is not moist when put into the a])paratus. for as a rule, several houi's elap.se from the 294 Special Part. time when it is cut to the time when it is distilled. With a temper- ature of about 65-70° in the sun, this suffices to remove a large portion of the moisture. The districts of production are more clearly indicated by the accom- panying map. The number of stills in operation in Ceylon is estimated at 600, with an annual output of 1,000,000 lbs. of citronella oil. Composition. The principal bearer of the citronella odor and, there- fore, the characteristi(3 constituent of the oil is citronellal. It is an aldehyde of the formula CioHisO. Although present to the extent of from 10—20 p. c. (jnly, it first attracted the attention of investigators. Owing to the instability of the aldehyde, it.s name as well as opinions regarding its composition have undergone repeated changes. Gladstonei in 1872 found the boiling point of '■citronellol," as he designated the substance, at 199—205° and a.ssigned to it the formula CioHieO. Wright-' in 1874 states that it boils at 210°. His analyses agree with the formula CidHisO. By shaking the oil with alkali bisulphite and regenerati(jn with acid, Kremers* obtained an aldehyde whicli decomposed when distilled. One of the fractions upon analysis yielded results corresponding with an heptoic aldehyde C7H14O. Scliimmel & Co. J' designated the compound, regenerated from the bisulphite derivative with soda and boiling between 205—210°, ■■citronellou," without decid- ing as to its ketone or aldehyile nature. Dodge "^ then ]iroiiounced it an aldehyde without, however, liringing any proof as to the aldehyde nature of the "citronella a.ldeliyde." This proof was sup])lied by Semmler" {lcS91) who oxidized the "i-itr(inellon" to an acid with the same number of carbon atoms, tlie <-itronellic acid, CioHisO^. F(n' this renson the sub.stance is now desiguiited as citronellal, a more riitiDual name desig- nating its (.■hemi(;al i-haracter. For the properties and derivatives of 1) .loiini. ('hem. Soc, l-'.". p. 1: I'har n. .Journ.. ll[. L'. p. i ^C) ; .Jaliresb. f. Ch 'mip, 1.S72, p. 816. -) Phariii. .Tourn., Ill, .j, p. 2?,;',. Oladstone a.s wi-ll as Wrif^b t {'rronenusly mention Andropoffon schoenanthufi as the plant from \vhioh citi-onella oil is ilerixerl. Their work, ho\ve\'er, shows with sulRcient certainty that tlie oils exatniueil Iiy them were true citronella oil from Andiopoi^on nardus L. ami not the oil from .1. schoenantliu.'i. On the other hanil, the "UnterHuchviuff des (")els von Andropo^i-on ivilnincusa" by Sten- house in 1S44 (Liebig's Annalen, 50. p. I.i7). whii-h he calls East Indian grass oil. does not pertain to palmarosa oil, bnt in all probability to citronella oil. Comp. "Ueber Palmaro.saol" by G. E. liildemeister and l-C. Stephan. .Vrchiv der Pharm.. 234, p. ,32.3. 3) Proc. Am. Pliarm. Assoc. H.'>, p. .",71; Chem. Centralbl., Isss. ]i. 8'.)8. ■1) Bericht von S. & (^>., Ocl. 1SS8, |). 17. 5) Dodge assigned to it the eoi-rect formnia CmHisO. ,Vmer. ('hem. .Toiirn., 11, p. 456; Chem. Centralbl., 1S'.)II, 1, p. 127. 0) Bcrichte, 24, p. 21(1. Oils of the Gramineae. 295 citronellal see p. l.j-t. A detailed chemical examination of a Lana Batu oil has recently been made by Schimmel & Co.i Citronella oil contains but 10 — 15 p. c. of terpeues. In fraction 157 — 164° camphene has been found (Bertram & Walbaum,^^ 1891). By passing hydrogen chloride into an ethereal solutir)ii of tliis fraction there is obtained, in addition to liquid products, a soliil chhji-ide. which, when heated under pressure with water at 100°, yields quantitatively camphene. By treating the same fraction with glacial acetic acid and sulphuric acid, isoborneol results. Furthermore there is present a second terpene of like boiling point which has not yet been identified. ^ Fraction 172 — 177° contains dipentene (tetrabromide, m. p. 124°). ^ Limonene* also is present and has been identified as tetrabromide melting at 105°. Of oxygenated constituents of an alcoholic nature the presem-e of borneol and geraniol has been determined with (/ertaiuty. (Jn a(/count of the small amount present (1 — 2 p. c), the former can Ije isolated only with difficulty. The melting point was found at 203 — 204°, its specific rotatory power [«]d^= — 31.82°, hence laevo borneol.* Geraniol^ constitutes al>out one-half of the citronella, oil. The alcohol can be obtained pure by treaiting the corresponding fraction with calcium chloride and decomposing the calcium chloride geraniol with water." Basing his conclusion on somewhat unsatisfactory a.naiytical data, Dodge"^ assumes tlie ])resence of an alcohol ('loHociO, b. p. 222°. idHiitii-al with citroiiellol (citronellyl alcohol) obtained by the redui-tion of citronellal. Tliis claim still requires verification.* Methyl heptenone," acetic and \'alerianic acids^'J as esters and liniUool" have also liepii found. .Inother constituent, methyl eugenol, has lieen fonml by Schim- mel & Co. 11 This proljably occurs only in tlie L;ni!i Batu oil, and to it the highei- s]iecific gravity of this variety possilily is due. Fi-oni the highest boiling jiortion of the oil a fraction was oljtained whicli pos- sessed the cjdor of methyl eugenol and which upon oxidation with 1) Bericht von S. & Co., Oct. 1899, pp. 13—22. 2) .Jourii. f. prakt. ('hem., II, 49, p. 16. 3| Bericht von S. & Co., Oct. 1899, p. 1."). i) Bericht von S. & Co., Apr. 1.894, p. l.T. 3) Ibid.: Oct. 1S9H, ]]. 11. 6) The preparation of geraniol I'roni citronella oil is patented. G.I. P. 70,4:i.~). Cheni. Zeitnng. IS, p. 13.T6. 7 1 Footnote 5, p. 294. 8) Flataii and Labbe claim to have found 6 p. c. of citronellol in citronella oil. As shown OTi p. 284 under jjalmarosa oil, the method which they employed to effect the separation of citronelhd and geraniol is altogether unreliable. 9) Bericht von S. & Co., April 189.5, 21. i«) Kremers, footnote 3, p. 294. 11) Bericht von S. & Co., Oct. 1898, p. 17. 29G Sperml Part. potasHiinii permanganate yielded veratric arid melting at 179°. Accord- ing- to a more recent investigation 8 p. c. of niethjd eugenol was found present.! If this occnrreni:-e explains the higher sp. gr. of the Lana Batu vai-ietv. the cause for the higher optical rotation is to )je sought in the larger ci:)ntent of strongly hievogyrate camijliene. The lowest fractious of the oil in which the methyl eugeiiol had been found, had au angle of rotati(H) «o = — ."5° 0'.^ Aci-ording to the recent investigation of Schimmel eV: (.'o. already referred to. the composition of the Lana liatu oil may be summarized as follows: a liquid caniphene, dipentene, limonene, citronellal (28.2 p. c), geraniol ( 32.9 p. c. i , linalool, borneol, terpineol ( ? ) , methyl eugenol ( 8 p. c. ), a light sesquiterpene (sp.gr. 0.8G48), a heavy sestjuiterpene (sp.gr. 0.912).'* So far as examined the oil from the Mana pangiri variety has the same con.stituents, liut the two oils differ decidedly in percentage com- position, the Majja, pangiri variety containing u]) to 91 p. c. of acetylizable constituents:-* ~ii)Ao — 55.34 p. c. citronellal, 88.15 — 31.87 ]i. c. geraniol, and only 0.7H — O.Hl p. c. of methyl eugenol. The low percentage of the last mentioned substance accounts for the low specific gravity. Properties, (jitronella oil is a yellow or yellowish-brown liquid, sometiTues green due to the jiresence of copper. Brownish oils f)-e(juently become green when exposed to the air. This cluinge does not take place if the i-opper is removed l)y shalving the oil with acid.^ The odor of citronella i:)il is ])leaKant and histing. Frequc^ntly the odoi- is desc-ribed as re.sendilin;^- that of Ijalin. This comparison is not pertinent inasmuch as the odoi- of b:ilni resenililes citral. and not citronelhil, the bearer of the i-itronellii, odor. With regai-d to physical ])ro])erties, the oils of the two vai-ieties of g7-;iss ])reviou.sly described diffei- decidedly. The first kind, whic-h may be designnted as 8ingapoi-e oil and which is regarded ns the better (]u:ility, has a s]>. gr. ()..S8()— O.IHIO. rotatory ])ower '/jD = — ()°34' to — 3°. and a geraniol content of from 80— 91 p. c. The oil distilled from Lana. Ba.tu constitutes the bulk of the coni- merciiil oil. Its s]i. gr. is 0.900—0.920, «i. = — 5° to — 21'-\ the geraniol content Viiries from 50 to ;it most 70 ]). c-. M Bei-icht roll S. & Co., Get. IS'.l'.l, j). 22. 2) Bericht von S. & Co., Oct. ISils, p. 17. 3) Nn mention is made of the citral found by Flatan, wiio clainiK to iiave oljtained — :!0 p. c. of citronellal and 2—.'", 11. c. of citral. (Hull. Soc. Cliim., Ill, 21, p. l.-,8. ■1) Bericht von S. & Co., Apr I'.lCO, p. 11. >-') Pharm. .lonrn.. Ill, 21, [). It22. Oils of the Grainineae. 297 The .solubility of both oils is about the same. A ^;-ood citroiiella oil yields a clear solution with 1— 2. parts of an 80 ]). c. alcohol. This solution, as a rule, remains clear if the quantity of a cohol is iiicrea.sed to 10 vols. Sometimes, however, the increase of the alcoh(.)l to 5 — 10 vols. eau.ses a slight turbidity, but even upon longer standing in a closed vessel no oily drops separate. Citronella oil does not yield a definite sapouificati yi number. On account of the slow decomposition of the citroiiell,-d by yieans of alkali the results will vary with the length of boiling. Examination. In testing the oil. the main attention is to l)e directed against the most common adulterants, fatty oils and petroleum. The latter reduces the sp. gr. of the o\t decidedly, whereas the fatty oils scjircely produce a change in this respect. Both adulterants can be detected by the behavior of the oil toward (SO p. c. alcohol. The follow- ing table 1 shows the solubility of pure and intentionally fululterated citronella oils. Spec, gravity at 1.5° Proporti on of oil t 3 80 p. c. of alcohol 1:1 3 -i 1 : 5 1 : 10 0.897 0.908 0.90O 0.905 (t 895 .soluble milky turbid .soluble milky turbid soluble slightly turbid milky turbid soluble ^lerinaii oil ^ The saniH with 10 percent 0.887 0.877 0.868 0.883 nnlky 20 percent ' | 30 percent ( Commercial oil adulterated | (, Commercial oils adulterated ) with fattv oils 0.893 895 0.898 turbid Com-lusions as to tlie kind and (piantity of the adulterant can l)e di-awn from the appearance (jf the turbidity, also from the behavior of the sub.sta.nce separating. Petroleum produces a nulky white turbidity, whereas fatty oils produce a turbid, but not a milky mixture. After [irolonged standing, fatty oil collects in the foi-m of (lr(jps at the bottom of the liquid, while petroleum rises to the surface. 1) Bericht von S. & Co.. Oct. IS.SO. \i. 21. '-i) DistiUefl Erf)ni rlry ritroiiella p:rass in Leipzig. 298 Spechrl Part. Citroiiella, oil adulternteil with fatty oils is soluble neither in 1—2 parts 7ior in 10 parts of 80 p. <:. alcohol. An oil adulterated with petroleum gives a. clear solution with 1—2 parts, hut becomes turbid upon the addition of more solvent and sejiarates (jily drops at the surface only alter pi-olonged standing. Strictly speaking, adulteration can be established only after the separation of oily drops, for a, mere turbidity is frequently ]>roduced by pure commercial oils. The exact ])r(jof foi- adulteration with fatty oils and petroleum is described on p. 201. Acetylization will be found useful in passing judgment on an oil: the higher the geraniol content, the more valuable the cjil. However, the geraniol content found upon acetylization does not correspond to the real alcohol content. Inasmuch as in tlie process of acetylization, citronellal is quantitatively converted into the acetic ester of iso]>ulegol GioHisO (Tie- mann and Sdnnidt^ ), the citronellal content is determined with that of the geriiniol. The term "tieraniol content." therefore, is improper, but for the sake of simplicity is retained in ])ra<-tice. A method for the determination of geraniol in the presence of citronelhd has not yet been worked out. Production and (Commerce. Ceylon and the Straits Settlements on the Malacca!! pe!ii!!sula, a!v the cou!it!'ies which pi'oduce cit!'oi!ella oil. The acco!!!j)a!!yi!in' !!!a]i shows the ]n'o(h!ci!ic (list!'icts ii! Cevlo!!. An i!re!! of 40,000 — ."iO,*^)!) ;ic!-es is said to be u!ide!- cultivatio!! in the island, with (iOO stills i!i ()pe!-atio!i. whii'h have an a!!!iual c.ipacitv of i!ioi-e than a millioi! ]i()U!i."). 01 7 lbs., valued at about .fa.'iO.Ol )().()(>. Tliis i-econl was bi-oken in ISOO with a total of 1,4:78,7.")(; lbs. The i()n!iti-ies to which this oil was shipped, with the a!i!ou!!ts. ai'c : For 1898. For 1899. KiiKlaiiil (;'.)0,S(;,S(i.", " F!-a!ir-e H. 4-1-0 " 1,467 ■■ Chii!a 2.24!) ■■ Singapore ."i()4 ' .\IVicn 25(1 " s,(;2() Totiil 1,3(15,917 lbs. , 1,47S,756 lbs. 1) Bericlite, 29, ]). 91 ;l. ^1 The.si-' two fiR-ureK are luisleailiTif;- iii.-isiiuirh as tlir Ocriiiaii iin|ioi-ta tioii,'^ aiiioniit- iiift to alfout 250, 000 lljs. are incluilt'i! in the lOnjilissl) iuiport,^. Oils of the Oramineae. 399 The enormous increase in production and consumption is strilvingly shown by the following statistics of exportation : Export of citronella oil from Ceylon. 1887.. 551,706 lbs. 1888 659,967 " 1889 641,465 " 1890 909,942 " 1891 603,974 " 1892 844,502 " 1893 668,520 ■' 1894 908,471 " 1895 1,182,255 " 1896 1,132,141 " 1897 1.182,867 " 1898 1,365,917 " 1899 1,478,756 " In comparison with these numbers the production of the Straits Settlements near Singapore is insignificant. The total ai'ea of the citronella estates in the peninsula is estimated at 2000 aci'es at the highest. The animal production of oil may not exceed 80,000 lbs. (Qualitatively, however, this oil is fjreferable. 51. Oil of Andropogon Odoratus. The grass Andropogon odonitus Lisboa, whii:'h serves the natives on the west coast of Inditi proper as a domestic i-emedy, yields upon distillation as much volatile oil as Andropogon schoenanthus. Properties. According to Dymock,i the oil is of a dark red color; s]). gr. 0.981 at :!1° ; au- — -2-2.75°; [«]d=— 24,43°. An oil (li.stilled from fresh grass possessed an odor ri-'sendiling that of ])mt' needle oil; s]). cr. 0.91."); «d = — 28°10'.2 53. Camel-grass Oil. (jRKiix. From Dioscorides u]i to the middle of the last century the hf^rl) of Andropogon hiniger Desf. has been carried in apothecary shops as Herba. schoenantln or Squin»nthj, as Juncun odonitiis oi- as Fcjpnum camekmimfi The plant is widely distributed throughout northern Africa ami Arabia, also in northern India as far as Thibet. In the desert it constitutes tlip principal food of the camels. L']5on distillation of the dried grass, as offered for safe in the Indian bazaars, Dymock* obtained 1 p, c. of oil. 1) Pharniacographia inOica, i)ai-t \l, p. ~.71, 2| Bericht von S. & Co., 'Apr. 1892, p. 44. 3) Pharmacogi-aphia, II. edit., p. 728. ^) Phannaeoi^raphia inilica, part W, p, .o64-. 300 Special Part. Pkopehties and Composition. Dymork observed the sp. gr. 0.905 at 29.5° and the anole f)f rotation «d = — 4°. Schimmel & Co.i found the ap. gr. 0.915 at 15° and the angle of rotation «d = + 34°3S'. The odor of camel-grass oil reminds of that of elemi oil, which resemlilance apjjears to be due to its phellandrene c(jntent.i The oil distills between 170—250°. 53. Oil of Saw Palmetto. Oeigin and History. The oil of saw palmetto is obtained from the berries of Serenou serrulata Michx. Hook, f., (Family Palmae), indigenous to the soutliern United States, especially to Florida. The oil is apparently first mentioned in 1894 by Bheri-ard,2 who claims to have obtained it from the chloroformic extract of the berries. Coblentz^ in 1895 obtained a small quantity of a volatile oil by distillation. The oil had, however, been distilled in much larger ciuautities as early as 1890 by J. U. Lloyd. ^^ Phepahation. The oil is obtained hj distillation from the fresh berries. The yield of oil is about 1.2 p. c. The, dried berries do not yield the oil.-' An oil has also been obtained hy expressing the juice from the berries and collecting the oily layer (Sherman and Briggs^), and by siphoning off the oily laj'er which separates from the fluid extract (Lloyd 5). Peopebties. The distilled oil of saw palmetto has a pleasant fruity odor, accompanied by a heavier, almost disagreeable odor. When distilled it is of a green to brownish color, which, however, disappears when distilled in a vacuum. The oil distilled in 1890 by J. D. Lloyd had in 1900 a sp. gr. of 0.8682 at 20°. The oil, wlieu distilled under diminished pressure, was colorless and had the following properties : B. p. (50—170° at 18 mm.; d|-o = 0.8G79; nD2o° = 1.41233. The oil is optically inactive (SchreinerS ). Two samples of oil obtained from the fluid extract had the sp. gr. 0.8651 and 0.8775. They .yielded by distillation with steam from 4 to 5 p. c. of a green to brownish oil of the sp. gr. 0.8650 and 0.8653 respectivel.y. An oil obtained by Sherman and Briggs^ by expression from the berries preserved in alcohol boiled from 70—270° under a pressure of 16 mm. 1) Bericht von S. & Co., Apr. 1S92, p. 44. 2) Proc. Am. Pharm. Assn., 42, p. 812. 3) Proc. New .Jei-sey Pharm. Assn., 189.5, p. 63. ■t) Personal cointnunication from .7. TJ. Llo.yd. •■i) Ptiarm. Hev., May, I'JOO. 6) Pharm. Archives, 2, p. lul. Oils oftlte Fiilniae and Arace;w. 301 Composition. Sheriuaii and Briggs i have made a thoi-ougli chemical study of the oil of saw palmetto obtained b^- expression from the berries preserved in alcohol. The oil was subsequently fractionated under diminished pressure. They found this oil to consist to the extent of about G3 p. c. of free fatty acids, caproic, caprylic. capric. lauric, pahnetic, and oleic acids, and about 37 p. c. of ethyl esters of these acids. No glycerides were found in the c)il obtained from the pulp of the beri'ies, although their pi-esence was demonstrated in the fixed oil from the seeds, in which the same acids, with the addition of stearic acid, were found as in the oil from pulp. The fruity odor of the oil is due to the ethyl esters. The fact that the oil consists so largely of free fatty acids and of ethyl esters of these acids, and inasmuch as the berries are kept in alcohol, has led to the suspicion that the esters may be formed by the action of the alcohol on the free acids. ^ This suspicion is supported by the fact that no volatile oil is obtained from the dry berries. 54. Calamus Oil. Oleum Calami. — €alamu». 3,52. Oils of the Anicea.e. 303 Calamus oil alwo contains saponifiable substances and a small amount of an alcoholic substance as becomes apparent from the saponification number (40 — 50) after acetylization. Properties. Calamus oil is somewhat viscid in consistency, of a yellow to brownish-yellow color, possesses a camphor-like, aromatic odor and a corresponding bitter, burning, spicy taste. Its sp. gr. is 0.960 to 0.970; angle of rotation «d= + 1I>i to +31°; 2 saponification number 16 — 20, after acetylization 40 — ."lo. Calanms oil is soluble in almost all proportions in 90 p. c. alcohol, but rather difficultly soluble in mrjre dilute alcohol. Of a .jO p. c. alcohol ai)out 1,000 parts are necessarj' to effect a clear solution. (The sohibility of the Japanese oil described below is yery different.) Upon distillation of a normal calamus oil nothing came over below 170°; between 170 — 275° 32 p. c. were obtained; from 275 — 300°, 60 p. c; leaving a residue of 8 p. c. Examination. Owing to the lack of knowledge of its chemical com- position, the examination of calamus oil is confined principally to the determination of its optical rotation, sp. gr., and solubility in 90 p. c. alcohol. Adulterations that cannot be readily recognized by their odor are turpentine oil, cedar wood oil and gurjun balsam oil. The first mentioned can be recognized by a lower sp. gT, and angle of rotation, and, if present in large quantity, by the diminution of solubility in 90 p. c. alcohol, and by fractional distillation. Cedar wood oil and gurjun balsam oil may influence the sp. gr. but little, but reduce the dextro-rotation materially oi- change it to laevo- rotation. Their presence may further be indicated by their sparing- solubility in 90 p. c. alcohol. 3 Inasmuch as the boiling points of both oils lie within the limits of tliose of calamus oil, they cannot be recog- nized by fractional distillation. 55. Oil from Calamus Herb. The fresh green parts of calamus, Ai/oru.v calamus L., yield upon distillation with water vapor an oil which closely resembles that from the rhizome. Its sp. gr. is 0.964; «d = +20°44'.4 1) Bericht TOn S. & Co., Apr. 1S9S, p. 15. 2) The anffle of rotation of the Oaliciaii oil i.s freqnenti.v lower than H- T0°. .1) Bericht ron S. & Co., Apr. 1,S95, p. 16. i) Bericht von S. & Co., Apr. 1S97, p. S of tatjle. 304 Sjieci,-il Fart. 56. Japanese Calamus Oil. .iMliauesc riilanms root, wliirli does not differ iiiorpliologically from the ordinary rhizome, is prob;d)ly derived from tlie same plant as the latter. It is ])ossible, hoAvever, that it is derived from Aeorus spurioms S(.'hott, which is common in Japan and the rhizome of which is said tq scarcely differ fr(.)m that of A. e;ibimu.'i L. ( Holmes. i 1879). The Japanese rt) p. r. alcohol, the German being solul)le in not less than 1,000 parts. ^ 57. Cevadilla Seed Oil. Sabadillsameiiiil. This oil is obtained by distillation of the comminuted seeds of SfdnuliUii officiiiiilis { Lili;iceaf), i>v of the fat obtained by benzin extraction in the preparation of veratrine (Opitz,* 1H91 ). The yield froin the fresh seed is aljout 0.-32 p. c,, from (jld seed much less. The sp. gr. lies be- tween 0.902 and 0.92H. Upon distillation the bulk ])asses over between 190 — 2.")0°, the esters present being largely decomposed. After saponi- fication the oil distills principally between 220— 2."')0°. [a]j = — 0°10'. From the alkaline saponiticati(jn liquid, oxymyristic aciil OiiHosOa, (m. p. 51°), and veratric ai-id. CiiHio04 (m. p. 179 — 180°), lia,ve been olitained. These acids seem to be present in the oi'iginal oil as methyl and ethyl esters. Lowei- aliphatii; aldehydes have also been found. 58. Aloe Oil. The faint but i-hiiracteristic odor of aloes is due to a minute quantity of V(jlatile oil. Upon distillation of .")0() lbs. of Ba.rbadoes aloes from Alor vulgaris Lam. var. .17oe h;)i'lMf]ensi,s. T, and H, Smith & I'o. of London in LS8() obtained 2 fl. dr. of oil. It was a light yellow, mobile liquid, sp. gr. 0.8G3, b. p. 26()— 271°.^^ 1) Pharni. .loiirn.. Ill, 1(1. ]). IHL'. 3) .ViTlliv d. Pharm., 229, p, 265. -'I liericht von S & Co., Apr. ISSU, p. 7. +) Pharm. .Joiirn., Ill, 10, p. 613. Oils of the Liliaeene. 305 59. Xanthorrhoea Resin Oil. Upon distillation of tlip Australian yellow xanthorrhoea resin lai-aroid re.sin, yellow grass treej;nm) frcjni Xnnthorhoea hastile E. Br. iSchimniel & Co.i (jbtained 0.37 p. e. of a yellow oil. storax-like in odor. Sp. gr. (.(.987. «D — 8° 14:', saponifieation nnnil)er 74.8, acid number 4.9, •ester number (59.4. The free acid was isolated by shaking with dilute sodium hydroxide solution and recognized by means of its melting point 138°, as eiunamic acid. From the saponification lye cinnamic acid was separated in considerable quantity, 200 g. of oil yielding about 40 g. of cinnamic acid recrystallized from water. The saponified oil boiled between 14.")— 240°. From the low boiling ])ortions a frac/tion 14."'i — 1'>()° possessing the properties of styrene was iscjlated. Upon the bromination in a cold ethereal solution styrene dibromide. m. p. 74 — 7~>°. was obtained in fine needles. 60. Garlic Oil. Upon di.stillation of the entire plant. Allium sativum L., 0.005—0.009 p. c. of an cjil2 are obtained, which is yellow in color a,nd possesses a most disagreeable garlicdike odor. Sp. gr. 1.04() — 1.0.''>7: optically inactive. The oil was first examined chemically in 1.S44. Ha.sed upon this e.xamination, Wertheim-^ arrived at the conclusion that garlic oil con- sisted principally of allyl sulphide (C'sHsjoS. This view was held for almo.st .50 years and has passed into all text books without being put to a test in a single instance. When SemmlerJ' reexanjined the oil in 1892 the fact was revealed that garlic oil does not contain a trace of allyl sulphide.'' Analysis revealed the ])resen(/e of sulphur besides carljon and hydro- gen, also the absen(;e of o.\vgen and nitrogen. Ina.smuch as the oil decomposed when distilled undei' ordinary pressure it was fractionated under reduced pressure. Under 16 mm. pressure it distilled between G.5 — 12.j°. Semmler isolated the f(.)llowing sultstances: 1. A disulphide CeHi^Wi (abt. p. c). 1>. p. (Mi — (19'^ under 1(5 mm. It is probably allyl propyl disulphide. C:jH.-j!S — SC'/jHt. 1) Bericht von S. & Co., Oct. 1807, p. G6. 2) Bericht von S. & Co., Oct. 1889, p. .^2; and Oct, 1890, p. 2.5. 3) LiebiK'R Annalen, .Tl, p. 289. 4) Archiv d. Phnrni., 230, p. 434. 5) Thi.s natui'ally dimpoHes of the Ktatements concerning other oils ^snpposed to be identical with garlic oil, such aw those of Thla.-ipi arvense L. and AlUaria officinalis L, 20 30G Spccml Pm-t. . ■2. A (liHiilphide CflHn,vS2 (abt. (50 p. e.) constitutes the bulk of the oil and is the l}eai-er of the pure garlic ortor. Sp. gr. 1.0*237 at 14.8°; b. p. 79—81° under 18 mm. its constitution probably is CgHoS — .SCaHg. 3. A substance CoHi„.S,s (abt. 20 p. c). Sp. gr. 1.081.') at l.j° ; b. p. 112—122° under Ki mm. Probable constitutional foi-mula: ("sHoS — 8 — S(:»H,-,. The residue shows a still higher sulphur content and possibly has the composition GiiHidSi. Inasmuch as alljd sulphide boils between .3(5—88° under 1.1. .j mm. pressure, and the first fraction of garlic oil between (50 — (5."i°. the presence of allyl suli)hide in garlic is excluded. Neither could tlie sesquiterpene of Beckett and Wright,' b. p. 2.">3.9° be found in the oil examined by 8emmlei'. 61. Onion Oil. The punj^ent. persistent odor of the garden oTiion. Allium eepa L., is due to a volatile (jil. of which a yield of 0.04(5 p. c. is obtained when the entire plant is distilled. ^ Onion oil is ;i dark brown, mobile liquid, sp. gr. 1.041(1 at 8.7° -^ or 1.03(5 at 19°; a o.D = — r>°. Inasmuch as the
    71. s) Ann. de (!him., 80, p. 185. — Trommsd(ji*ff's Joiirn. d. Pharni., 21, J, p. 206. f>) Trorarasdorff'H Neuee Journ. d. Pharm., 0, p. 6o. — Berl. Jahrb. f. Pharni., 24, I, p. 160. 7) Inasmuch slh the terpenes possess hut a slight odor it weenis probable that the characteristic saffron odor is due to the presence of a small amount of an oxygenated substance. 30.S SjiPcia! I'nri. 64. Orris Oil. Oleum Iridis. — Irisiil. — Essence d'liis concrete. Benrre (le Violettes. OuKiiN AND I'liEPARATtON. Tlip sti'iuii distillation of tlip rhizome ot whitp fliiy' for tlic ])ro(lucti(ni of orris oil is ii ])r;ictice of ino-ei-manicn,, is inferior and seldom used for distillation. Still poorer is the Morocco or Mogadore orris !-oot, also derived from I. gevmanicu. It is darker in Oils of the IriclHceae. 300 color and has but a faint odor. In ovder to vender it ligliter in color, it is sometimes bleached with sulphur dioxide, thus rendering it unsuitable for distillation. Occa.sionallj' Indian rooti has appeared in the London market. It was, however, of such poor quality — due probably to poor methods of collection and treatment^as to be unfit for distillation. Upon steam distillation ^ orris root yields but 0.1 to 0.2 p. c. of volatile oil. The distillation is rendered difticult and tedious by the frothing, due principally to the high sttii-ch content of the rhizome. To facilitate distillation, the addition of sulphuric acid lias been suggested, whereby the starch is partly converted int(j sugar. This process, how- evei-, did mjt stand the test of experience, inasmuch as it affected the odor of the oil. On account of the small yield arid high price, the use of the oil is restricted principally to flnei- perfumery. In re(;ent years, orris oil is used together with ioiioue in the preparation of artificial violet perfume. Properties. Orris oil is a yellowish-white to yellow' mass, of rather firm consistency at ordinary temperature, and an intensive odor remind- ing of the dried orris root {Veilchenwurzel) \ it melts at about -lA — 50° to a yellow or yellowish-brown liquid.* Orris oil is slightly dextro- gyrate. The acid number, about 218 — 222, corresponds, to 8.5 — !)0 p. c. of myri.stic acid. The saponification number is 2 — (5. (JoMPOSiTiox. The bulk of orris oil, about 8.5 p. c, is composed of the completely odorless myristic acid.* The bearer of the violet odor is irone, a ketone of the formula. C1.3H20O (Tiemann and Kriiger,-' 1898). Besides these two constituents, the oil contains small amounts of the methyl ester of myristic acid, oleic acid and its esters, also oleic aldehyde. For the preparation of the irone, the rhizome is exliausted with ether, and the ethereal residue is distilled with watei' va.por. In the 1) Bcricht von Sehimniel & Co., Oct. 1S9G, p. 4.5. 2) Pi-ot. H. Hirzel in his "Toiletten-Cheniie," i. ed. (1892), p. 215. states that orris oil cannot be the normal distillate of orris root, because m;,'ri.>5tic acid is not volatile Avith "water vapor. The fact, however, is that the oil is obtained by steam distillation and since myristic acid is its principal constituent, there can be no doubt that the acid is volatile with water vapor under the conditions tinder which the distillation is conducted. 3) In order to avoid detrimental over heatinj?, the oil is melted b,y placing- the bottle in warm water having: a temperature of about ii^ — 60^. *) Fliickiger (1876), Archiv d Pharm., 208, p. 481. (>f older references comp. Vogel, .Journ. de Pharm., II, 1, p. 483; Trommsdortt's .Journ. d. Pharm., 24, II, p. 04; and Dumas, .lourn. de Pharm., II, 21, p. 191; and Liebig's .\nnalen, 15, p. 158. s) Berichte, 26, p. 2675. 310 Sjiecinl Part. ivsidne tlit-re remains a part of tlie inyristic- acid, iregeniii, iridic acid, and esters of mjTistic and oleic acid, whereas part of the niyristic acid and its methyl ester, oleic acid and one of its esters, and oleic aldehyde distill over with the irone. Ui)on repeated steam distillation of the first distillate, irone passes over first and can thus be separated somewhat from the other constituents. The irone is farther ])urifled by convertini;- it into its phenyl hydrazone and regenerating it l)y means of sulphuric ac'id. Perfectly pure irone is obtained by convertinu- it into the crystallizal.>le ironoxime and reg-enerating it by means of dilute sulphuric acid. In the preparation of iron(? from orris oil, the myristic acid is first reniowd by shaking with dilute potassa solution. This solution is shaken with ether, the ether extrart di.stilled fractionally with water vai)or and tlie irone ]nirifled as stated al)0ve. Irone lias a sp. gr. of 0.939 at 20°. boils at 144:° under Hi mm. pressure, and in a. 100 mm. tube turns the plane of ]:)olarized light alxiut 40° to the rigiit. In water it is almost insoluble, but readily solulile in ali-ohol. etlier. chloroforni. benzene and ligroin. The odor of pure irone is ]iungent and in a coni-entrated state seems to differ entirely from tha.t of the violet. The latter, however, becomes apparent when irone is dissolved in a large amount of alcohol and the solutio7i eva|)orated. Adulteration. A li(piid or semi-licpiid oil is sometimes found in commeri-p under the name of orris oil, whic.li has been obtained from orris root by distillation with ceda.r oil or other oils, or whidi is merely a mixture of sucli oils with some orris oil. Several years ago a mixture of 97. ."i ]). of .icetanilid and 2..") p. of orris oil was brcmght into commerce as "irisol" anil sold at an enormous ]irice. 65. Curcuma Oil. Orku.x .\.\d Puki'.vr.vtion. The curcunm plant. Cuvcuuin loit^n L.. N. (). Zini(iliPi';icp;ii\ is indigenous to sinithern Asi.a. aTid is cultivated cm a.ccount of the yellow dyestuff wliich it contains, Iti India and in southern .-ind eastern Chimi. Upon distillation with water vapor, curcuma root yields ,"> — .">.."i ]>. c. of volatile oil. Properties. (Inrcuma oil is an orange-yellow, slightly fluorescent li(|uid. which has a slight odor of curcuma and a sp. gr. of 0.942. With % to 1 vol. of 90 ]). c. alcohol it i)roduc-es a clear solution which is rendei'ed milky u]ion the a,ddition of more alctohol. Oils of the Zingiheniceae. 311 CoMPOSiTiox. According to Bolley, Suida and Daubei (18(58) cur- cuma oil beginw to boil at about 220° and is in complete ebullition at 250°. Above this temperature decomposition takes place. Upon the addition of ammonium sulphide to fraction 230 — 250° they obtained crystals which were regarded as carvone hydrosulphide. Fliickiger^ (1876). however, could not obtain a hydrogen sulpliide addition product with any of the fractions, thus indicating the absence of carvone. Jackson and Menke^ (1882) analysed the fraction distilling between 193 — 198° under GO mm. pressure, assigned to it the formula CiyH2sO, and called it turmerol. It is an alcohol which yields a chloride, turmei'vl chloride, with strong hydrochloric- acid. Its sp. gr. is 0.9(116 at 17°. ["-Id = +33.52°. Under ordinary pressure turmerol boils at 285 — 290° with decomposition. With an excess of hot pei-manganate solution it is oxidized to terephthalic acid, ('hromic- a(;id yields different oxidation products. Ivanow-fjaievsky* obtained valerianic and capronic acids from fraction 28(> — 290°, The lowest boiling portion of curcuma oil consists of phelhindrene.-'' 66. Oil of Zedoary. Oleum Zedoriae.—Zitwerwurzeliih— Essence de Zedoaire. Origin and History. TIip rliizome of the zingiljeraceous plant Curcuma zedoiirm Eoscoe (C. zerumhet Roxburgh) is at pre.sent brought into commerce from Ceylon via Bombay. The plant has been cultivated in the island for a long period because some of the inhabitants are fond of it as a vegetable (Fliickiger ;" Dymock'''). The distilled oil of zedoarj^ is first mentioned in the price ordinance of Berlin of 1571,8 j^ those of Worms and Frankfurt-on-the Main of 1582, also in the Dispensatorium Noricum of 1589. Exannnations as to yield and properties of the oil were later made bj' Neumann » (1785), Delmeio (1779) and (leoffroy^i (1757.) 1) .Journ. f. pr. Chem., 103. p. 474. .(ahresli. f. Pharm., 1S6S, p. 47. -■i Berichte, 9, p. 470. 3) Amer. Chem. .Journ., 4, p. 8GS, 4) Berichte, n. p. 1102. s) Bericht von S. & Co., Oct. 1890, p. 17. fi) Phai-macosno.sie. p. 8(i9. ^) Materia medica of Western India, p. 772. 8) Estimatio mateviae medicae ... in gi-atiara et iLsuin pnblicuni civitatum Marchiae BrandenbnrgenKiM. Autore Matthaen Flacco. Berolini 1574. 9 1 Goettling's Almanach fiir Scheidekilnstlei-, 178,5, p, 118, 10) Crell's ChemiHches .Journal, 3, )i. 20. 11) Tractatus de materia medica, vol. M, Ji. 2(;,'i. 312 Special Pnrt. I'ropekties and Compokition. Oil of zedoary is a. Hoinewhat viscid, oily liquid. In tliin layer its color is somewhat g-reeuisli, in thicker layer strikingly greenish blaijk; in transmitted light its color is reddish. The odor reminds of that of ginger, but differs from the latter by a camph(K--like odor due to the presence of cineol. Its sp. gr. is ().i)9(.i — T.(.)l. The ]-otatory power has not yet lieen observed on account of the ilark liolor of the oil. It it soluble in V/2 — 2 vol. of 80 ]). c. alcohol. Upon distillation only a small amount of oil come.s over lielow 240°. In this fraction cinefjl 1 was shown to lie present liy means ol the hydroliromide. The linlk of the oil distills l)etween 240 — 300°. a small amount above ;!00°. 67. Kaempheria Oil.. Kafinjifmn rotuinln L., X. (). Zui°W. It is miscible with % and more parts of 91) p. c. alcohol; of 80 p. c. alcohol 10 — 20 parts are necessary to effect a clear solution. It bods lietween 170 and 27.')°. r'oMPOsiTiox. The only known constituent of galangal oil is cineol i identified by means of the hy°. A large portion of the oil distills below 2:50°. Fraction 2~>r) — 2(j.")° j^ielded upon saponification with methjd alcoholic potassa an acid melting at 184° — probably cinnamic acid. 73. Ginger Oil. Oleum Ziug-iberis. — Iiij^weriil. — Essf^nce de Gingembre. OrKtIx axu History. The rhizome of Zingihnr officinale Koscoe {Amoinum zingiljer L. ), whii-li is originally indigenous to southern Asia, 1) Bericht von S. & Co., .A.pi-. 1K90, p. 21. 2) Kon. Akarl. v. Wetensch. te Am.sterdatn "1808, ji. 5.50. 3) .S'Land.s Plant, te Buitenzorg, 1897, p. yij. 314 Special Part. and which is <:-iiltivated there to-day as well as in the south Asiatic archipelago and in other countries, seems to have been used as a spice by the ancient (Jhinese and Indians. The Greeks and Komans with whom it was a favorite si^ice obtained it via the Red iSea route and, therefore, considered it an Arabian product. In the third century, however, it W'rts already enumerated among the Indian products brought to Europe, via the Red 8ea and Alexandrin. Ginger was introduced into the West Indies by the Spanish about the middle of the sixteenth century. As early as l.")4:7 ginger was shipped from JaTuaica to Spain, from San Domingo in 1.")^.") and from B-1:. The first mention of distilled ginger oil is found in the spice ordinance of ('openhagen of 1(572. Tlie yield was determined in the course of the eighteenth century by Neumann,! Ge.sner.- Geoffroy,^ and Cartlieuser.* The rhizome yields about 2 — 3 p. c. of volatile oil. At present African ginger is mostly used for the distillation of the oil. Of interest is tlie observation that ammonia is formed in the process. Its formation has not yet been satisfactorily explained. Propehties. Ginger oil possesses the aromatic, not very strong, but persistent odor of the rhizome, but not the pungent taste of the latter. It is viscid and of a greenisli-yellc)w color. The sp. gr., which lies between O.ST") and 0.885, seems very low if the iimount of high boiling constituents is taken into consideration. The angle of rotation varies between — 2."i nnd — -15°. Giugei- oil is one of the least soluble in alcohol, 50 — 100 parts of a 96 p. c alcohol beint;' requisite to effect a clear solution. When distilled over a direct flame, the oil pa.sses over between 155 and yoo°. but a considerable residue of de(;omposition products remains in the tlask. The distillate from Japanese ginger differed from the oil from African or Jamaica ginger. Inasmuch, however, as but a few kilos of tlu' rhizome were used in the experiment, the oil may ni>t have been nornuil. Its sp. gi-. was as high as 0.894; its angle of i-otation was dextrogyrate, viz. md = 9° 40'; and it was soluble in 2 p. of 90 p. c. alcohol. No ])ositive test for ])hellandrene was obtained. Moreover, an oil dtstilled in Japan," did not differ in its properties from the ordinary oils. Its s]). gr. was 0.88:{, a-o = — 2(i°52'. With sodium nitrite tind glacinl acetic acid it yielded a positive test for ]ihella7idrene. 1) Ch.vmia medica, viil. 2, p. r>;!,s. a) Trai-tatus de mat. meil.. v.)l. 2. p. 2(i5. = 1 Dissertatio dc ZiUKibere. Altilm-f, *! ElemeiUa I'hymiae, y p. c. of oil. In an experiment in which the seeds and the empty capsules were distilled separately, the former yielded 4 p. <■.. the latter (1.2 p. c. of oil. 1) The first inventigation of ging-er oil *) De artificiosiM e.vtractioiiiliiis, fol. by Papoiiseiv in 1852 tlirew no liffht on itts 22fi. compoHition. Sitzungslterichte fler Akafle- f-) f'hoinia niedica, vol. 1, p. o2S. mie der \\'iKsenHC'haften zu Wien, 0, ]i. 815. '') Schweig-ger's .Fourn. f. Clieni. nnd — Liel)io:"s Annalen, 84-. p. ?j~i2. Pliyn., 8, p. 311. 2) .Ion™, f. prakt. Oliemie, II, 4tl, p. 18. 7| C'anlanionii liistoria et yiiidiciae. 3) I'harni. .lourn.. Ill, 12, p. 24:!. S) PliarmacoKfapliiu. 2nd ed., p. I\H. 316 Special Part. Propekties. The Ceylon <;ardamom oil is liglit yellow, somewliat visi'id. It possesses the strong aromatic odor of the cardamoms, and a pleasant, cooling taste. Sp. gr. 0.895— (.).9(.)5 ; «d = + 12 to + 15°. The oil is clearly soluble in 1—2 and more parts of 80 p. c. alcohol. With 70 p. e. alcohol it yields a turbid solution. The saponification number lies between 30 and 70. The above mentioned oil from the seed has tlie following pi-operties : sp. gr. 0.908, «D = +l:!°14:'; that of the empty capsules: sp. gr. 0.908, «D = +9° 48'. Composition. After repeated fractionation of Ceylon oil. Welieri in 1887 obtained the following tour princijial fractions: 1.) 170—178°; 2.) 178—182°; :5.) 182—190°: 4.) 205—220°. By passing hydrogen chloride into fraction 1, a dihydrochloride, CioHi«2HCl. melting at 52° was obtained. With bromine no crystalline bromide could be obtained. On account of the somewhat high melting point (2° higher than that of dipenteiie dihydrochloride), Webei- leaves it undecided whether the dihydrochloride obtained is due to the presence of dipentene or not. Fraction 2) contains tei-puiene, a, terpene which is characterized by the Tutrosite melting at 155° and which liad not been found previously in any volatile oil. Fraction 4j consists of terpineol. Weber obtained with hydrogen chloride a chloride melting at 52°. and with hydrogen iodide an iodide melting at 7(5°. Although neither dipentene tetrabromide, obtained by Wallach- from terpineol, nor i)henyl terpinyl urethane^ could be obtained, the negative i-esults (jf Weber must be attributed to impurities which act as disturbing- factors in the test. In the course of the distillation water was split off, foiinic and acetic acid were also formed. The latter indicate the presence of esters, the annmnt of which according to the saponihcfition numl)er ( comp. proper- ties) viij-ies fron) alxjut 10 — 20 p.c. From the residue of the fractionation a solid substance separated whic-h, upon recrystallization from alcohol, constitutes light laminae of a silvery lustre melting at (iO — Gl°. 74. Malabar Cardamom Oil. Orimn. On account of their high price, the officinal Malal.iar (and Madras) cardamoms from Elettarin cairlunioinuin Wluts et Matton are 1) EiebiK'K Annalen, 238, p. lis. 3) Ibkl., p. 267. 2) T^iebift's Annalen, 280, p. 26G. Oils o{ the Zingiheraceae. 317 seldom used in the manufacture of the volatile oil. The yield varies between 2 and 8 p. e. Properties. The odor of ilalabar rardamom oil differs but slio-htly from that of the Ceylon oil. Sp. gr. 0.988 (HaenseP) to 0.948 (8ehimmel & Co. 2); ao = + 2(i° i to +84° .',2'.-' It is soluble in 4 and more jiarts of 70 p. e. alcohol. Saponifli-ation number 182. Co.MPOSiTiON. In an old specimen of Malabar cardamom oil, Dumas and Pelig-ot^ (1884) found prismatic crystals of terpin hydrate, CioHiB . 8H2O. Their presence was undoubtedly due to their formation from terpineol shown to be present later. According to Schimmel & Co.,* the high saponification number is due to terpinyl acetate. Tlie silver salt from the saponification li(iuid corresponds with silver acetate. (Found ()4.8 and 65 p. c, Ag.. calculated 04.09 p. c.) From the saponified oil crystallized d-ter])ineol was obtained by fractional distil- lation under diminisheil pressure (l-")() — 104° under 14 mm.). M. p. 85 — 87°; «D ^ +81° 87' (in the molten condition). It was chemically identified by means of dipentene dihydriodide (m. p. 78 — 79°); terpinyl phenyl urethane (m. ]). 112 — 118°); (also optically active [«]d = 88°.")8' at 20° in 10 ]i. c. alcoholic solution); and terpineol nitrosoehloride. Tlie piperidide from the last melted at 151 — 152°, eight degrees lower than that of the inactive isomer. The oil also contains cineol. In a recent investigation Parry' has also sJiown the pi'esence of hmonene. 75. Siam Cardamom Oil. Orkhx. Under the ufime of "Camphor seeds." so called on account of their camplior-like odor, the seeds of tlie Siam cardamom from Amomum eardnmoimini L. occasionally find tlieir way into tlie London market. Upon distihation, 8chimniel & (^'o.* obtained 2.4 p. c. of oil. Properties, At ordinary temperature, this oil constitutes a semi- solid niass having the odor of camphor and borneol. In order to redis- solve the crystals, the oil had to be heated to 42°, at which temperature the oil had a sj), gr, of 0.905 and an angle of rotation of +88° 4'. The saponification number was 18.8, after acetylization 77.2. corresponding to 22.5 p. c. of l)orneol in the original oil. The oil is soluble in 1,2 vol, of 80 p, c, alcohol. 1) Sudd. Apoth.-Zeitinig, 1896, p. Osy. i) Beiicht von S. & Co.. Oct. l.syT, p. 9. 2) Bericht von S. & Co., Oct. 1897, p. 8. 5) Pharni. .loiirn,, 0;i, p. 10.-,. 3) Ann, d, Chim, et Phys., II, 37, p, 8,33. 318 Speeiiil Part. Composition. In order to separate the stearoptene, tlie oil was cooled in ice and placed in a centrifuge. From 800 g. of oil, 100 g. of crystals were obtained. From the petroleum ether solution, about -40 g. of almost pure borneol separated upon cooling. When purified by means of the benzoyl ester, it melted at 204-°, and in a 10 p. c. alcoholic solution had a specific rotatorj' power [a]D = + 42°.55' at 20°. The petroleum ether motlier liquid, upon evaporation, left a granular mass which, after recrystallization from HO p. c. alcohol, melted at 176—178° and posses,sed all the properties of camphor. The oxime melted at 118°. The rotatory power determined in alcoholic solution at 20= was [r/.]D = +1:5°17'. Thus the crystals which separate from Siam cardamom oil i consist of d-borneol and d-camplior, present in about equal parts. 76. Oil from Grains of Paradise. Obihin axd History. The seeds of the zingiberaceous Amomum mplegueta Eoscoe, which is indigenous to the coast of tropical West Afi-ica, were formerly much used as spice and were known in the apothecary shops as Gi'fina pui'mlhsi, Semiiin eardaniomi majoris or Piper melegueta. The plant grows from the Congo to the Sierra Leone and a part of this coast district is known l)y the name of the drug as the Pe]iper- or Melegueta coast. Upon distillation cm a small scale of the grains of paradi.se, 0.8 p. c- were obtained, upon a larger scale 0.7-") p. c. of oil.* This oil was distilled by Porta* at the beginning of the seventeenth century and u.sed medicinally. Properties. The oil from the grains of paradise is a yellowish liquid, of a spicy but scarcely characteristic odor. Sp. gr. 0.891:5 au = — 8°'j8'. it begins to boil at 2y°; «d = — 12° 41'. It foi-ms a clear solution with one and moi'e parts of 8(!) p. c. alcohol. Upon distillatioii the bulk of the oil passes over below 220°, leaving, how- ever, considerable residue in the flask. Composition. The onlj'' known constituent of the oil is cineol. It was identified by means of the hydrobromide, regeneration of the pure cineol boiling at 175 — 176°, sp. gr. 0.924:, and conversion into cineolie acid (ni. p. 197°). Inasmuch as the charactei-istic cardamom odor is wanting, the Bengal oil cannot take the place of the Ceylon oil and is, thei-efore, without practical value. 78. Cameroon Cardamom Oil. Ori&in. The pliint from which the so-called Cameroon cardamom is obtained, is not yet known. Upon distillation of the fruit Schimmel & Co, obtained 2.33 p. c. of oil. Properties. The oil smells strongh' of cineol and cannot, there- fore, be taken as a. substitute for the Ceylon oil, 8p. gr. 0.907 ^ to 0.9071 (HaenselS); «d=— 20°34'2 to — 20° 30'.s The oil forms a clear solution with 7 — 8 p. of HO p. c. alcohol. Composition. The only known constituent is cineol. identified by means cjf the cineol-iodol reaction. ^ 79. Korarima Cardamom Oil. Koi'arima cai-damorns, formerlj' known as Cnvdamomuin ninjus. have the form and size of a small fig. They come from the countries south of Abyssinia, but are seldom found in the European markets. The mother plant of this species, t\\9 Amomum inigustifolium 8onnerat attains a height of 4 — 5 m. and has orange-yellow blossoms and scarlet fruits. The latter are eaten by the natives. The plant is common along the rivers in British Central Africa, and occurs also in the islands of Mauritius and Madagascar (Hanbury*), The roots have a slight ginger-like taste, the leave.s are more aromatic,-' The oil from the fruits was distilled by Schimmel & Co,« in 1877, a yield of 2.13 p. c. being- obtained. 1) Bcric-ht von S. & Co., Apr. 1897, 4) Science Papers, p. 112. p. 48. 5) Bull. Royal Garden.^ Kew., No. 142, 2) Bericht von S. & Co., Oct. 1897, p. 288.— Ref. Apt.-Zt., 13, p. 872 p. 10. 6) Bericht von S. & Co., Jan. 1878, p. 7. 3) Sudd. Apoth. Zeitung. .36, p. 083. 320 Slier j;il r:irt. 80. Oil of Black Pepper. Oleum Piperis. — Pfefferol. — Essence de Poivre. Origin and History. The unripe, dried berries from Pipei- nigrum L.. a cliiidier of tlie family Piperaceae. whii'li was orig-inallr iiidig'enons to southern India., are obtained from plants cultivated in different parts of southern India, in numerous islands of the Indian Arehi])elag-o, the Philipjiines and in the West In(), first described the process of distillation. In medical treatises, it is fii-st mentioned in the l.")89 edition of the Dispensatorium Xoricum, in the "Apothekertaxe" of Berlin for l.'i74 and that of Frankfurt for l.").S2. Rheede also descril>ed oil of pe]iper in KiS.S. Tlie first examinations of the con.stituents of pepper were made by Neumann T^ and hj Ga.uliius,^ later by Willert,^ Oerstedt^ and Pelletier.'"^ Preparation. The comminuted lilack pepper, tlie unripe fruit of Pipf'i- iiigriun L.. U])f)n distillation with water vai)or yields 1 to 2.-'! ji. c. of volatile oil. Worthy of notice is the formation of nnnnonia, which is also otiserved in the distillation of several other oils, viz. the oils of ginger, pimenta and cubebs. White pepper, which is obtained fi'om the ripe beri-ies, also the pericarp removed in its prejiaration, contains volatile oil." Whether tills agrees with the oil from black pep])er is not known. i| Oriindlifhc mit Experiiiien ten i-i-wicKpn.' Chyiiii.'. EilitioC. H. Kesscl. IT.s'.l. \'(,|. 2, Purt 4, ]>. '.}. 2) Oaubii, Ai.lver.sai-ioi-uni varli iirRiiinenti libor uims. 1771. ('hup. .">, ii. .T.-,. 3) Trommsilorff'8 .Jmirn. der Phannacie, 20, II, ji. 44. 4| Schweig-g'er'H .lourn. fiir C'heniio nnd I'hysllc. 2U, y. 80. •<) TroinniMdorff's NtMie.s .lourn. d. Phai-ni.. i;. II, ]i. 288. "I Lncii (Trdiiini.sdoii't's 'J'a.^ichenlinidi flu- ChiMniker und PharmacentiMi, 1S22, p, SI) obtained l.GI p. c. ol oil front white pepiier. Oils of the Pipenweae. 321 Properties. A colorless or yellowish-gTeen liquid of more or less distinct phellandrene-like odor, and a mild, by no means sharp taste. Sp. . 4(17; Berk'hti'. S. p. 13.")7. -) Ijiebift's Annalen, 2.S.S, p. 7.S. 3) This was first obtained h.v .Soulieiraii and rapitainp in 1840 (Liebig's .\nnalen, 34, p. 823), and recognized by tlieni as .se.sriuiterpene diliydrocliloride. Later it was examined b.v Schmidt, Schaer & Wyss, also by Wallach. *) Cnbeb camphor was first observed by Teschemacher at the beginning of this century. It was also examined by Miiller in 1832, Lieblg'.s Annalen. 2, p. 90 ; by Blanchet & Sell in 1833, Liebig's Annalen, 6, p. 2114: by Winckler in 1833, Liebig's Annalen. 8, p. 203; by Schmidt in 1870, Avchiv d. Pharm., 191, p. 23, and Berichte, 10. ]i. 188; also by Schaer & Wyss in 187.'j, .\rchiv d. Pharm., 200, p. 316. ^>) Schmidt, Schaer & AVys.s, loc. cit. *>) Schn^idt, loc. cit. 7) Schaer & AVyss, loc. cit. ^) AVinckler, loc. cit. ") This low boiling point tor a sesqni terpene i.s rather remarkable and probably due t<-> the partial decomposition. 1") Archiv d. Pharm., 234, p. 238. Oils of the Pipfvacette. 325 Upon di(°, and is colorless; sp. gr. 0.8.''>4 at 20°; «d = + 22°. Fraction 2, constituting 84 p. c. of the oil. boils between 280 — 25.")°. and is colored yellow; sp. gr. 0.921S ; optically inactive. At 270° a bluish-green fraction is obtained. From a fraction 110 — 148° under IT mm. small crystals separated upon standing, whicli after recrystallization from chloroform melted at 164°. 1 An elementary analysis j'ielded results i-orres])onding witli the rather improbable formula ("loHio . 2H2O. 86. Matico Oil. Oleum Folioruiii Matico. — Maticoiil. — Essence de Matico. Origin. Piper angnstifolium Ruiz et Pavon. indigenous to Houth America, is stated to be the mother plant of the matico leaves. Ina.s- mueh. however, as the term Matico is applied to a number of plants, the leaves of which can hardly be distinguished from the genuine, it is not sui-prising that mistakes are frequent and that the genuine article cannot be had at times. Recently imported matico leaves differ but little in appearance from those formerly in commerce, but considerably in the amount of oil they I'ontain and in the properties of this oil. Whereas foi'merly 1 — 8.5 p. c. of an oil lighter than water was obtained, now 3 — 6 p. c. of an oil heavier than water results. Properties. The matico oil of former years had a sp. gr. of 0.93 — 0.99 and was slightly dextrogyrate. It was a viscid, more or less dark colored liquid the odor of which rendnded of cubebs and mint. The more recent matico ^ oil is j^ellowish-brown ; has asp. gr. 1.06— 1.13; slightly laevogyrate ['-'■]d— — 0°25', or dextrogyrate up to + 5° 84'. The odor reminds of that of Asarum europneum. Tlie oil is soluble in 10 p. of 80 p. c. alcohol and in equal parts of 90 p. c. ali-ohol. CoMPOSiTlox. Matico camphor whicli was di.si-overed l)y FliickigerS and which has been examined as to its pliA'sical properties only, is the only known constituent of the old matico oil. It wjts obtained by distil- ling off those portions of oil boiling below 200°. From the residue 1) Possibly this sub.stanoe is identical with tlie stearopteiie. of like melting point, found in juni])er oil. 2) An oil, which evidently was obtained fi-oni a third variety of leave.* (yield O.R p. e.i, hart a sp. gi-. of 0.922 and a rotatory power ai> ^ — 27° 28'. 3) Pharniacognosie. Ill ed., p. 747. 320 Sjipciiil Part. the camplior crystallized out iu hexagonal ]ii-isms 2 riii. long- and •" Tiim. thick. Frequently it also crystallized from the oil when exposed to the cold. Matico camplior, wliich wiien pure is odorless and tasteless, is readily soluble in alcohol, ether, chloroform, benzene ;ind petroleum ether. The melting point of the crystals lies jit 94° (Hintzei). It is optically active (Traube-). In chloroformic solution [ajn = — 28.7^!° at l."j°. In a molten condition, calculated for 1.")°, [a]ij = — 29.17°. The specific rotatory power of the crystals is about pigtit times ;is great, being- — 240° for a plate 100 mm. thick. The identity of matico camphor with ethyl camphor, CKiHisfCaHslO, was regarded probable by Kiigler^ wlio based his supposition on an elementary analysis. The fart, however, that ethyl camphor* is a liquid having the odor of camplior, whereas matico camphor is odorless with a great tendency to crystallize, seems to speak against this assumption.-'^ The new matico oil contains no matico camphor. Froiii an oil distilled by Sehimmel & Co.s (sp. gr, 1.077; ud = — ••°2.")') a substance separated which, after repeated crystallization from ])etroleum ether melted at G2° and which proved to be asarone. The dibromide melted at 8") — 86°, and the asarylic acid, obtained by oxidation with perman- ganate, at 144°. The oil possibly also contains methyl eugenol, for u])on oxidation with permanga,nate it yielded an acid melting at 174° whicli probably was identical with veratrie acid. 87. Oil from Artanthe Geniculata. The leaves of Artanthe f^enicuhita Miq., known in Brazil as "false jaborandi," yield small amounts of a light greenish oil, of a spicy, somewhat mintdike odor and pungent, burning taste." 88. Oil of Betel Leaves. Olenm Folioriiiii Betle. — Beteliil.— Essence des Feuille des Betel. Orikin. The ancient custom of betel chewing practiced in the Malayan Ariliipelago and in southern Oliina, consists in chewing a betel leaf (Sirih) ') Tscherinak's MIm'ral. Mittli., lsT4, ]<. 227. 2) Zeitschr. J. Kryst., 22, p. 47. 3) Berichte, 10, p. 2S41. 4 1 Compt. rend , 63, p. 222. 5 1 Berioht von S. & Co., Oct. 1S9S, p. 37. *') Peclvolt, Pharm. Rundschan, 12, p. 286. — Artnnthe goniciilata Miq. and Piper atifi'iisfffoliuni Kuiz et Pavon are aufordinj? to Lih'sse i, Medic. Piiarm. Botanilv, vol. 2, ]). .".14, synonymouH terms. TliiK oil, therefore, is probably identical Willi one of the oils described under matico oil. Oils of the Pipeiricpae. 82? from Piper hetleh. (Chariea hetle Miq.) with some lime, ij,-ambier (from Vncaria ganibir Roxb.) and a piece of betel nut from Areca catechu L.i The betel leaves owe their spicy, burning taste to a volatile oil which has been repeatedlj'' prepared and investigated, l)ut which has not yet found anj^ practical application worth mentioning. History. When and by whom betel oil was first distilled is not known : it is highly probable that the prepai'ation of the oil by Kemp 2 in 1885 was not the first. A superficial examination of Siam betel oil in the laboratory of Schimmel & Co.-' in 1887 revealed the presence of a phenol in fraction 2.j0 — 2G0°, which seemed to correspond with eugenol. Eykman,-^ who in 1888 examined an oil distilled by him- self in Java, found no eugenol, but a new phenol which he called chavicol. A second examination in the laboratory of Schimmel & Co. revealed the fac't that Siam betel oil contains neither eugenol nor chavicol, but a third phenol, a previously unknown isomer of eugenol, which Bertram and Gildemeister " in 1889 termed betel phenol. Properties. Betel oil is a light yellow to dark brown liquid of aromatic, somewhat creosote-like odor, reminding of tea, and with a pungent taste. The sp. gr. varies between 0.958 and 1.044; the oil from fresh leaves being lightei' both in w-eight and color than that distilled from the dried material. The rotatory power was observed on three samples of oil from fresh leaves. Of these two were laevogyrate (an up to — l°4."j') and one dextrogyrate ( '.id = + 2° 4.')' ) . With ferric chloride the alcoholic- solution of betel oil produces a greenish to bluish-green coloi'. Source, yield, physical properties and composition of the betel oils thus far examined are given in the following table (see next page). Composition. Of the two phenols found in betel oil, betel phenol and chavicol, only the former has l:)een found in all oils and may, therefore, be regarded as the cliaracteristic constituent of betel oil. Chavicol, which so far has been found only in the Java oil, does not occur in the Manila or Siam oils. 1) The details cfmceniina' betel chewing and the constitnentw of the "'Retel-Apothelie" owned by alnlo^^t every Malay family are described in Tnchirch's work. "Indische Heil- und N'utzpttanzen" (Berlin 1892; p. 138. See also True, Pharni. Review, 14, pp. 130, 177. 2) Pharmacosraphia indica, part VI, p. 188. 3) Dericht von S. & Co., Oct. 1887, p. 34. 4) Chemiker-ZeitnnK, 12, p. 1338. 5) .lourn. f. prakt. Chemie, II, 31), p. 340. 328 Sper-hil Part. Origin, ^laterinl used and Yield Si-. Gr. «!> Constituents I. Siam.i Leavp.s dripf] on liot plate."*. Yield 0.6 p. c. 1.024 at 15° — Betel phenol, II. Siam.^ Leaves dried by e.\- posure to the wini. Yield O.y p. c. 1.020 at 15° — C'adineiie. in. Manila. - Fresh leaves. Yield 0.27 p. c. 1.044 at 15° — 1 Betel phenol. IV. Java.'' Fre.sli leaves. 0.05!) at 27° — 1°45' Chavicol, Betel jihenol, Sesquiterpene. V. .Tava.'t Probably fresh leave.s. 0.058 at 15° + 2° 45' Not examined. VI. Bombay. !i Fresh leaves. 0.0404 at 28° Slightly laevogyrate Betel phenol (chavibetol), (J111H12O2, contains the same side ehiiinss as its isomer eugenol, but in different positions. 1 C /\ HC/ \CH I I I HCx /COH \/ Engenol. C3H5 I C HC/ vCH HC- -CoCHs \/ COH Betel ]ihenol. HC/ HC^ xCH I COH Chavicol. Betel jihenol '■' is n liqnid with marked refractive power, and possesses a peculiar, not unpleasant but persistent betel odoi', which differs g-reatly i| Bertram & (iilclemelster, .Iimrn. t. prakt. Chemie II. 39, 11. :U'J.— Ilerieht vi.n S. &Co.. Apr. 1S8S, p. 8; Apr. 1 Ss'.l, p. G: Oet. 1889, p. 6; Apr. 1890, p. 6: Oct. 1891, p. .">. 2) Bericht vim 8. & (•„., Apr. 1891, ]>. .fj, and Oct. 1891, p. .j. 3) Berichte. 22, p. 27;t<;. 1) Bei-iclit vim 8. & Cu., Oct. 1893. ji. 4.j. S| I'harni. .lourn., HI, 20, ji. 749. 15) Bertram tS; OilderiH'i.'.iter, liii'. eit. Oils of the Piperncene. 829 from that of the closely related eugenol. When pure, l.)etel phenol boils without apparent decomposition at 254 — 255° (at 181 — 132° under 12 — 13 mm. pressure) and has a sp. gr. of 1.0(37 at 15°. In alcoholic but not in aqueous solution it yields an intensely bluish-green (>olor with ferric chloride. Betel phenol can be identified by means of its benzoyl derivative, which crystallizes in laminae and melts at 49 — 50°. (Benzoyl eugeuol melts at (39 — 70°). Acetyl betel phenol boils at 275 — 277° and melts at — 5° (acetyl eugenol melts at 3(.) — 31°), and upon oxidation with pernm.n- ganate yields acet-isovanillic acid, m. p. 2(^7°. Chavicol.i also a phenol, has so far been definitely' shown to Ije present onl^y in betel oil from Java. Ohavicol or para, hydroxy allyl benzene (comp. p. 179) boils at 237° and ha.s a sp. gr. of 1.04-1 at 13°. Its aqueous solution is colored intensely blue with ferric chloride, the alcoholic solution but faintly blue. An oil distilled by de Vrij in Java, when examined in the laboratory of Schimmel & (^lo,^ was found to contain in addition to lietel phenol a second phenol, which is probably identical with clia.vicol. The benzoyl compound crystallized in long needles and melted at 72 — 73°. Another oil distilled in Manila from fresh leaves and examined by Schimmel & Co.* contained no other phenol than betel phenol. The phenol separated from the soda solution had a constant boiling point of 128 — 129° under 11 mm. pressure and yielded exclusively a benzoyl compound crystallizing in laminae and melting at 50°. Another constituent, possibly to be found in all betel oils, is cadinene, O15H24. So far this hydrocarbon has been isolated from the Siani oiH only (dihydrochloride, ni. p. 118°). Probably the sesquiterpene (b. p. abt. 260°, sp. gr. 0.917) found by Eykman in the betel oil from Java is also cadinene. The Java oils from fresh leaves contain a considerable amount of low boiling c-onstituents. Eykman" did not succeed in isolating or identifying a pure terpene of constant boiling point froiu the fractions between 173 — 190°. Probably .several terpenes are present, but apparently no pinene. Fraction 173—175° (sp. gr. 0.848 at 1(5°: ao = — 5° 20') yielded neither a. solid bromide nor a crystalline hydro- chloride. Fraction 190 — 220° contain.s substances having a minty odor (menthone oi- menthol?). 1) Eykman, loc. cit. *i P.errram & Gildeineister, loc. cit. 2) Berlcht von S. & Co., Apr. ISiiO, p. 7. 5) T,oc. cit. ■■!) Berlcht von S. & Co., Oct. 1891, p. 5. 380 SpecinI Part. Thf' oil distilled from dried Siaui leaves was devoid of low boiling- fractions, only a few drops coming over below 200°. Whereas the absence of terpenes in this oil may be accounted for by the character of the c-rude material, the absence of chavicol in ^^iam and Manila oils and the occurrence of this substance in Java oil may be accounted for by differences in climate and soil of the respective countries. 89. Oil from Potomorphe Umbellata. The fresh leaves of Potomorphe umhelhitn Miq. (YainiXj Piperaceue) contain O.O.") p. c. of an oil, the taste and odor of which remind of pe])per (Peckolti). 90. Oil from Ottonia Anisum. From 12 kilo of the air-dried root of wild jaborandi. Ottonia anisum Spi'eng'. (Serronia jaborandi Guill. ) 10. ."ii g. ( = 0.08^ p. c. ) of a viscid oil were obtained. It possesses a peculiar, somewhat pepper-like odor and a Ijurning taste which l>enumbs the tongue. Sp. gr. 1.08.") (Peckolt^). 91. Oil from Poplar Buds. The leaf-buds of the black poplar, Populun nigra L., (Family Salica- ceae), which were formerly found in apothecary shops under the name of Onili populi and used in the preparation of ointments, yield about K p, c. of volatile oil upon distillation with water vap(ir. It is light yellow in color and has a pleasant odor reminding somewhat of chamomile. It is insoluble in 7()— 90 p. c. alcohol, but yields a clear solution with V2 p. or more of O.'i p. c. alcohol. Sp. gr. 0.900— 0.90."> ; «d = + 1° ol's to +5°-")l'; saponification number 13. Poplar bud oil distills between 2.5-"i— 2G.")°3 and consists principally of a, In-drocarbon (C5Hs)x boiling at 200— 2(51°. Piccard* (1878) judges from its vapor density that it is a diteri^ene, t'2oH82. whereas its boiUng point indir-ates a sesrjuiterpene. Fieliter and Katz" in a recent investigation of this oil, found it to consist principally of a sesquiterpene boiling at 268-2(59°. The com- pound was identified as humnlene by means of its nitrosochloride, nitrosate, both the blue and the white nitrosite, and the piperidine and lienzylamine bases prepared from these. Besides liumulene there is pro- 1) Phann. Hundschau, 12, p. 241. 4] Berichte. G, p. S90: 7, ]). 1+86. -') riiariii. Rundschau, 12, p. 287. =) Berichte, 82, p. 3183. 3) Bericht v.ju S. i: Co., .ipr. 1887. p. 36. Oils of the Myi-icacene. 331 l)ablv rontaiiipcl in the oil a second sesquiterpene, and about ]i p. c. of paraffin, C24H50, ni. p. .38—68°. Tlie bodies to which the pleasant odor of the oil is due passed over in the lowest fraction. 92. Dutch Myrtle Oil. Upon distillation of the fresh leaves of Myrica gale L. (Family Myrkaceae), O.G.7> p. c. of a brownish-yellow- oil (Kabenhorst,i 1837), sp. gr. 0.876, are obtained. At 17. .j° it congeals partly, at 12.5° com- pletely to a crystalline mass. The odor is peculiar balsamic, pleasant ; tlie taste mild at first, then temporarily burning and permanently astringent. It is said to contain 70 p. c. camphor (?). 93. Bayberry Oil. The leaves of J/rz-ica cerifem I^. (Family Myrieaceae) yield 0.021 p. c. of volatile oil, 2 of greenish color, and very pleasant aromatic, spicy odor. Sp. gr. 0.886; au = — '>°'>'. 94. Sweet Pern Oil. Tlie dried leaves of Myrica anplenifolia Endl. (Cowptonia aspleni- folia Alton) yield upon distillation about 0.08 p. e. of volatile oil. It has a strong spicy, cinnamon-like odor. Sp. gr. 0.026. When cooled in a freezing mixture the oil congeals. ^ 95. Oil from Walnut Leaves. The aromati(; odor of the fresli leaves of Jnglans ivgia, L. (Family ■Tnglandaceae) is attributable to the volatile oil they contain. Upon di.stillation of 800 k. of fresh leaves, Schimmel & Co.* obtained 23-5 g. of oil. It is yellowish-green in color, solid at ordinary temperature, and lias a pleasant tea-like odor. 96. Sweet Birch Oil (Wintergreen Oil). Oleiiiii Betiilae Lentae. — Birkeiiriiuleiiol. — Essence de Betula. Oricjin and History. Cherry birch or sweet or black birch, Betiila Ifiita L. (Family Betulaceae) is a tree 15 — 20 m. high which grows on ■ -■ood forest soil throughout southern Canada and the n(3rthern United 1) Bepert. Pharm., 60, p. 214. Oinelin, Organ. Cheniie, IV Eil., ^'ul. 7, p. 33.'>. 2) Bericht \«n S. & Co., Oct. 1.S94, p. 78. Comp. also Hamliright llS63l. Am. .Toiirn. Pharm., 'A'y. p. 193. .1) Bericht von S. & Co., Oct. 1890, ]). ."0. i) Bericht von S. & Co., Oct. 1890. p. 49. 332 SpecUil Part. States. westwMi-d as far as Minnesota and Kansas, and to the south as far as GeorRia and Alabama. When chewed its reddish-bronze colored bark develops a peculiar fragrance a,nd taste, and on this account has Ijeen used by the natives for chewing and in the preparation of refresh- ing and medicinal beverages. Next to turpentine oil, the oils of sas- safras, wintergreen and birch bark are among the first oils obtained by distillation in the United States. The similarity in odor and taste of bir(;h bark oil with true oil of wintergreen from Gaulthevhi proeiim- bens was known before 1M1,S (BigelowM- The chemical identity of the principal constituent of both, however, was demonstrated by Proctor 2 in IH-t;!. As the demand for wintergreen oil increased, sweet birch bark was distilled indiscriminatly with wintergreen leaves or even distilled alone as substitute ^ so that the commercial natural oil is at present obtained almost exclusively from the bark of Betuhi lenta. L. Preparation. For purposes of distillation, the young trunks and branches were formerl,y used. These were cut into pieces 1 — 4 inches in length which were macerated for 12 hours previous to distillation. For the latter operation stills like those described under wintergreen oil were used. More re(;ently the bark of the trunk and the larger branches is ]5eeled off in late summer and either cut, or torn by means of toothed rollers, and freshly distilled with water from copper stills. If wintergreen grows abundantly in the neighborhood it is added to the bark in the still. According to the abundam-e and the convenience with wliiidi the one or the other can be obtained, preference is given to the clieajjer material. Ac^cording to Kennedy, maceration for 12 liours is considered indispensable to a good yield. A ton of 2.240 lbs. of birch bark yields about .") ponmls of oil ^ 0.28 p. c. A like amount of wintergreen yields al)out IS lbs. of oil.-^ Upon rational distillation, however, as much as 0.() p. e. of oil can be obtained from the bark. Proctor already recognized in 1H-I:8 that the oil did not preexist in the liark, but results upon the interaction of two constituents in the presence of water, similar to the fornmtion of the oils of bitter almonds. I) Americjin Afedical Botjin.y, vol. 2, ])p. 2S and 241. ^1 Am. .Touril. Phann., 1.5. p. 241. 3| Iletiila lenta and Gaultherla prticumheiis grow togptlier in thu wooded monntain- OUK regions of tile North Atlantic states. In a report on tlie wintergreen oil industry, Kennedy (Am. .lonrn. Pharni., .52. p. 49) in 1882 ealled attention to tile tact tliat tlie cost of collection of birch bark was but \'^ of that of wintergreen leaves; also that the yield of oil from the bark was but 0.2.5 |). c.. whereas that from wintergreen was O.SO p. c. According to these figures the cost of production of the oil from birch bark is but half as great as that of wintergreen leaves. -1) Am. .Triurn. Pharm., .54, pji. 40— .58. Oils ol the Betnhweae. 833 mustard, ete.i According to more recent investigations by Schneegans^ these substances are betulase, a ferment, and the glucoside gaultherins which crystalhzes with one molecule of water : .OH Gaultherin Water Methyl salicylate Grape sugar. CiiHisOs + H2O = C8H4 p. c cau.stic potash solution whicli dissolves methyl salicylate immediately without the formation of a precipitate, leaving other oils undissolved. Chloroform can also be detected in this way. Five percent of foreign constituents can l)e recognized in this way. Inasmuch as the odor of methyl salicylate disappears completely in tlie alkaline solution, the nature of the adulterant can usually be rei-ognized by its odor. Tlie amount of methyl salicylate can be determined by isolating and weighing the salicylic acid or volumetrically. For the gravimetric determination Ewingi (1802) rec(niiniends the following process: l.Ti— 2 g. of the oil are saponified in a flask of .50 cc. capacity with a slight e.xcess of soda solution. To the liquid, transferred to a se])aratiiig funnel, 1) Proc. Am. Pharni. Aks., 40, p. 19(). Oils of the Betnlncene. 335 liydi'oehloric acid is added in excess and the liberated salicylic acid shaken out with ether. In order to remove traces of sodium chloride from the ethereal wolution, this is shaken with water. The ethereal solution is evaporated in a tared capsule on a waterbath. The residual salicylic acid is weighed after having been dried to constant weight over sulphuric acid. This method of assay presupposes a pure oil, for foreifiu additions such as sassafras oil, would pass into the ethereal solution with tlie salicylic acid and remain upon evaporation of the solvent. For the volumetric estimation, E. Kremers and M. James i give the following directions : 5 g. of oil to be dissolved in an excess of standard soda solution and the solution to be boiled for five minutes to effect saponification. The excess of soda solution is ascertained with the aid of normal acid and the number of ccs. of normal alkali consumed in the saponification multiplied by 0.152, the methyl .sahcylate factor. Tlte as.soy can also be effected by determining the amount of salicylic acid present according to tlie metliod of Messinger and Vortmann.- This method is based upon the supposed fact that in the presence of much alkali salicylic acid is converted by iodine into a diiodo salicylic acid iodide. The excess of iodine is ascertained by titration with standard tliiosulphate solution. The reaction is supposed to talce place according to the following equation : CuH4(OH)COOK + yNaOH+61 = C6H2l2(OI)COOK + :iKI + 3H20 The application of this method to winter'green oil has been suggested hj Kremers and James : i A weighed quantity of oil (abt. 3 g. ) is saponified with normal alkali, care being taken to employ at least 7 molecules of potassium hydroxide for every molecule of methyl salicylate. The sai)onified liquid is diluted to either 2.50 or 500 cc. Of this solution 5 or 10 cc. res|)ectivelj- are heated in a flask to 60°. Decinormal iodine solution is then added until the color is permanentl.v yellow. Upon shaking a deep red precipitate results. Upon cooling, the solution is acidified with dilute sulphuric acid and diluted with water to 250 or 500 cc. In an aliquot part (abt. 100 cc.) of the filtrate the excess of iodine is ascer- tained by means of X/10 thiosulphate solution. 1 JIol. Methyl salicvlate 151. 0-t '- '■ = = 0.19974:!11. 6 Atoms Iodine 750.2 By multiplying the amount of iodine found (in ccs.) with the facl:or 0.19974.314: the amount of methyl salicylate jjresent is found, from which the percentage of ester in the oil can be calculated. A good oil should contain at least f>8 p. c. of methyl salicylate. 1) Pharm. Review, 16, p. 1«0. =) Beriilite, 22, p. 2821: 28, p. 27 3.30 Specinl Part. 97. Oil of Hops. Oleum Hiiimili Liipuli.—Hopfeiiol.— Essence de Houblon. Origin axd Histohy. On account of their peculiar aromatic odor mid taste, the frnit of Huinuhis lupuluN L. (YamWj Moraceae), which is cultivated in most countries, has been used since the middle ages for the aromatization of barley beer. Hops, therefore, are mentioned in litei-ature since the eighth century.^ Medicinally hops are l^eing used only comparatively recently. The medical use of lupulin was suggested in 1820 liy Ives, 2 a New York physician. The volatile oil of hops seems to have been first distilled from the glands by Payen and Chevallier,^ but thus far has found but little ,'ipplication. Prepakation. Oil of hops is prepared from the strobiles as well as from the lupulin. The yield from hops varies from U.3 — 1 p. c, from lupulin as much as 3 p. c. are (jbtained. The latter, however, is less pleasant and, therefore, inferior. The aqueous distillate — especially tliat from lupulin — is strongly acid and contains valerianic acid (Per- sonnel <^nd probably also butyric acid (Ossipow). Unbleached hops must be u.sed for distillation, otherwise the oil has an unpleasant sulphurous odor. Properties. Oil of hops is a light yellow to reddish-brown thin liquid which becomes viscid upon prolonged standing. It has an aromatic odor and its taste is not bitter. Sp. gr. 0.8.").")— 0.880; '/■D = +0° 2.S' to +(.»°40'. In alcohol it is very difficultly soluble, especially older oils do not yield a, clear solution with even !).5 p. c. alcohol. This may possibly be attributed to polymerization products resulting from S(i-called oleflnic terpenes present in the oil. CoiiPOsiTiox. Although oil of hops has frequently been examined rliemically,* not a single constituent had been isolated and characterized until recently. In 189.' Chapman 5 showed that, aside from small amounts of oleflnic terpenes. oil of ho]:)s consists principally of a sesquiterpene, Iramulene. The oxygenated constituents, however, to which the oil evidently owes its peculiar aroma, were not investigated by Chapman. 1) I'harniacoffraphia. i>. .%.51. 2 1 Silllninn's .J mini, of Sc. & ArtK, 1820, p. ;!02, 3J .loilrn. (le Pharmacie, s, pjj. 214 & 533. i) Pa.yen & Chevallier, loc. cit. — \Vagiiei- (1S53), .lourn. f. jirakt. Cheiii., .58, p. 3."1. - Personne (1834), Compt. i-ond., 88, p. 309.— Kiilinemann ilSTTi, Berichte, 10. p. 2231. -Ossipow (1883 & '8G), .Journ. f. prakt. Chem., II, 2S, p. 48, and 34, p. 238. 5) .Jonrn. Chein. Soc, 67, pp. 54 & 780. Oils of the Mornecfip. .'i87 The fact that the analysis of fraction 166—171 (sp. ^r. 0.789) agrees with the formula C10H17. seems to render it probable that it consists of a mixture of two hj'clrocarbous, viz. CioHis and GioHiij. Tlie latter is possibly identical with one of Semmler's i olefinic terpenes. Bromine and hydrochloric acid are absorbed energetically, but do not yield crystalline derivatives. Upon oxidation, oxalic acid alone was obtained. Almost two-thirds of the oil consist of humulene, a sesquiterpene boiling at 263—266°, sp. gr. 0.9001 at 15°. Isolated by fractionation it is obtained either slightly laevo- or dextrogyrate. When perfectly pure it is probably inactive. With bromine and hydrogen chloride liquid addition products only are obtained. A charactei'istic derivative was obtained b.y passing nitrosyl chloi'ide into the chloroform solution. This nitrosochloride melts at 164 — 165° and may serve for its characterization. The humu- lene nitrolpiperidide obtained from it melts at 153°, the nitrolbenzylamine base at 136°. Caryophyllene from oil of cloves yields similar derivatives which ai-e, however, quite different in melting point. Caryophyllene also readilj'' yields a crj'stalline hj^drate, whereas humulene does not. The latter, therefore, i.s to be regarded as a new distinct representative of the class of sesquiterpenes. 2 AdtjLTeratiox. Oil from copaiba balsam is mentioned as an adulterant of hop oil. The higher sp. gr. and larger angle of rotation should, however, readily betray its presence. According to Chapman, s the statement made by Personnes that the oil upon oxidation yields valerianic acid is incoi'rect. This acid, however, results upon oxidation of the extract of liops with per- manganate. 98. Oil of Hemp. The various statements concerning the properties and composition of the volatile hemp oil differ considerably. According to Personne* (1857) the oil from Cnnnnbis indica is lighter than water and congeals at 12—15° to a butyraceous mass. It is said to consist of two hydrocarbons : the liquid canabene. CisHao, 1) Berichte, 24, p. 682. 2) For a detailed comparison of tliese two hydrocarbons see I'tinnn. Arcli., 2, p. 27.S. 3) Chem. Centralbl., 1898, 11, p. .360. *) .Journ. de Pharni. et de Chim., IH, 81, p. 48. 23 338 Special Part. which lioils at 2:!.")— 240°, and caiiiiabene hydi-ide, ('12H24, whirh ciystallizes from ali'ohol in scales with a fatty lustre. Valentpi (ISSO) examined an oil that was obtained from Italian Cnnuabis indk-ti. It consisted principall.y of a sesquiterpene, C1.5H24:; b, p. 2r,6— 258° ; sp.gr. 0.9209 at 0°; [ajo = — 10.H1°. With liydrog-eii chloride it yielded a solid liyilrochloride. Tlie same sesquiterpene is found in tlie oil from the male infioreseeni;e of <':inn;ihis gignnten. Upon steam distillation of the female flowering- plant, Vignolo^ (188.")) obtained a mobile aromatic oil which b(jiled between 248 and 2()8° and did not congeal when cooled to — 18°. When distilleil over sodium, a stearoptene remained behind which was not further examined, wdiereas a sesquiterpene (b. p. 2.">(j° ; sp.gr. 0.897 [?] at l."i.;?°) passed over. The formula ('1.5H24 was established by elementary analysis and vapor density determination. A crystalline hydrochloride was not obtained. Schinimelc%Co. 8 obtained upon distillation of the non-flowering herb of Ciiuiinbis indica 0.1 p. c. of a mobile oil with narcotic but not unpleasant odor. At 0° it congealed to a butyraceous mass. 8p. gr. 0.982. Whether the sesquiterpene found in the oil is identical with any of the known conqDounds does not become apparent from the scant literature on the .subject. The cannabene hydride of Personnes is ])Ossibly nothing more or less than paraffin which is frequently found in volatile oils. 99. Sandalwood Oil. Oleum Ligni Santali. — Ostiiulisehes Sandelliolziil,— Essence de Sautal. History. On account of its pei/uliar. very pleasant odor, as well as on account of its durability, sandalwood from Santiiluw nlhuin L. has lieen used since antiquity. Medicinally^ and ei'onomicaily it has an important and very interesting historj-. In mediaeval writings and in the later treatises cin distillation, however, sandalwood is but .seldom mentioned, the oil having been u.sed only in recent periods for medicinal and other purposes. Previous to this century the oil has been distilled by Saladin ► (1488), Gesner-'^ (15."i-j), and Hoffmann*" (1722). Neumann and Dehne'^ (1780) ascer- tained the yield, and (^hapoteaut« first examined the oil in 1882. 1) I'iazz. ohim. ital., 10, p. ."i-Ki, * 11, p. J) Ein kJistliohei- Schatz. p. 246. 191.— Berichte, 13, p. 2431, & 14, p. 1717. «) Obsevvatorium ph.rsico-chemiearum, -') Gazz. chim. ital., 25, I, p. 110. p. 6!). 3) Bei-k-ht von ,S. & Co., Get. 1895, p. 57. 7) Cveir.s Cheinisches Journal, .3. p. 18. *) fompendinm aromatarioruin, fill. ;!4y. s) Bull. Soc. chim., II, 37, p. 303. Oils of the SanUiku-eae. 339 In Ceylon, distilled .sandalwood oil is reported to have been used tor the embalming of the dead bodies of native princes since the ninth century, i Origin and Pheparation.^ Smitalum ulbuiulu. (Family Saiitalaceae), a tree 6 — 10 m. high with dense foliage, is indigenouH to the mountains oi India and either grows wild or is cultivated in dry open places, rarely in forests. ^ The wood of the trees growing in dry rocky mountainous soil is harder and richer in oil than that of trees cultivated in fertile soil. The territorj- which produces sandalwood is a strip 250 miles long which extends fi-om tlie Nilgiri mountains to the north and northwest through My.sore and C.oimbatore to (^'anara. The tree grows from sea-level up to altitudes of 1000 m. The trees ai-e property of the state. In the presidencies of Madras and Mysore the wood and the roots are arranged according to grade into 18 classes* and sold at auction. Wood destined for the European market is shipped via Tellichery or Bomliay. A considerable amount is u.sed in Asia for ritualistic purpo.ses, and some of it is used in the primitive distillation of the oil at the place of production. Bidie^ describes the process as follows : "Tlie bodj' of the still is a large globular clay pot, with a circular mouth, and is about 2)^ feet deep by about 6 feet circumference at the bilge. No capital is u.seci, but the mouth of the .still, when used, is closed with a clay lid, having a small hole in its centre, through which a bent copper tube about 5% feet long is passed for the escape of the vapor. The lower end of the tube is conveyed inside a copper receiver, placed in a large porous vessel containing cold water. When preparing the sandalwood for distillation the white or sap wood is rejected, and the heart wood is cut into small chips, of which about 2 maunds or 50 lbs. are i)ut into the still. As much water is then added as will just cover the chips, and the distillation is carried on slowly for ten days and nights, by which time the wdiole of the oil is exti'acted. As the water from time to time get.s low in the still, fresh sui^plies are added from the heated contents of the refrigerator." According to another report" the distillation lasts 21 days and yields '2Jj p. c. of oil of a sp. gr. 0.980 and higher. The prolonged distillation is sufficient explanation for the dark color and high specific 1) Pharniacographia, II ed., p. o99. 2) J. L. Pigot, conservator of forests in Mysore, India, has written an interesting pamphlet on the sandalwood cultivation in India accompanying the exhibition of the British Colonial Governments at the Paris Exposition 1900. 3) Holmes, Pharm. .lourn., Ill, 16, p. 819.— Petersen, ibid., p. 757. — Kirkby, ibid., p. 8.57. — .Sawer, Odorographia, vol. I, p. .315. *) Bericht von S. & Co., Oct. 1898, p. 44. 5) Holmes, loc. cit. 6) Chemist and Druggist, May 2e, 1804. 340 Special Part. gravity 1 of this oil contaminated witli decomposition products. Only a small part of it is brought to Europe, most of it being exported to China and Arabia. Sandalwood is also produced in eastern Java, and in the islands Sumba (t^oemba or Tjendana) and Timor. This variety is brought into the market as Macassar sandalwood via Macassar (in the Celebes). It does not contain as much oil as the East Indian wood, lait the oil can hardly be said to be inferior. Owing to a more complete comminution as well as to perfected apparatus for distillation a larger yield of oil is obtained in Europe than in India: from East India sandalwood 3— ."> p. c, from Macassar wood 1.0—3 p. c. The European oil is light colored, has a pleasant odor and compares favorablj^ with the Indian oil which is contaminated with empyreumatic products. Phopebties. East Indian sandalwood oil is a. rather viscid, light yellowish to yellow liquid of peculiar, faint but per.sistent odor, and of an unpleasant, resinous, harsh taste. The sp. gr. of a normal oil lies between 0.975 and 0.980. The Indian oils, as already stated, have a higher sjieciflc gravity and a darker color due to decomposition pro- ducts. The angle of rotation varies between narrow limits, viz. — 17 to — 19°. With 5 p. of 70 p. c. alcohol, sandalwood oil yield a clear solution which is not rendered turbid by the further addition of alcohol. Upon age, especially under the influence of light and air, its solubility diminishes and it then jdelds turbid mixtures in the ratio mentioned. The santalol content determined by acetylization and calculated for CisHoeO is 93 — 98 p. c. Under 11 mm. pressure about 9."5 ii. c. of the oil passes over between 15.5 — 170°, ^ under ordinarj' pressure between 27.") — 29.j° (Umney,s 1895). The saponification number is 5 — 15. Composition. According to the investigation of Chapoteaut* (1882) sandalwood oil consists almost exclu-sively of two substances C15H24O and C15H26O. The former boils at 300° and is regarded as an aldehyde, whereas Ci5ll2«0, with a boiling point of 310° is supposed to be the coi'responding alcohol. Phosphoric acid anhydride abstracts water from tlie oil, two hydrocarbons resulting: to the one boilinti- at 215° 1) Conroy has shown experimeutally tliat the sp. kt. of ,an oil is increased from 0.0S9 when heated Avith water to .50° for ten days (Chemist and Druggist, Aug. 19, 189:-!). -) Bericht von S. & Co., Oct. 189:!. p. HI. 'J) Pharm. .Journ., Ill, 25, yi. 1044. The statement of Chapman and Burgess, how- ever, (see under composition) do not fully agree with these data. *l Bull. Soo. chini., II, R7, p. mS. Oils of the Santalaceae. 3il. the fomiula C13H22 is assigned; and to the other, b. p. 260°, the formula C13H34,. When the oil is heated with glacial acetic acid to 1.50° the acetic ester of santalol, C15H23O . COCHg results, also a substance CgoH^eO (?)• Inasmuch as the low specific gravity of Chapoteaut's oil (, p. 118. *) Pharm. Ztg., 44, p. 2,18. 342 Sppcial Part. .small amount of an ak-ohol boiling' at 160— K;.')" umler 7 mm. jire.ssure wa.s obtained. They also found an acid melting at l.')4° in the oil. (xuerbeti ha.s recently inve.stigated sandalwood oil, but his results iiiu.st l)e taken with caution as the oil investigated had a very low sp. gr. and was therefore either adulterated or else an abnormal distillate. He found the following constituents : 1. Two sesquiterpenes : «-santalene. b. p. 2.52— 252.. 5°, .sp. gr. O.QVU at 1()°, «d = — 13.98°; ,J-santaleiie. b. p. 261—2(32°. sp. gr. 0.9139 at 0°. «d = — 28.55°. The latter is identical with that found by Von Soden and Midler. 2. A mixture of two alcohols. d.-iHaoO, of different rotatory power. 3. An aldehyde. (''i.'iB[240, saiitalal, b. p. 180° at 40 mm. : it has a strong pepperdike odor. Its .senncarbazide melts at 212°. 1. An acid, Ci.-HoiOo, santalic acid, a viscid, colorless lir[uid boiling at 210 — 212° at 20 mm. 5. An acid, OioHiiOo, teresantnlic ai-id, m, p. 157°. Small amounts of strongly smelling sub,stances, to wliich the odor of the oil is principally due were found in the more volatile portions of the oil. ExAMisATiox. Inasmuch as the physical constants of sandalwood oil are subject to slight changes only, additions of almost any nature can usually be detected b,v means of the speeitie gravity, optical rotation, and solubility in 70 p. c, alcoliol, t'edar wood oil, the principal adulterant, is readily recognized by an increase in the optical rotation, lowering of the .sp. gr. and the diminution of solubility. Very similar changes are produced by the oils from copaiba- and guriun balsam; the former, however, usuallv diminishes the angle of rotation. AVest In. c, never less than 90 ]i. c. santalol. Parry- first suggested the conversion of santalol, Ci.-,H2oO, into its acetic ester, Ci.-,Hi\-,( » .('0('Ha, by heating it with glacial acetic acid 1) Compt. rend., 18(1, p. 417: .loiiin. de I'Imriii. ft Chim., VI, 9, p. 224. 2) T'hiinii. .Ii.urn., .">."). p. lis. OUn of the S.nntalacPcie. 348 Fig. 02. Santalwood Tree. .314 Special Part. in a closed vesnel to 1.jO°; and to saponify tlie ester witli alcoholic potassa. According to Schimmel & (!o.,^ however, it is more expedient to make the alcohol assa.y of volatile oils with aiietic anhydride. The process is ronducted as follows :^ About 20 g. of sandalwood oil are gfiitly boiled for 1^ hour witli an equal volume of acetic acid anli.vdi-idc and a small amount of fused sodium acetate. The product is washed with water and soda solution and the resulting- oil dried with anhydrous sodium sulphate. Of the dried oil, 2— .5 g. are boiled with an excess of N/1 potassa V. S. and the excess of alkali ascertained b.v titration with N/1 sulphuric acid V. S. The amount of santalol is calculated with the aid of the following formula: aX22.2 P = s— (aX0.12) P = Santalol content of the original oil. a ■= Number of cc. N/1 potassa \. S. consumed. s = Amount of acetylized oil, expressed in grams, used for saponification. In most instances the determination of tlie physical constafits will sufHc-e to distinguish a pure oil from one adulterated. Positive assur- ance can, however, be had by making a determination of the santalol content. It is, therefore, as unnecessary as it is unscientific to resort to color reactions which have been suggested. 100. South Australian Sandal-wood Oil. SantBlum preisshmum Miq. known as "quandong" in Australia bears edible fruits known as native peai/hes. The wood is dark brown, of very dense and tough texture and uruisually hard and heavy. It contains o p. c. of a viscid, cherry-red oil, sp. gr. 1.022. The odor is pleasantly balsamic reminding somewliat of roses. Upon standing the oil .separates crystals, which by i-e(!ryst:dlization are olitained in prisms melting at 101— l().j°.» Composition. The ciystalline C(jnstituent of the oil has been examined by Berkenheim^ (1892). He found the melting point 101—103° and assigned to it the formula CisHsiOj. The substance is an alcohol, the jicetic ester of whicli crystallizes in hexagonal plates melting at (58.5 to 69..")°. AVith phospliorus trichloride it yields a chloride, ('15H23OCI, ni. p. 119— 120.. ■)°; phosphorus pentacliloride does not act on the 1) Rerieht von S. & Co., Oct. 1S9.">, p. 41. 2) Bericht von S. & Co., Apr. 1897, p. 40. 3) Bei-lcht von S. & Co., Apr. 1891, p. 49; and Oct. 1801, p. «:i. +) ZeitKChr. il. Riiss. phvs. chem. (rcs., 24, p. (588 : .Abstr. Cheni, CeiUralhl., 189:i. I. p. 98G. Oils of the Santahwene. 345 alrohol. The methyl ether obtaiueil by means of the sodium compound of the alcohol is liquid. Potassium permauganate oxidizes it to a liquid acid C7H14O2. 101. West Australian Sandalvirood Oil. The wood of Snntaluni cygnoi-um Miq. (Fusaiw.s spiaitus K. Br.) is exported from Freemautle, W. Austr.. and is kuown in the Singapore market as Swan river .sandalwood. In India and ('hina it is used as substitute for the Indian sandalwood from Santaluin iilbiim. The wood c-ontains 2 p. c. of oil having an unpleasant resinous odor; sp.gr. 0.9531 — U.065 (Parry 2); «d = + 5°20'. West Australian sandalwood oil, therefore, has very different proper- ties from those of the East Indian oil and cannot be used a.s a. sub- stitute for the latter. The oil was distilled as early as 187.5 by Sehiuunel & Co.; recently the distillation of the oil has been taken up in Freemantle.^ Parry- found the saponification numbers 1.1 — 1.6. After acetylizatiou he obtained saponiflt-ation numbers which seemed to indicate an apparent santalol content of 75 p. c. Whether the alcohol of this oil is identical Avith that of S. allmm has not yet been established. 102. Fiji Sandalwood Oil. The wood of Santaluin yasi Heem* from the Fiji islands was exhibited at the Colonial Exposition at South Kensington in 188G. Upon distillation it yielded (5% p. c. of a volatile oil with a faint but not very delicate odor, thus rendering it unfit for perfumery.-' Sp. gr. o.i)7G8; «D = — 25.5° (MacEwan," 1888). 103. African Sandal-wrood Oil. The botanical origin of this oil is not known. The w(.)od designated sandalwood, from which this oil was distilled, was dark brown in color, very hard and tough and had lieen brought to Europe from Tamatave (Madagascar) via Zanzibar. Upon distillation it yielded 8 p. c. of a ruby red oil of the consistency of East Indian sandalwood oil, which it also resemlded in odor." Sp. gr. (».!)<)9. 1) Bericht von S. & Co., Oct. 1888. p. 36; and .\pi-il 1891. \i. -tM 2) Xotes on Santal Wood fJil, p. 0; Chein. & Drug., ~>S, p. 708. 3) Berkht von S. & Co., Oct. 1898, p. 4.5. ■1) Phai-ni. .Jonrn., Ill, 16, p. 7.".7 & 820. ■"•I Bericht von S. & Co., Apr. 1888, p. 3'.l. 6) Pharni. .Jonrn,, III, 18, p. 561. 7) Bericht von S. & Co., Apr. 1S91, p. 4i). 346 SpecinI I';irt. The wood is possibly identical with Hasovanto, a wood occui-riny in northern Madagascar which is said to possess properties similar to those of sandalwood.! 104.. Oil of Asarum Europaeum. Oleum Asari Eiiropaei. — HaseliviirzOl. — Essence d'Asaret. The root of Asavum europneuni L. (Family Avifitolochincene],v;\\\v\i grows in the shady hard wood f(jrests of Europe, Siberia and the Caucasus, upon distillation yields 1 p. c. of a viscid brown oil heavier than water with an aromatic odor and a pep]iery. burning- taste. Often the oil congeals soon after distillation, sometimes crystals of asarone separate only after ])rolonged standing. Sj). gr. I.OIS— 1 .0()8. On account of its dark color, the angle of rotation has not yet been observed. Composition. The separation of a solid substance from the oil was first observed by Gorz-' in 1H14. Lassaigne and FeneuUe'^ (1S20) seem to have rega.rded the stearoptene obtained by the distillation of the root with water vapor, as camphor. Further reports on this sulistance were made by (jriiger^ in IHHO anil V)y Blanchet and Sell"' in 188;! who made the first elementary analysis of as;irum camphor. Schmidt" (184."i) studied principally the crystallographic characters (if the sub- stance to which he assigned the name asarone which is still in use. Rizza. and Butlerow''' recognized that asarone contains three raethoxy grou])s and assigned to it the formula Ci2Hi(jOa. which was later shown to be correct. Poleek and Staats,* however, found at first the formula C^HioOl., later (WaHiTOs and finally Ci:iHis08. The relative position of the three methoxy groups was ascertained by Will" in 1888 who showed thtit asarone is a derivative of oxy- hydroquinone. The recently accomplished synthesis of asarone by Gat- termainii" shows it to have the formula CoHl' . C:iH.-, . (0CH3).s = l :2:1:.'. 1) Odoroffraiihia. ^-ol. 1, p. :J2.'. = ) PFafJ, System der .Mat. Mi'il.. vol. 3. \i. L'Hii. ^) -Journ. (le Pliarni., 0, ]) 5'il. — Troiniii.-.;(loi-ft"rs Xi-ues .Tourii. d. I'hariii., .~. 11, p. 71. + ) Diawertatio de Asaro Eiirojiat'o. (rottiiif^. 0) liiebip^'s Annalen, C», p. 296. *'l Liebiff's Annalen, ijM, ]i. 15(j. ') Bei-ichte. 17, p. ll.j'.l.— Zeitsehr. d. Uiis.s. pliys. elieni. lie.s., I'.i, 1. p. 1; Berielile 20. Kclei-ate, p. 222. N) Hericllte, 17, p. lilTi, — Cheni. ZeUung, ',), |i. I+IU. — .laliresb. (. Pliarni., Iss.".. I). ;S;{1. — Tagebt der 50. A*er.samnilnnff deut.sclier Natniiorscher, lss(;, p. 127. — .(alti-esl). f. I'luuMTiaeie, l.s.SO, p. 2.S:{. ai Beriehte. 21, p, 614. 10) Beriflite, H2, p. 2811, Oils of t/ip AriKtolocliinceiw. 347 Eykmaui made a study of the i-itructure of tlie CgH-.-radiral in l.ss<>. From the index of refraction and the dispersion he came to the con- clusion that asarone was a propenyl and no allyl-derivative. Properties and derivatives of asarone are described on p. 181. Upon fractionation of the constituents accompanjing the asarone^ Petersen 2 obtained a laevogyrate fraction boiling at 162 — 105° which contained 1-pinene. Upon direct bromination it yielded a litpiid mono- bromide; after heating to 2.~)()° dipentene tetrabromide melting at 122° was obtained. The higher boiling constituents distilled principally at about 2."i()° yielding a. fraction of the composition CiiHi4,02. With sodiinn nitrite and acetic acid a nitrite melting at 118° was obtained. When heated with hydrogen iodide, methyl iodide was split off. Upon oxidation with potassium permanganate, vera trie acid was formed. Petersen (1888), therefore, regarded the substance boiling at 2."')0° as methyl eugeuol. MittmannS (1889), however, is of the opinion, that it is not methyl eugenol, but methyl isrjeugenol, basing his i-onclusion on comparisons made with the synthetic methyl ether prepared from bay oil eugeuol; also with the natural ether occurring in bay oil. Inasmuch, however, as the phenol from bay oil. from which Mittmann prepared the methyl ether, must have been a mixture of eugenol and chavicol, as was shown later, the methyl ether of Mittmann can hardly have been pure :ind thus his comparisons are rendered valueless. It, therefore, still reiuains an open question whether asarura oil conta,ins the methyl ether of eugenol or of isoeugenol. The highest boiling fr;ictioii is rohired green by ii sul)staiice not yet examined. 105. Oil of Canada Snake-root. Oleum Asiiri Caiiadensis, — Caiiadiselies Sfhlaiisenwnrzeldl.— Essence de Serpentaire dii Canada. Annvum eunadense L. is known in the United States as Ciinada snake- root, wild ginger, and Canadian asaraliacca. The rliizome i-ontiiins a fragrant volatile oil which is u.sed extensivel.y in perfumery in North America. Upon distillation, the dry rhizome yields ;!.."i — !.."> p. c. of oil. Tlie rootlets contain somewhat less oil than the rhizome. 1) Berichte, 22, \i. :(172. S) Archiv il. Ph,ann., 227. |> 2) Archiv d. Phanii., 220, ]p. SO. 348 Sjiecml Part. Properties. The oil has a yellow to yellowish-brown color and a strong but pleasant aromatic odor and taste. It is soluble in 2 p. of 70 p. c. alcohol; sp. gr. 0.98—0.96. Composition. According to Power' (1880) the oil c-ontains the following subtanees : 1. A very small amount of an inactive terpene, CioHio. boiling at K;;!— 166° which possibly' is identical witli pinene.^ 2. Asarol alcohol OioHisO; b. p. 196—199°: sp. gr. ().S74 at 17°; '-(D=+l°. Its odor reminds of coriander and in the oil it is partly combined with acetic and valerianic a(iids as ester. It ap]3ears to be identical with linalool. 3. An alcohol CioHisO, isomeric with the former but boiling betw- 222 — 226°. Its odor resembles that of geranium oil and possibly con- sists largely of geraniol. 1. Methyl eugenol. Fraction 2.'')4:— 2.")7° has the composition (JiiHi4,02, and upon oxidation with permanganate yields an acid which Petersen has I'ecognized as veratric acid. Methyl eugenol niay, therefore be considered as one of the constituents of the oil of Asariim auiadense L. •J. Fraction 27"( — 8-"50° is l:)lue. has no con.stant lioiling point, and is indefinite in composition. 106. Oil of Virginia Snake-root. The rhizome and roots of Ari.stolocliia nerpentni-ia L. and of .1. reti- cuhitii Nutt. (Family Aristolochhicene) are official in the U. S. Phar- macopoeia under the title of Serpentaria. As the rhizomes of Ijoth plants are similar morphologicallj' and as to their therapeutic properties, so the oils from both are closely related. Aristolochhi serpentnria' L. upon distillation yields 1—2 p. c. of oil of valerian-like odor and a s]). gr. of from t).98 — 0.99. Spica * (1887) has shown the principal constituent to be borneol. Aiistolochhi retinilatu 'Nntf., distilled in small (juantities by Peacock* (1891) yielded but 1 p. c. of a golden-yellow oil of camphor- and valerian-like odor. 8p. gr. 0.971— 0.97S ; „.o^ — 4:°. The oil contained a teriiene boiling at l."')7°, probably pinene; also l.)orneol, which is com- bined with an acid not yet identified. 1) On the constituents .if the i-hizimie of Asariim i\linj(Jeiise L. Dissertation, Stras.s- ))ui"a'; Proc. Am. Pharni. Assoc., 2-S, p. -H;;4. 2) Comp. Petei-seu. Arch. cl. Pliarni., 22G, \i. 12S: P.ericlite. 21, )i. 1004; also I'ower, Pharni. Riindschan, fl, p. 1(^1. :i> Gazz. chini. Ital., 17, p. 313: .lahresij. f. I'liavni., ISST. )i. 4,j. ■'I .Vni. .lourn. Pharni., (i.'i, p. 2."T. Oik of tlie CbpnopodUiceae. 349 107. Oil from Aristolochia Clematis. Osterlnzeiol. The oil from the rhizome of Ai-istolochJn rleinatis L. was prepared by Winekleri in 1849 and by Friclvhinger- in 1851, the former obtaining 0.4 p. c. Walz'S in 1853 distilled the entire plant and obtained a golden-yellow, Yi.S(.-id oil of acid reaction and a sp. gr. of 0.903. 108. American Wormseed Oil. Oleum Chenopodii Antlielmintioi. — Chenopodinmol oder amerikanisclies Wnriii- saineniil. — Essence de Seiiieii Contra d'Aiiieriqiie. Origin. In the neighborhood of Baltimore the oil is distilled from the entire plant, Cheiiopodhuti amhrosioides L. var. anthehmnticum Gray.* Westminster in westei'n Maryland is the center of production. The fruits are said to owe their anthelmintic properties to the oil they contain. Upon distillation, the fruit yields 0.(5 — 1 p. c, the leaves about 0.35 p. c. of volatile oil. Pkopebties. The odor of the colorless or yellowish oil is very penetrating, offensive, camphor-like ; the taste bitter and burning. The sp. gr. of good commercial oils has been found to be 0.97; the rotatory power between — 5 and — 6°. A clear solution resulted with 10 p. of 70 p. c. alcohol. Oils with a lower sp. gr. and slight dextro rotation were not soluble in 70 p. c. alcohol and were shown to be adulterated with American turpentine oil. The data obtained from an oil distilled by Schimmel & Co. show that a lower sp. gr. and a lesser solubility alone cannot be regarded as proof of adulteration. In order to justify the conclusion that turpentine oil is present, pinene. which does not appear to occur in the pure oil, should be shown to be present. An oil distilled by Schimmel & Go. from the seed^ had a sp. gr. of 0.900; aD=— 18°55'. The oil from the leaves had a sp. gr. of 0.879 ;« and an angle of rotation of — 32° 55'. Neither of these two oils was clearly soluble in 70 p. c. alcohol. The seed of Chenopodiiim nmhrosioidea L., a closely related plant, are used in Brazil as a popular anthelmintic. According to Peckolf' they contain a volatile oil with a strong aromatic odor, bitter, burning taste, sp. gr. 0.943. 1) .Tahrb. f. prakt. Pharni., 19, ii. 71. =) Bericht vonS. & Co., Apr. 189i. p. 56. 2) Repert. f. d. Pharm., III., 7, p. 1. «) Ibid., p. .57. 3) .Jahi'b. S. prakt. Pharm., 2G, p. C,'j. 7) Pharm. Kundsehau, la, p. 89. 1) Am. Joiu-i], Pharm., 22, p. P.Oi; 2(1, p. 303. 350 SjwciaJ Pint. ~ X Oils of the Rnnuiicuhiceae. 351 The le.ives of this plant yielded upon distillation O.^.'i p. c. of a volatile oil with a repulsive eamphor-like, narcoti(; odor, reniindiuo- of triinethylaniine, and sp. gr. 0.901.1 Composition. The constituents of American wormseed oil have as yet been but little iuvestij;-ated. According to an examination conducted by Grarrigues- in 1854 the oil contains a hydrocarbon boiling at 176° (possibly limonene), and a liquid substance ('loHioO. 109. Oil from Paeonia Moutan. The rootbai'k of Paeoiiia moutan Sims. (Family lianuui-ulaceiif') is much used as a drug in Japan and China. On the inner surface as well as un surfaces made by fracture, white prismatic crystals of paeonol are found. These can be obtained by distillation with water vapor, or better by extraction with ether. The crude oil (yield 3 — 4 p. c.)-' is purified by shaking the ethereal solution with soda solution, which takes up the impurities onl,y; then combining the paeonol with sodium hydrate and regenerating it with sulphuric acid. Paeonol was first isolated by Martin and Jagi* {187H). Basing their conclusions on the elementaiy analysis of a calcium derivative, these chemists regarded it as a fatty acid closely related to caprinic acid. According to Xagai-' (1891) paeonol has an aronuitic odor, crystallizes in colorless, shining needles melting at ."J(J°, and has the composition CbHioO." It is sparingly soluble in cold water, readily in hot water, alcohol, ether, benzene, chloroform and carbon disulphide. The arjueous as well as the alcoholic solution is colored reddish-violet by ferric chloride. Ac]iueous solutions of the caustic alkalies dissolve paeonol and form well crystallizable derivatives. According to Nagai, paeonol is p-methoxy-o-hydroxyplienyl methyl ketone: C0H3. COCH3 .OH. 0CH8 = 1 : 2 : 4. When fused with potassa, or when boiled with hydriodic acid, paeonol yields resacetophenone, CeHs . COCH3 . OH : OH = 1 : 2 : 4, m. p. 142°, Acetyl paeonol, m. p. 46.5° is oxidized with permanganate to p-methoxysalicylic acid, CaHs.COOH. OH . OCH3 = 1:2:4. The oxime of paeonol ciystallizes in fine needles, the pjhenjd hydrazone in light yellow needles melting at 170°. « Taha.ra, ''' in 1891 prepared paeonol sj'uthetically by methylation of resacetophenone. 1) Bericht vim S. & Co., Apr. 1891, e) Tiemann in 1891 (Berichte, 24, p. p. 49. 2854,) found the m. p. of p\ire paeonol at 2) \m. .Journ. Pharm., 26, p. 40.5. 48°. Further derivatives of paeonol are 3) Berichte, 19, p. 1776. de.scribed : Berichte, 2.5, p)). 1284, 1306. *) Archiv d. Pharm., 21:3, p. :3.3,T. and 29, p. 17.o4. 5) Berichte, 24, p. 2847. i) Berichte, 24, p. 2439. 352 Special Part. 110. Oil of Nigella Sativa. The seeds of Nigella, sutiva L. (Ger. Sehnarzkummel) yield 0.4(3 p. c. of a volatile oil of a yellow color, whieli does not fluoresce and has an unpleasant odor. Sp. gr. 0.875: aD= + l°26'. It boils between 170—260°.! 111. Nigella Oil from Nigella Damascena. The seeds of Nigella damascena L., which are sometimes also called Schwarzkummel, yield upon distillation ^ 0.3 p. c. of an oil with a beautiful blue fluorescence, that jjossesses the agreeable odor and taste of the wild strawberry. Sp. gr. 0.895 to 0.906: aD = + l°4'. In 90 p. c. alcohol the oil is imperfectly soluble, but miscible with absolute alcohol in all proportions. The fluorescence of the oil is due to daniascenine, CioHioNO,!), which boils at 168° and melts at 27°. According to Schneider 3 it belongs to the alkaloids : with acids it forms crystallizable salt, with the chlorides of platinum, gold and mercury it forms double salts. With the general alkaloidal reagents it yields the reactions cliaracteristic of alkaloids : with iodine potassium iodide a purplish-brown precipitate ; with potas- sium bismuth iodide a brown; with potassium mercuric iodide and phospho molybdic acid white precipitates. Solutions of daniascenine containing an excess of nitric acid are colored a beautiful violet upon standing (daniascenine red). Upon heating of the nitrate, daniascenine blue results.* Pommerehue"' has recently studied daniascenine which was isolated hj extracting with dilute hydrochloric acid, making alkaline with scida and shaking out with petroleum ethei'. The blue fluorescent petroleum ether solution is then again shaken with hydron-hloric acid and the acid solution evaporated. Pommerehne sets up the formula C8H9(0CH3)2N0, based on an analysis of the platinum double salt and a methyl deter- mination. 1) Bericht von S. & Co., Apr. 189.j, p. 74. 2) Bericht von S. & Co., Oct. 1894, p. .T5. 3) Pharm. Centralh., 31, pp. 173 and Ifil. C'omp. also Inauf!;. Dissertation of the Kamo author, Erlaagen 1890. ^) The earlier reports are frequently contradictory, because the examinations -were conducted in part with the seeds of Nigella damasceDR Li., in part with those of Nigella sativa, L.— Greenish (1882), Pharm. .Tourn.. III. 12, p, 681.— Reinsch (1841), .Tahrbuch 1. prakt. Pharm., If, 4, p. 384.— FJiickiger (1854). ibid.. Ill, 2. p. ICl. 5) Archly d. Pharm., 237, p. 47.5. Oils of the ilagnolim-p.ii'. 353 112. Champaca Oil. The oil fliwtilled from the flowers of tlie champaca tree, Mkhelin chmn- j):icii L. (Family Magnoliaceae), which grows in Java and the Philippine islands, possesses decided fragrtmce, which strongly resembles that of the flowers of Acacia favnesiaua, AYilld., but also reminds of thiit of violet and ylang-ylang.i Inasmuch as the oil is very costly it can be had, if at all, in comparatively small quantities only. The rather mobile oil is of a light yellow, or reddish-yellow to brownish color. Sp. gr. 0.907— 0.935 ; aD = — 12°18' to — .'')2°. Saponi- fication number 77 (one determination). In alcohol it is difficultly soluble, for it does not even give a clear solution with 10 ]}. of 90 ]). c alcohol. As to its composition, hardly anything is known. Like yhing-yhing oil it has a rather high ester content, and like this oil contains benzoic acid (m. p. 121°) which sometimes crystallizes from the oil.- 113. Oil from Michelia Longifolia. The flowers of Michelia longifolia Bl. (Fcimily Magnoliaceae). which grows in Java, yield upon distillation a limpid, very volatile oil, the odor of which reminds of basilicum. Sp. gr. 0.883; «d ^ — 12°50'.3 114. Star Anise Oil. Oleiiiii Aiiisi Stellati. — Steruanisiil. — Essence de Badiaiie.^ The various species of Illicium are indigenous to middle and isouthern East-Asia. Japan, and the islands of the Chinese and Indian seas. On account of the similarity (jf the fruits of the diffei'ent species, the statements concerning the origin of the various commercial vai-ieties have been contradictory up to the present time. Liniie fii-st ■called the tree, which Ijelongs to the Magnoliaceae, Badanifera, anisata/' later lUicium anisatiiw.*^ A "variety cultivated in Japan, especially in 1) Guaiac oil from Bulnesia Ravmienti (see thi.s) which has recently been intro- duced into the market as champaca wood oil has nctthing in common with genuine ehampaca oil. 2) P.ericht von .S. & Co., Apr. 1882, p. 7; Apr., 1804, p. .58; Oct. 1891, p. 10; Ajir, 189T, p. 11. ••i) Bericht von .S. & Co., Apr. 1894, p. 159. ■t) In Europe, star anise was formerly known as Anis de la Chine, de la Sibcrie, Foeniculum sinense, Badian. The last name, taken from the Arabian BAdiydn for fennel, was employed by Pierre Pomet, the author of the Histoire general des drogues llivre 1, p. 48). published in 1694. and remained in use for a louji time. 5) Mat. med, e regno vegetabile, lib. 1, p. ISO. 0) Species plantarum, p. ()64. 23 354 Special Part. Oils of the Mas-noliacene. 355 the grovess of Buddhist temples, was described iu 1(390 by Kampfer.i in 1781 by Thunberg- and again in 182.") by von Siebold,-' wlio termed FiS. 65. Tonkhi Distilling Apparatus. it niicium japonkum, which term he changed to /. religiosum in 1837. Jos. Hooker the younger, sliowed in 1886 that the official and com- 1) Amoenitate.s exoticae, p. 880. 2) Flora .japoniea, p. 285. 3) Het gezag van Kampfer, Thunberg, Linnaeus en anderen, omtrent den botanisehen: oor-sprons van den steranijs des Handels. Leiden, 18.37, p. 10. — Kein, .Japan, 188(5^ vol, 2, pp. 160 and 307. 350 Sjifcial Part. mcjn star anise is not derived from tlie siieeies tei-nied 7. nnisntum hy Linne, and named tlie tree /. veruni. The volatile oil was distilled in the course of the eigliteenth century, but did not And wider application until tlie nineteenth c-entury. As to its constituents and percentage of volatile oil, star anise was examined by Neumann and Cartheuser, '^ later in 1818 by Meissner.- Peepabatios. At present, star anist^ oil is imported principally from the northwestern provinces of C-hinji and from the French colony Tonkin. In Ijoth districts it is prepared on a large scale. The distillation is conducte(.l in a primitive manner. According to English-^ and French reports the method in Tonkin is the same as in the Chinese provinces. Fig. (3(;. Chiiii'se Distilling Ajipavatiis. The still (fig. 6.0) consists of a strong, va.por-tigbt "wooden barrel or of an iron c.vlinder, the bottom of which is frequently perforated. This rpsts on an heniispbcrieal or flat iron kettle fasten<'d in a hearth of masonry and heated b.v direct ftiv. The n|i|]er part of thn barrel or cylinder is so constructed that the charging and discharging can take place from above, and that the vapors escape through a central opening and tube into the condenser situated above. This consists usnally of an earthenware jar covered by a tin kettle. The latter is filled with water, supply and exit tubes con.sisting of bamboo. The barrel or cylinder is tilled with connninuted star anise. After all joints have been se.aled, the water in the kettle below is heated. The vapors 1) Eleinenta chyniiae-inedicae, vol. 2, ji. 827. 2) Buehholz. Ta.schenb. f. Scheidekiiiistlev. u. Ajiotli. au! das .Jahi- 1.818 \ind 1819, p. 1. :') Decennial Kepnrts on tlie trade, etc., in Ctilna and Coi-ea. Statistical series No. 6, 1SS2 to 1801, )i. 6;"',). Oils of tlw .M;ignolince;ie. H57 of water ami oil eomU'iisi' on the lower surface of the henii.sidiei-ical uiiper wall of the eoudeuser and How through a tinned tube from the (condenser basin into a basin usually made of wood and lined with tin. The Chinese apparatus is not essentially different. Tlie receiver, liowever, consists of two chambers and is so arranged that the lighter oil flows into the second chamber, whereas tlie water is ])reveuted from flowing over by means of a siphon (fig. 60). In Tonkin a kind of Florentine flask is used and the ai]ueous distillnte is allowed to How back into the still. As a rule, the stills contain 3 piculs — 180 k. of .star anise. The distillation lasts about 45 hours. The yield averages o]4 k. or about 3 ]i. c. of oil, which is shipped in lead canisters of 7.5 k. Composition. Aiietliol is tlie most important ami valuable con- stituent of star anise oil. The congealing point stiows whether the oil is relatively rich in anethol ; an exact method of assay lia.s not vet been devi.sed. Inasmuch as from 80 to 00 p. e. of anethol can be obtained fiTjm good anise oil by re]jeated freezing, tlie true content may 1)6 regarded as somewhat higher. Anethol was first recognized in star ani.se oil by' Cahonrsi in 1841. who established the identity between the stearoi)tene of fennel, anise and stai- anise oils. Shortly after- ward, Persoz2 obtained anisic acid from anethol by oxidation with chromic acid. He called the acid badianic aciiL For ])roperties and derivatives of anetliol see p. 170. The remaining 10 — 20 p. c. of the oil consist of a mixture of at least five different substances. The lowest fraction 1.57 — 17."j° contains two terpenes.-^ 1) d-Pinene: b. p. l.'>7— 1(;:!° ; '/d= + 21°;50' ; m. p. of the nitrol- benzylamine 122 — 12;i°. 2) hPhellandrene : b. p. 170—175°; '/.i,= — .1°40'; m. p. of the nitrite 102°. 3) Methyl chavicol (para methoxy ahyl benzejie). the isomer of anethcjl (para methoxy propenyl benzene), has not yet been isolated in a pure form from star aui.se oil. Judging from the properties of the corresppnding fraction its presenc-e c-an not well be doubted. •<• If star anise oil is freed as far as pjossible from anethol by repeated freezing, a mobile oil is obtained which suffers striking changes when boiled with alcoholic pota.ssa (Eykman's method). The boiling point rise.s, the index of refraction is increased, and upon freezing large amounts r_)f i| Compt. rend., 12. p. 1213; Liebig's .\nnalen, H'j, p. .31«. 2| Compt. rend., 13, p. 433; JJeblg'H Aniialen, 4-J-, p. 311. 3) Bericht ron S. & I'n., Apr. 18'.l3, p. 06. i] Bericht von S. & Co., Oct. 18i).i, p. Ij. 358 Specin! Part. anethol are again depurated. This lian evidently been formed by tlie action of the potassa. on the preexisting- nieth^i cliaA'ieol. 4) Hydroquinone ethyl ether.i CoHiCOH) . OC2H,-,, bnt mere traces of wliicli are present, can only be obtained by shaking- out large amounts of star anise oil with aqueous a Ika-h. When pure it cr.ystallizes in color- less laminae of pearly lustre which melt at (j4°. •"■() Safrol is considered to be present though a satisfactory proof of its i)resence has not yet been given. Oswald 2 (1801) attributes the difference in odo7- of star anise oil from that of anise oil to safrol. Twti substances, which are found not only in star anise oil, but in every oil containing anethol are anisic aldehyde and anisic acid. They are said not to preexist in the oil but are f(U'med by oxidation due to exposure to air. The older the oil, the larger the amount of these two substances present. Phoperties. .Star anise oil is a colorless or yellowish li(iuid of great refractive ])0wer. On account of the high percentage of anethol it congeals in the cold. It has an anise-like odor; an intensely sweetish taste; sp. gr. O.OH to (1.99; rotation slightly laevogyrate, «o up to — 2°.-^ The oil f(U'ms a clear solution with three or more parts of 90 p. c. alcohol. The congealing point lies between + 14 and + 18°.* Under certain conditions, espei-ially in closed vessels and when slowly cooled, star anise oil can be cooled far below its congealing point with- out being solidified and may then remain liquid for a long time. The congealing is usually induced by some external impetus, by a particle of dust or by shaking, and takes place the nu)re readily the lower the temperature of the oil. The best way to cause a cooled oil to solidify is to drop into it a. particle of anethol or to scratch the innei- side of the dish with a, glass rod. It is noteworthy that an old oil which has been kejit for a longer ]jeriod in partly filled containers or which has been exposed to the air by I'epeated melting, gradually loses its power to congeal on account of the partial oxidiition of anethol to anisic aldehyde and anisic acid. M Bericht von S. & Co.. Oct. IS'.I.''., p. II. ■J) .\rchiv il. Phunii., 229, p. 8(i. :t I In a few instanccK Mli<;ht flextro rotation has been observed. + 1 lEecently f»ils have found their wa.v inttj the niarltet that liad a lower conj>:eaiing poiTil bnt were nnaduiterated. The properties of five of sucli oils were a.s follows: sp. lit: o.i)8S— 0.998; «„=+0°ll' to -,0°.'!2'; congealing point H SS/, to 13%°; all Hidnbie in IVj p. of 90 p. e. alcohol. These "flower oils."' as they have been designated, are not, however, obtained from the flowers of the star anise tree, l>nt from the unripe I'rnits whieh are picked to facilitate the ripening of the other fi-uits. Thr.ngh not ailulter.'ited, the.se oils cannot be regarded as the eiinivalent of the oil from the ripe rruil and sholil to 10 p. c of petroleum. Sp. gv. ('onsealinp point Solubility in 00 p. c. alcohol |i- Pure oil The same with petroleum The same with 10 ]>. c. ]ietroleum 0.986 0.978 0.970 -1-18° + 16!^° 1 ;2.2 and more. not clearly soluble in 10 jiarts of 90 p. e. alcohol. From the above data it becomes apparent that adulteration with petrcjleum is more readily recognized by the determhiation of the specific gravity and solubility than Ijy the congealing point. For this reascni an oil should be required to stand the tests of .specifie gravity and scjlubility even if it conforms with the requirements made with regard to the congealing point. 1) Eykman (1881). Mittheil. d. ileutsch. (jcaellscli. f. Xatur- iind Vdlkerkunde Ost- asienH, 28. — Uniney. Phai-m. .lourti.. Ill, 10. p. 647. — Simire, ibid., HI, 24. p. 104. — Umney, ibid.. Ill, 25, p. 947. 2) Bericht von S. & Co.. April 1897, p. 42. 3(;o S/ifcial Piwt. On tlie other hnnd, niiadiilterated oilw that are normal witli regard to is]iecifl<3 gravity and sohiljility, may l)e defertive as to anetliol content. Inasmnch as the oil is vahialile in the ratio of its anetliol ecjntent. and as the congealing i)oint rises with the latter, the congealing p(jint may be regarded as a direct measure of the quality of the oil. Deterni in ation of tlic congealing point. When taking a sample of tlie oil, care should be taken that the contents of the canister are completely melted and well nii.xed. 200 g. of oil aiT trausfprvcd to o, tiask and filtered if uecpssar.v.i Xn accui'ate tlicrniometer, indicating lialf degrees, is di)iped into the oil and this cooled by means of chopped ice or ice water. During the ])rocess of cooling shaking is to be avoided, aeither is the liquid to be .stirred with the thei'mometer in order to avoid premature congealing. .Vfter tlie oil has been cooled to about + G to 8°, crystallizatioji is induced by the addition of a particle of solid anetliol or solid star nnise oil, or by scrateliing the iinier wall of the flask with the tliei'uiometei'. During tlie solidification, the mi.Ktnre is continuously stirred in order to facilitate the jiroces.s of congealing. In the course of this operation the temperature rises rapidly. The highest point which the mercury i-eaehes is the congealiug point. The determination can lie made with less niatci-ial with the aid of Beckmann's apparatus foi- the detei'mination of molecular weights described on p. 187. In order to olitain uniform results, care should be exercised to induce crystallization at a. temperature of about ti to 8°. The melting- point of the oil would be just as serviceable as the congealing point were it not for the fact that the latter can be ascertained much more ai-curately. The congealing point of star anise ciil should not be below l."i°. The oli;ice;ie. 361 2.000 picnis or 3.000 — 4.000 eases which ai-e iilsn ship]ii'il t(i Honii-lcoiifj,- via the jiovt Pak-hoi. The Tonlciii-Cliiiiese border district lias produced aljout 400 piculs or SOO cases in recent years. This is talcen by rail and steamer to the T(.)nkiu-Chinese port Hai-jihons' wlience, favored by special duty regulations, it is shipped exclusively to Frame. (_)n account of its high anethol content, it has met with s|iecial f;iv(n- in recent yenrs and is preferred to the C'hinese oil. Total export of star anise oil during tlie last 40 years: From Pak-hoi and Lappa iMacaoJ FroDi Hai-])hons' (Tonkin ) Total 1888 1889 1890 1891 1892 1898 1894 1895 189(j 1897 976 Piciil, 810 ■' 1294 " 507 1803 '■ 862 '■ 1998 " 489 '■ 2:!69 " 1398 " 150 Picnls 200 " 2;i0 " 288 18 485 899 1126 Piculs 1010 " 1524 •■ 795 " 1808 " 802 ■' 1998 " 502 " 2.S01 1797 ■■ The price of the oil is also subject to considerable fluctuations. During the last twenty years it has varied l^etweeu .fl.80 tind -12.2.5 per pound. Since several years the congealing point .serves as basis for its valuation. The principal Hongkong and Tonkin firms are famili;ir with tlie method and have the necessary equipment. 115. Star Anise Leaf Oil. The mitives of the Pe 8e district obtain an oil by distilling the leaves and even the branches of star anise trees. The yield is :i,bout 0.75 p. c. (Himon-). In odor the oil differs slightly from that of the fruit, the odor i;)f anisic aldehyde being far more pronounced. It has a higher sp. gr. tlian the oil from the fruit, 0.987S at 15.5°; au= + l°.-^ According to UmneyS the proportion that boils above 2;iO° is quite different from that of the oil from the fruit. Star anise Iruit oil. Star aiiisp leaf oil. Below 225° 20 p. c. 10 p. c. 226—230° 65 " 60 " Above 230° 15 " 80 " i| 1 Pioill = 2 lases with a net content of 30 kilo. Pnrins the .yeai-K 1S(I7 aiul isfis the total e.xpoi-t has been valued at .If.-).-)!), 000. 0(1 and .$37."). 000. 00 respectirel.v. 2) Cheni. & Druggist, 53, ]j. 87.5. 3) Cheni. & Druggist. 54, p. 323. 302 Special Part. The anethol content is small and its cong-ealiug- point correspondingly low, for which reason it has been designated as liquid star anise oil i and aippears to be used as an adulterant and a substitute for the oil from the fruit. 116. Japanese Star Anise Oil. The oil from the leaves of Illicium religiosum tSieb. (Japanese Sliikinii), the Japanese star anise tree, which is ill-famed on account of its ]ioisonous fruits, was examined by Eykman^ in 1S81. U])on distillation of the leaves he obtained 0.44: p. c. of volatile oil. sp. gr. l.OOG at 1V>.~,°. [a]o = — 8°6'. It contains a terpene (b. ]i. 17;!— 17(3°; s]). gr. ().S.">.") ; «D^ — 22.5°) and 2.") ji. c. of a liquid anethol which yields nitrdanisic acid melting at 174°. According to a second contribution by the same autlior-^ (188.")| the shikimi leaf oil consists of eugenol, a terpene '■shikimene". (l:i. j). 170°; sp. gr. O.SGo) and ".shikiniol"' or safrol. It is noteworthy that Eyknian determined on '■shikiniol" the constitution of safrol CeH.g : 02CH2(C3H5 ). The fruits of the Japanese star anise tree also contain a volatile oiH of a disagreeable (idor. which has nothing in common with that of the true star ani.se oil. iSp. gr. 0.984; aD = — 4°.")'. 117. Winter's Bark Oil. Ai'i'ording to Arata and (ianzoneri ^' (1889). the genuine Winter's bark of Driiny.s winteri Forst. contains ().(!4 ]). c. of a dextrogyrate volatile oil. This consists principally of a hydrocarbon, "winterene'' boiling at 2(50—205°. which the authors regard as a triterpene. Probably, however, it is a sesquiterpene. 118, 119. Ylang-Ylang Oil and Cananga Oil. Oleum Anoiiae. Oleum Canangae. — Ylaiig-Ylaiigol. Canaiigaiil. — Essence de Ylaiig-Tlang. Essence de Cananga. OuKiiN AND History. Ylang-ylang oil is obtained l)y the distillation of the flowers of Ciliningn odoratn, Hooker et Thomson (Faniilv Anonneeae). Tliis«tree occurs in the Malay Archijielago and in the Philippines and is cultivated in the latter and throughout southern 1) f'heni. & DruRgiBt. ."i^. pp. 8+e, ST.j. -) Mitth. d. (leutKcli <.ieH. fiir Xatvir- \i. X'tHkei-knnilc 0.stnsicns. 23: Bt'rii-hte. 14. Krf.. |>. 17211. 3) Kec. trav. fhnn. (tes V. B.. i, p. .^2; Bericliti-, Is, ltd'., p. 2sl. •i) Beric-ht roii S. & Co., Sept. 1S85, p. 29; Ort. IS'.i;!, p. 4r,. ■■) .Tahi-esb. f. Pharin., 1SS9. p. 70. Oils of the Anoiiacene. 363 Asia. The first stateiiieiit in Europoaii literature coiirerning this tree is made by tlie English botanist John Ray (born 162iS, died 1705), who described the tree under the name Arhuv Snguisen. Eumpf, a contem- porary of Eay descril)ed and illustrated it as BovgH Cananga. Lamarck called the tree Urnvia or Unonia odovnta. Roxburgh became acquainted with the tree, wliich had been transplanted from Sumatra to the l>otanical garden in ('alcutta, in 1797. The first correct illustrations of flower and fi-uit were published by Blume in 1829. Notwith.standing the exceeding fragrance of the blossoms and the desire of the European colonial powers to find profitable commercial articles in the Mfday Archipelago, the manufacture of .ylang-ylang oil was first conducted by Gei'mans in the island of Luzon in the early sixties. The oil became known to wider circles through its exhibition at the Paris Industrial Exposition in 1878 by the Manila men.-hants Oskar Reymann and Adolf Roensch. Ylang-ylang oil is distilled in the islands of Luzon and Java. The blossoms of the trees growing in dense fore.sts are said to be less fragrant and poorer in r)il than thcjse of i-ultivated trees or trees stand- ing in clearings. In the proi/ess of distillation, the oxygenated constituents and the e.ster.s. the substances to which the fragrance of the cananga blossoms is due, pass over first ; later the sesquiterpenes predominate. In Luzon, and recently also in Java, the first part of the distillate is kept separate and brought into the nuirket as ylang-ylang oil, whereas the second part of the distillate or the entii-e oil is sold as cananga oil. On account of the delicacy of the flavor, the collection and distil- lation of the blossoms requires special knowledge and care. Foi' thi.s reason but few distillers have succeeded so far in manufacturing a uniformly good article of like qualities. COMPOSlTiox. Although the ylang-ylang oil consists principally of the lower and cananga oil of the higher fractions, the difference between tliese two oils is of a quantitative rather than a qualitative nature. The first examination of ylang-ylang oil was made by Gal i in 187;l. Upon saponification of the oil with alcoholic potassa he obtained Iten- zoic acid, thus indicating the presence of a benzoic ester. Reychler,- who later (1891) made a more cai'eful examination of both oils, also found acetic acid to be present as ester. 1) Comiit. reiiil., H\. p. 1+.S2 2) Bull. Soc. c-liim., Ill, 11, jip. W~. -""i; iind l(i4.-.: ibi to 2 volumes of '.>() ]). c. alcohol but. :is a rule, this solution l.iei-omes turliid upon the addition of more alcohol. Inasmuch as the odov is largely dependent on the ester.s present, the determination of the saponitication number (betwi^en 7.j and 120 for go had a ,sp. gr. of ().<.)74. 1) liericht vim S. & (.'o.. .Viir. Isyfi. p i;i.>. 2| Berk'ht von S. i>i Ce.. A]n\ ls9i;. p. i;7. -') .ii-ch. il. Piiiinn.. 218. ii. L'4 ; al,-io Rcyihler. lou. v\t. *) Co iiiit. rem!.. TG. |i. 14S2. ■'O Kcrlfht von .S. & C'o., Oi-t. 1n;mi. p. 47. Oils of the Anonfiivup. 865 The differeueehi existiiifi' in tlin properties of ]iure oils reiiiler ditflciilt tire detection of adulterations. To pfiss indginent on the qualitj- of yh?i n,<;'-ylang oil is. therefore, often a matter to be decided liy the j)er- fumer rather tliau by tlie chemist. Properties of Cixang-v Oil. The o(lor of ('ananjiU oil is similar to that of ybing-yhmp- oil. but not as tine. Owing to the different methocLs of preparation, the physical pjropertie.s aiv subject to con- siderable variations: sp. gr. 0.91 — 0.04; «d= — IT to — .55°. In 90 p. c. alcohol cananga oil is not completely soluble. Of 95 p. c. alcohol lYi to 2 vols, are mostly necessary, but the solution become.s turbid on the further addition (jf alcohol. However, no drops sejiarate from the resulting opalescent liquid upon standing. The saponification number is 10 — 30. In general an oil with a high saponification number may be regarded as the best, provided this is not due to the presence of cocoa nut oil. Cananga oil from dried flowers.- Dried cananga blossoms frrjm Samoa, known there as Mosoi yielded 1 p. c. of oil u]:)on distil- lation. Its odor was somewhat different from that of the oil from fresh blossom,s but had the same general character. Like ordinary' cananga oil. it contained benzoic acid and had a sp.gr. of 0.922. Adulteration-. In recent years adultei'ation with cocoa nut oil has been observed repeatedly in connection with oils coming via Amsterdam. ^ Such addition can readily Ije re(;ognized. Specific gravity and rotatory power are influenced but little, but the saponification number is con- siderably increased and the oil ceases to be soluljle in 95 p. c. alcohol. From the turbid mixture of cjil and alcohol drops of oil separate upon standing. Crjcoa nut oil can also tie recognized without difficulty liy exposing the suspected oil to the temperature of a freezing mixture of ice and .salt. Whereas a pure oil remains liquid, an oil adulterated witli larger amounts of cocoa nut oil congeals to a butter-like mass. This test can readily be cai'ried out by anyone and should nevei- be omitted. Small amounts of fat as well as other oils that do not congeal at low tempjeratures remain liehind uyion distillation with water vapor and Avill be fcjuiiil in the residue. It should be borne in mind, however, that undulterated oils also leave a resiilue of about 5 ]). c.. which amount .should be deducted in an approximate quantitative determination. 1) Bericht vou S. & Co., Oct. l.s'Jii, p. 48. 2) Bericht yon S. & Co., Oct. 1897. p. 8. 300 SpecUtl Part. 120, 121. Oils of Mace and Nutmeg. (Uenni Macidis. Oleum Nucis Moschati.— Macisiil. Miiskatnnssi)!.— Essence de Macis. Essence de Miiscade. Ork^ln and Histokt. The nutmfo- tivp, Mvi-i.stiai thigriins Hout- tliuyii (M. offiemalis L., .1/. mosehata Thniiberg). \yhicli belongs to the_ family M,vrifitic;ice;iP and -wbieh attains a height of 20 meters, is in- digenous to the Molucca, Banda and Smida ishinds. It ha.s been cnltivated extensively in these islands and also in other countries. The distilled oils of nutmeg and mace were well known to the authors of the "Destillirbiieher" al)Out the middle of the sixteenth (putury and later Cordusi. Ryffs, Gesuer^, Porta^^, Winther^ and others repeatedly mention the oils. Botli oils are first mentioned in the apothecaries' price ordinances of Berlin of 1574, those of Frankfurt and Worms of l."S2, and in the 15H9 edition of the Dispensatorium Xorieum. These oils were first examined l)y Neumann, •' (1749). Valeutini''' (171!)j, and Bonastre^ (1824). Tpon distillation nutmegs yield iS — 1~) p. c, mace 4 — 15 p. c. volatile oil. Properties of Oil of M.we. It is colorless or yellowish, liecoming' reddisli-yellow with time. It has a pleasant though strong mace odor which with age becomes unpleasant and terel.iinthinate. The taste is mild attirst, then pungent, aromatic. As a rule the specific gravity cif oil of mace is somewhat higher than that of oil of nutmeg and varies between (».«9() and ().1):!0; «D = + Ht to +20°. The oil is clearly soluble in ^! parts of 90 p. i-. alcohol. Properties of Oil op Nutmeu. This is a mobile, colorless liquid which, owing to the absorption of oxygen, becomes viscid with age, ha.s a cliaracteristic nutmeg odor and a. s])icy taste. According to the nature of the crude matprial. the sp. gr. of the distillate varies between ().8i;5 and 0.920; «„= + 14 t(. + 2S°. The oil is i-learly soluble in :') parts of 90 ]>. c. alcohol. \\'hen distilled, about <\0 ]i. c. pass over below 180°. When evaporated, a small amount of a fatty sub- stani-e. consisting principally of myristic acid, remains behind. Oil of nntmeg clearly resenit>les oil of mace in all of its ])roiiertie.s and is scarcely distinguishal)le from the latter. i| .Viinotatione.s. etc., De ui-tifi. extr. lili.. fol., 226. -) Neu gross Destillirbuch. Kd. I-'rankf.-a.-M.. t'ol. Isl. ■■!| EiTi Uiistlichei- Schatz, etc., ii. 215. *) Magiae lUitiiraliH. Lib. rie dest.. par.s 1, ]>. ;!7S. ") Ciiiintheri, Andernacei cle niedicina veteri et nova. I'.a.'silae l."i71. \i\i. I'.SO — BSo, ''} Cliyniin, rnedica. vol. 2, part -S, p. 4.37. 'I -MaciK ynlgo ami perperara, JMuskatenbUinie dicta. Dl.'ssertatio. Oiessen 1719. >^) Troiiiiasdorffs X. .lourn. der Pliai-tii., 8, II. p. 281. Oils of tlie Mjristicaceae. 367 Composition. On aceouiit of the great siniilarity between the two oils, frequently no commercial distinction is made. As a result, the true origin of tlie A'arious oils that have been examined is not ascertainable. For this reason it will be expedient to discuss the composition of both at the same time. This can be (lone without hesitation because so far no ipialitative difference has been observed. i Quantitatively tliev vary in so far as oil of nutmeg generally contains more terpenes than oil of mace. Although numerous older examinations are recorded. ^ individual constituents were but recently deflnitel,y characterized and determined. However, thei'e are still a nmuber (jf problems which demand further investigation. The following constituents have thus far been found : 1. Pinene. This terpene was found l)y Wallach-^ in the lowest boiling fraction of the oil (pinene nitrolbeuzylamine, m. p. 123°). It is ]iresent as an almost inactive mixture of dextro- and laevogyrate pinene. As early as l.S(j2 Sehacht liad isolated pinene, his "macene" and prepared from it the solid hydrochloride. 2. Dijjent ene.* This is jiresent in fraction 175 — l.S()° and has been identified as tetrabrDnude.-'' y. Myristicol. The contradictory statements concerning this substance make a revision very desirable. According to Gladstone, myri.sticol has the composition (']oHi40, boils at 224°, has the sp. gr. 0.9466 and a i-otator^- power of +31°. Wright gives the boiling point a.s 212° and considers the formula GioHinO to be correct. This formula at least ex]ilains tlie foi-mation of cymene liy the action of zinc chloride or phosphorus pentachloride on myristicol. Distilled under a pressure of 10 mm., myristicol is found in fraction 71) — 144° (about 15 p. c.) of the oil. .SI), gr. 0.913 (Senindpr-"'). 1) KoUer pronounces both nils iileiitical (N'. .rahrb. Pharni , 2y, p. 13G: .Jahresli. f. <'hem., 18H4, p, 5.36), -) .John (IS21), r'heniische Schriften, 6, p. 61. Abstr. in .Jonrn. f. Chem. u. Phys. von Schweisger n. Meinecke, .33, p. 2r>0. — JIiiMer (lS3tl), .Jonrn. 1'. pralit. Chem.. 17, I>. 102, and Liebig's Annalen, 81, p. 71. — Sehacht (1862) Archiv a. Pharni., 162, li 10(5. — Cloez llS6i). Compt. i-eiid., ."8, p. 133. — Oladstone (1872), Jonrn. Chem. Soe., 2-,, p. 1. Ab.str. in .Jahresb. f. f'heni., 1872. p, 816. — Wright (1873), .Joiirn, rlieni. Soc, 26, p. ,')4r). Abstr. in .Jahresb. f. Chem.. 1873, p. 369. — Pharni. Joiu-n., Ill, 4, p. 311. 3) Liebig's Annalen, 227, p. 288; 2.52, p. 10,5. *) The so-called myiisticene of Gladstone, like the terpene (b. p. 16.5°) of Cloez, was a ini.\tnre of dipentene and jiinene. AVright's statement that oil of mace contains cviiiene is open to qnestion inasmuch as he used concentrated sulphuric acid in order to identify it. This reagent, however, is not permissible when terpenes are present. Semmler could not find cymene in the oil. .-.) Berichte, 23, p. 1808; 24, p. 3818. :ifi,s Spfcial Part. 4. Myristicin.^ CvjUn^ )■'.■'- Aftw trentmeiit with metallii; sodium, tlip liifi-hfst boiling- fraetion (b. ]i. 142— li!*"^ niidfr Hi mm. pressure) contains a suljstanee that melts at :',(f. has a sjj. gi'. of ^.l'li)'[ at 2.")-. au intense odor of mace and has been termed myristii-in. Aci-ordiny to iSemmler it is oxymetiiyl oxymethylene butylene benzene. '\\'lietl]pr tlie position of the side eliains is as indicated in the fii-st or second formula has not yet been ascertained. Accordiug to a ])rivate communication by Professor Semnder. more recent observations seem to agree with those made in the lalioratories of Schimmel & (,'o., viz. that the oil originally I'ontains a phenyl ethei- which undergoes modifications in the processes tc) which tlie oil is sub- mitted during its examination. Tlie fact tliat the fraction which after the treatment with so(]ium yields jiiyristii-in, in its original state does not solidify when exposed to a freezing mi.xture," and the coefficient of refraction being much less liefore than after the treatment, renders it highly probable that the OiHT-group changes its position under the influence of sodium. The same cliange evidently takes place liere that eugenol undergoes when i-onverted into isoeugenol. of safrol into isosafrol, of methyl chavicol into anethol. Should tliis prove to be the case, the solid substance slmuld pro]ierly Tje termed isomyristicin. whereas the name myristiiin should lif iiuide to apply to tlimetiine« crvHtullizi-s frnni old oils and « liich. iis has lieeii sliuwii by Fluikisei- in 187+ (Phiirni. .lonrn., Ill, ."i. \i. l:i(-,i, conKiHtM of niyristie aeid. -I U'rii^ht asHUined the fornmlii Cj,,n,.j(^^, for Tn\-|-iMti'-ii]. ^'1 Ob8er\'ation in the laboratorieK of Scluniniel ^ Co. *} Seninder, loc. eit. Oils of the Moniniiaceae. 369 oil. the odor of which is cvmeiif-lil^f and reminds slightly of peppermint. 8p. gr. 0.91.J to 0.94.5; slightly laevogyrate, an— — l°-i:()': it boils between 17.> and 2.50° and produees a green color with ferric chloride. ^ The oil contains terpenes and oxygenated substances that have not yet been closer examined (HanausekS). 123. Atherosperma Oil. The bark of Athero.vpermn moselmta Lal>illard. {Moniniiaceae) yields upon distillation 1 p. c. of volatile oil ( Maiden °|. On account of its sassafra.s-like odor the tree is also called Victorian sassafras. According to Gladstone,-'' the oil has a yellowish-brown color and a sp. gr. of 1.0886 at 20°. It is slightly dextrogyrate. + 7" in n 10 inch tube. It liiegins to distill at 221° and passes over almost completely at 224:°. IS^?. Oil of Citriosma Oligandra. On account of its unpleasant odor, the tree O'frio.s/yj;; oligandra -In]., i Monimiaceae) is known in Brazil as Xegra Mina, Catinga de negra. or Catingueira. The leaves upon distillatir)n yield 0.51: p. <:. of volatile oil wliich is of a light yellow color with greenish fluorescence and an oilor that faintly reminds of bergamot. Sp. gr. 0.899 (PeckoltSj. 135. Oil of Citriosma Cujabana. Citriosma cujabana Hart, is known in Brazil as Linioeiro domato, and L. bravo or wihi lemon tree. The fresh leaves yield n.l8 p. c. the fresh twigs <).<)7 and the fresh bark 0.22 p. c. of volatile oil. The oil is a mobile liqtiid. sp. gr. 0.891. tlip odor of which resembles that of a mixture of bergiimot and lemon oils (Peckolt S). 126. Oil of Citriosma Apiosyce. Citriosma apiosyce Mart, is known in Brazil as Limoeiro bravo. Cidreira melisse, or Cafe bravo, wild coffee tree. All jjarts of the shrub, especially the leaves and unripe fruits, have a strong odor of melissa (lemon balm) or lemon. From the fresh leaves Peckolt obtained 0.11 p. c, from the twigs 0.06 p. c. of volatile oil.° 1} Bericht von S. & Co.. .\pr. 1888, p. 13- — Claude Verne. Etude .lur le Boldo. Thdse presentee et soutenue k I'Ecole Superieure de Pharmacie de Paris. Paris 1874. According to Pharm. .Tourn., Ill, 5, p. ^O."!. 2) .Jahresb. f. Pharm., 1877. p. 79. 3) Useful native plants of Australia, p. 2.j4. i) .Journ. Chem. Soc, 1864, 17. p. ."i. Kef. .tahresb. f. Them., 18G.3, p. r,io. — Chem. New.s, 1871, 24, p. 2S,S. Sj Berichte d. dentsch. pharm. (jes.. G, p. '.i.3. 24 370 Specinl Pnrt. 127. Oil of Paracoto Bark. Pararoto bark is brouglit into eominerce fi-(nn Bcilivin and derived from an unknown species of the Monimiitcene.'^ Tlie oil wliirh is obtained as a byproduct in the preparation of cotoin, was first examined hj Jol)st and Hesse- in 1ST9, later (1H92) 1)y Wallach and Rheindorff.3 Properties. Paracoto bark oil is a moliile, (colorless liquid of a very pleas:int odor. Sp. ,ur. (l.027"i; "u = — 2.12°.- CoMPOsiTiON. 1. A(.'cording to .lobst and Hesse, fraction 1G()° (sp. ixv. 0.8727; ['/.]ri = + 9.:U°) is a hydrocarbon C12H18 named «-paracotene by them. 2. Fraction 170—172° (.sp. ,nr. O.N84(i; ['/.]d = — 0.lder trees camphor is found in a crystalline condition in cavities of the tiamk. Principally, however, it is found dissolved in a volatile oil that permeates the entire tree. This oil occurs most abundantly in the roots, less abundantly in the trunk and still less in the branches and leaves. The amount of oil also seems to vary with the height of the trunk, diminishing with increasing height. With the age of the tree and the density of the wood, the amount of oil, how- ever, inci'eases. The ratio of solid camiihor and camphcn- oil seems to vary with the age of the tree, the season and the temperature. Tlie younger trees yield upon distillation more camphor oil and less camphor. The same is true with increasing temperature, so that the yield of oil is greater in summer than in winter. In recent times, and more particularly sini/e the acquisition of Formosa. Japan has become the principal proilucer of camphor and camphor oil. The method of preparation is generally as follows -.^ On the slope of a hill iienr a supply of water a sufficient area is leveled. On this a stove is erected with crude stones having a hpiglit of about 1 in. 1) Weil. Ge8chichte der Chalifen. jVtannheim, 1846, p. 75. 2 1 D. E. Grasemann, Der f'ampherbauiii. Mittheilungen der Deiitschen Gesellschaft fiir Natur- u, Volkerkunde Ostasiens. Tokio, 1895, 6, pp. 277 — .328. 372 Special Part. and an inner diameter of 0.70 m. Tlie opening for the fuel supply is rather small, 0.40x0.30, and covered with a roof. ()n this the di,stilled chips (flg. 67 h) are dried to be used later as fuel. A flat kettle provided with a strong, perforated, wooden cover is placed on top of the stove (fig. dH b) and over this a barrel or tub. This has the shape of a truncated cone (flg. 67 c) and is 1.15 ni. high; the upper diameter being 0.30 m. the lower 0.87 m. The cover to the kettle fits as a bottom to the tub. To one side, just over the cover of the kettle there is a rectangular opening in the tub 0.30 m. high and 0.2.5 m. wide (fig. 68 e). The head-piece of the barrel or tub consists of a Fig. (>8. rcimovable, well fitting cover provided with an opening that can be clo.sed by a plug. The tub is coated with a layer of clay 0.15 m. thick and held together by a network of bamboo. Near the top a baniboo tube 2 ni. long is carefully inserted, which leads to a condenser farther up on the slope. This condenser. Oils of tlip Lanraceae. 373 in its simplest form (fig. 69), consists of two boxes of wliicli the upper serves for the condensation of the camplior and the lower for the reception of the cooling- water. The upper box is 1.60 m. long, 0.90 in. broad and 0.42 m. high. The inverted bottom is covered with water, the aides projecting 10 — 12 cm. over the bottom. The camphor vapors enter the box over the surface of the water. To pass them through the water has not proved suc- cessful. B.y means of partitions 18.5 cm. apart the condenser is divided into sections. These partitions are each provided with a rectangular opening at the top, one in the right corner, tlie other in the left corner, etc , so that the camphor vapors must pur.sue a circuitous path. From the last chamber the vapors can pass out through a bamboo tube slightl.v plugged with straw. A lateral tube allows the water to flow from the bottom (= cover) of the upper box into the lower. The upper box inverted with its opening downward is placed into tlie lower box which is somewhat longer and wider but not as high, so that the water in the latter rises to about one-half of the height of the former on all sides. A lateral exit tube allows the excess of water to flow out. In order to avoid a rapid heating of the water in the condenser, this is protected by a roof made of boards. Frequentl.v a third smaller box, 0.80 ra. long, O.-'il- m. broad and 0.2.o m. high, is placed over the upper one. This box is likewise open on the lower side, standing in water 10 cm. deep. The sides hkewise project over the top so that a la.yer of water 5 em. high remains on it. The vapors from the last chamber of the larger condenser pass through a tube (fig. 68 h) into this smaller box where more camphor is condensed. This small upper condenser is provided with a small exit tube for the vapors. The following utensils are used in connection with this apparatus: a wooden shovel of the shape of a spoon-oar for shoveling the distilled chips into the fire place; also an iron poker. In order to protect the stove and tub a roof of straw and reed is constructed, also a wall of straw matting to the wind- ward (valley) to protect against draft and rain. The production of camphor is conducted as follows. After the kettle has been filled with water, the chips are introduced through the upper opening into the tub, and all cracks and crevices carefull.y luted so that the vapors cannot escape. Ordy a moderate fire is maintained. In the course of the distillation the kettle is frequently refilled through the opening c (fig. 68). The vapors pass through the perforation into the tub (fig. 68 d) and convey the camphor vapors from the heated chips through the bamboo tube (fig. 68 /') into the condenser where they are deposited. In the earl.v part of the distillation, camphor oil only is found in the condenser, later also solid camphor. Most of the camphor condenses behind the 3rd, 4th and ."Jth chamber of the seven-part condenser. The tub will hold 112. .5 k. of chips, a Fig. 69. 374 S/ifcial I':irt. ((uautity that can be distilled in 24 lionrs. The exliansted ohi])H are i-emoved li-om the lateral opening (tig. 68 e). Every week the condenser is opened and tlie cani|.ihov and camphor oil contained therein removed. On tlie surface of the water in thn i^ondenser there eollect.s a granular crystalline mass i-eseinbling a juixture of snow and ice, whii^li in the first few chambers is mixed with cam]ihor oil and is colored yellow. < In the walls of the condensing chanibei-s the ]]Ui-e, ^vhite ci'.vstalline camphor is depo.sited. The yellowish or brownisli-black canijihor oil Hoats i>n the surface where it mixes with the granular camphor. Properties. Normal eanipli(.)r oil. i. e. the oil with nil coiistitnents as it is obtained liy the distillation of the camphor wood, is a semi-siilid mass, or a liquid mixed with campliDr. Usually, however, the jiroduet which remains after the camphor has been renn)ved by filtration and expression is known as camphor oil. This was the oil tliat came into the market alxjut the middle of tlie eighties. It still contained large quantities of (■amphor which could be obtained by fractionation and cooling. At ]iresent this operation appears to be carried out in .Ja]inn as well, for the oil now found in the market is ahnost free from i-amijhor. Distinction is made between two kinds of oil which ciften vary largely in their composition. The measure of their value is their specific- gravity. 1. White (Jamphoi- Oil. This consists cif the lowest lioiling fractions and contains terpenes ahnost exclusively, also some cineol. Sp. gr. up to about 0.800. 2. Black Camphor Oil. It is that ]iortion of the oil that boils higher than camphor and contains safrol, eugenol and sesquiterpenes. Sp.gr. mostly from O.flOO up to over l.oon. The normal oil. as well as the individual fractions, is dextro- gyrate. All frac-tions have the odor of camphor. In the so-called black oils, however, this oilor becomes subordinate to that of safrol. The oil from the ro(3ts and leaves is like that obtained from the wood. (Jam])hor roots i .yielded upon distillation 4 p. c. of an oil that was partly solid :it ordinary temperature. AYhen eonqdetely liquified its sp. gr. at 45° was O.O.'T. The liquid portion of the oil boiled between 165 — 270° and possessed the properties of ordinary camphor oil. An oil obtained from dry leaves i (yield l.N p. e. ) also I'outained solid camphor. The liquid portion lioiled between 170 — 27. c. of camphor, by far more than did the first oil. After the camphor had been removed, the oil had a sp. jiT. of 0.9814; «i, = + 27"^. Composition-, ("amphor oil is an exceedin.i;iy ci>niplex mixture of hydrocarbons and oxyg-enated substances, which belon-:- to a large number of classes of chemical compounds. Aldeh.vdes are represented by acet-aldehyde : the ketones bv camphur: the alcoliols by terpineol; the phenols and the phenol etliers \)\ eugenol and safrol ; the oxides by cineol; the terpenes by pinene, phellandrene and dipentene ; and tinalh^ the sesquiterpenes by cadinene. Arranged according to their biiiling points, they ma.v be enumerated in the following order : 1. Acet-aldehyde. CHsCIK.). This sub.stanee. whicli is possibly found in all oils t(j the extent of mei-e traces, makes its presence known wdien large quantities of oils are rectified. In part it is removed with the aqueous distillate, in pai't it is also found in the low-est terpene fractions. 2. Dextro-pinene.i CioHki, has been found in the fraction l»oil- ing below 16n° and was identified bv means of its nitrosochloride and conversion intin)arali(in uiid pai'kiiiK of Ce.ylon fnninmon is desoribert in detail in A- Tseiiiroli's [ndische Heil- iind Xii tzptlaazen, p. .SG. Oils of the Lauriiceiie. 379 The yield of volatile oil from cassia ami cinnamon barks was deter- mined by the following observers: (t. W. Wedel in 1707; Fr, Cartlieuser, C. Neumann and Ph. F. Gmelin in 170:3; J. F. A. Goettling- about 1803; by Dehne about the same time; aJso by Buchholz in 1813. Phopebties. The oil is a light yellow liquid wliich has the aoreeable- tine delicate odor of the ('eylon ciunamoi}, ami a spicy, sweet, burning- taste. The sp. gr. lies between 1.021 and l.OlO; oirtically it is slightly laevogyrate. '/D = up to —1°. Tlie oil is clearly soluble in 2 parts of 7t) p. c. alcohol. It contains between (J." — 7."> p. c. of cinnamic aldehyde. CoMPOSiTiox. Blaucheti in 1833 (observed that in the distillation of Ceylon cinnamon two oils separate in the receiver, one being lighter than water, the other heavier, whereas Chinese ilnnamon jdelded only the heavy oil. The older diemists, however, concerned themselves only with the heavy oil. Dumas and Peligot^iu 1831 ascertained, that like the oil of ca.ssia, the heavj' oil of the (Jeylon cinnamon consisted principally of cinnamic aldehyde. That the heavy oil of the Ceylon cinnamon contains eugenol as well was ob.served later. The amount of eugenol in the oil from the liark is but 1—8 p. c, much less than in the leaf oil. Of the constituents of the light oil but one is known, viz. phellan- drene. wliich has been isolated from the fraction boiling about 175° and has been identified bj' the nitrite'* melting at 102°. The substance to which the characteristic odor of the (Jeylon cinnamon oil is due is not yet known. Adultekation and Examln'ation. tteylon cinnamon oil is frerjuently adulterated with the mudi clieaper oil from the leaves. None of the oils from Ceylon ajjpear to be pure bark oils, for all of the oils froin this source examined thus far contained considerable quantities of leaf oil. Whether the two oils are mixed, or whether the leaves have been distilled with the bark, naturally cannot be decided. Inasmuch as the addition of leaf oil increases the eugenol content and diminishes that of the cinnamic- aldehyde, its recognition is not difHcult. All that is necessary is to iletermine with approximate quanti- tativeness the amount of both substan(/es present. After the deter- mination of the specific gravity, which is increased hj the addition of larger amounts of leaf oil, the aldehyde content is determined aceording 1) Liebig's Annalen, 7, p. 168. 2) Ann. de Chini. et Pliyw., 57, p. H0."» : Liebiff'n Annalen, 14, p. .50. 3) Bericht von S. & r:(i., Oct. Is',i2, p. 47. 380 fipecwl Part. to the method deycribed under cassia oil on ]). 890. If the aldehyde content is less than 65 p. c. or more than 75 p. c, the oil is suspicious. If the oil contains less than 65 p. c. of aldehyde, the amount of euji'enol in the non-aldehyde portion is detei-mined according to one fif several ways. The most accurate results are obtained according to the somewhat complex method of Thorns, ^ the eugenol being- convei-ted into benzoyl eugenol and weighed. (Coinp. under oil of cloves.) Unniey^ has suggested to sliake the oil with 10 p. c. potassa solution and to i.letermine the eugenol content from the diminution in the volume of the oil. Inasmuch, however, as the strong potassa solution dissolves appreciable amounts of non-phenol constituents, the results are inaccurate and about 10 p. c. higher than those obtained according to Thoms' method. The error can be reduced by using a 5 p. c. potassa solution. For ordinary purposes at least, this method can be considered of sutH(;ient accuracy to ascertain whether an oil is pure ov adulterated. Adulteration may be a»ssumed if the eugenol content rjf the original oil exceeds 10 p. c. The extent to which the adulteration with leaf oil is carried on becomes appai-ent from the r-esult of examinations published l)y Umney^ and Schimmel & Co.^ Every one of the seven oils was strongly adulter- ated with leaf oil, three containing at least 8(> p. c, the other four not less than 50 p. c. The four last mentioned oils had the follcjwing prijpertie.s : Percentage of cinnamic aklehyde 29 p. C. 2« " 29 " 24 " The following reaction enables the qualitative distinc-ti(.in between the bark and leaf oils: 2 A drop ol' genuine einnanion oil dissolved in ."i drops of alcohol jirodiiees a |)ale gi-een color with ferric chloride, wliereas leaf oil and oil adulterated there- with produce a deep bine color. The cinnamon oils adulterated with cassia oil have a higher specific gravity and, as a rule, also a higher cinnaiaic aldehyde content. Oils with more than 75 p. c. aldehyde, if not .suspicious, are of inferior value. Whei-eas the cinnamic aldehyde content is the critericni of value of the cassia, oil. this is not the case with the cinnamon oil, for in the latter Sp. sr. a-a 1) 1.039 — 0°5.o' 2) 1.010 — ()°2S' 3) 1.041 — 0°5T' i) 1.019 — 0°22' Pereentap:e uf Cusenol (HCcordinj; to Tin nils) 11.9 p. c. 39.1 ■' 17.7 " 1.5.7 ■' i| Berichte der pharni. Ges., 1, p. 279. 3) Berioht von S. & Co.. (Jct. l,Stl5. p. 48. 2) T'harrn. .Jouni.. Ill, 2.", p. 949. Oils of the Laiiriieeae. 381 the non-aldehyde constituents are the mf)re vahiable as is sliown by the fact that the cinnamon oil with the smaller aldehyde content commands several times the price of the cassia oil. 130. Oil of Cinnamon Leaves. Oleum Folioriiiii Chinaniomi. — Ziiiimtblatteriil.— Essence de Feuilles de Caniielle de Cejiaii. For a time the oil from the leaves of the genuine cinnamon, Ciuna- moinum zeylnnieum Brejnie, was designated commercially as cinnamon root oil. After Schimmel & Co. had shown in 1802 that an oil, distilled by themselves from (Vylon cinnamon leaves (yield 1.8 p. c.) corresponded in all its properties with the so-called root oil, the erroneous designation could no longer be retained. Two oils, which corresponded in every resjiect with the home distillate and which were c(jrrectly designated as cinnamon leaf oil, had previously been obtained from the tSeychelles and from the botanical garden in Buitenzorg, Java.^ The oil formerly exported as cinnamon leaf oil was a thick, viscous oil of the consi.stenc.y of West Indian sandalwood oil. It has since dis- appeared from commerce a.iicl nothing definite is known as to its origin. Properties. Cinnamon leaf oil is of a light color, rather mobile, and has the odor of cloves and cinnamon. S]). gr. 1.044 — 1.065 ; an = — 0°.')' to +1°18'. Witli 8 parts of 70 p. c. alcohol it forms a clear solution, whi('h, howevei', sometimes becomes turliid upon the further addition of alcohol. Composition. Stenhouse^ (1855) found large amounts (70—90 p. c.) of eugenol in cinnamon leaf oil. Schaer^ (1882) later confirmed this report. In the <:iil distilled by themselves, Schimmel & Co. found cinnaraic aldehyde (0.1 p. c. ). Weber* made a detailed examination of two different oils. The first, obtained from the Seychelles, had a sp. gr. of 1.0552 at 18.5° and contained eugenol (benzoyl eugenol, m. p. 69—70°), cinnamic aldehyde (phenyl hydrazone, m. p. 1(57°), and terpenes that were not identified. The other, still purchased by Schimmel & Co. under the erroneous name of cinnamon root oil, was also leaf oil. Its sp. gr. was 1.041 at 19°. It varied somewhat in its (.'omposition from the preceding. Weber found eugenol, safrol (piperonylic acid, m. p. 22(j to 227°), terpenes and benzaldehyde (phenyl hydrazone, m. p. 150—151°), but no cinnamic aldehvde. 1) Bericht von S. & Co., ,\pr. 1S!I2, p. 3) Archiv d. Pharm., 220, p. 492. 45; Oct. 1892, p. 47. *' Archlv d. Pharm., 231), p. 2.32. 2) Liebig'e Annalen, 0.^», p. 10.3. 3S2 SpfcinJ Part. iStenhouse had found benzoic ,ii-id wliii-li is probably combined with an alcohol. Later investdgators do not mention tliis constituent. Whether the lienzaldehyde found by Weber is an original constituent of the oil or an oxidation product of the cinnamic aldehyde, remains undecided. 131. Oil of Cinnamon Root. The oil of cinnamon root is an almost colorless li(|uid with a strong odoi- of ciiniphor. Even at ordinary temperature a part of the camphor. i whi(_'h is identical with the ordinary laurus c-amphor, separates out. Other constituents are cinnamic aldehyde and a hydrocarbon (Holmes, 3 ],S9(I). That the roots contain camphor has long loeen known. It was mentioned by Trommsdorff.s also by Dumas and Peligot* (1835). Cinniinioninm zeyhinh-nm affi:)rds an interesting illustration of a plant, the root, leaves and bark of which afford oils of totally different (■r)mposition. In the root oil Ave find camphor as characteristic consti- tuent, in the leaf oil eugenol ]n'edominates and in the liark oil cinnamic aldehyde. 132. Oil of Cassia. Oleum Ciimamoini Cassiae. — Cassiaiil, Chinesisclies Zimtol, Ziiiitbliithenol. — Essence de Caniielle de Chine. Origin and Prep.\ration. Although the plant which yields the oil of cassia, the Cinnninnwum aissin BL, has been known for a long time, considerable uncertainty existed as to the part of the plant fi-om which the oil was obtained. It was supposed, by way of illustration, that the nnri])e fruits, the Florea cas.sine of commei'ce, were the source of the oil which for this reason was called "Zimtbliitheuol." As early as l.S81,-5 however, it became known that near In-lin, north tif Pakdioi, the leaves of the cassia bush were distilled for oil. The oil was, however, rejiorted as being thickei-, darker and less fragrant than the cassia oil. H. Schroeter,'* in the description of his travels through the cassia district in 1886, also mentions the production of oil from leaves. It was sup- posed, however, that the leaves yielded but a small amount of an inferior oil. In order to ascertain the properties of the leaf oil, Schimmel I.V: Co. secured, with the aid of Melchers & Co. of Canton, not only the leaves, l.)ut all pa.rts oi the cassia shrub that might come into consider- i| Bericht vol) S. & Cii., Oct. 18!I2, II, +6. S) DeutscheH IlaiidclK-.irfhiv, Sept. 2, 2| Pharm. .lourn., Ill, 20, p. 74'.l. ISSl. p. 2G2. 3 1 Hanilbucli der Pharmacie, p. 66(j. C| Bericht iibei- eine Keise nach Kwang- 4 1 Liebig's .Amialen, \i, p. no. si. Itu Herbst ISSG untcTnoTuinen. Oils of tlie Lauraceae. 383 atioH in tlie distillation of the oil.' Upon distillation, the bark, flower.s, flower stalks, twiji's and leaves yielded oils that were similar in proper- ties and aldehvde content. Inasmuch as the bark, the flowers and flower-parts are exchided on account of theii- high price, the leaves and branches alone can come into consideration as tar as the production of the commercial oil is concerned. As a, matter of fact, the leaves- only, with possibly some Avaste from the bark, are used for distillation. FiR. Cas.sia Oil Distillation in China, Thi.s was definitely ascertained by 0, Struckmeyer, who made a trip through the Cassia district in 1895 at the request of Wiemssen of Hongkong.- The distillation is conducted in the valleys of the provinces Kwang-si and Kwang-tung at points wliere a sufficient water supply can be had. I) Bericht von S. & Co., Oct. 1.S92, p. IL 2) Ibidem, Oct. 1896, p. 11. 38-t Specwl Part. The apparatus in uspi (fig. 70) consists of a brick oven with an iron i)an let into the masonry. On this rests a wooden cylinder lined on the inside with sheet-iron and oi>en above. After tlie cylinder has been charged with leaves and half filled with water, tlie opening- is closed with a peculiar shaped helmet of sheet-ircjn. The joint is sealed with wet cloths pressed between. The helmet has a groove on the inner side into which the condensed vapors flow and thence through a tube into the receivers. The receivers ai-e arranged cascade- like and in them is deposited the heavy oil. The water is useil for the next distillation. Cassia oil is shipped iu lead canisters with a capacity of 7.5 k., of which 4 are packed in a case. The interstices are filled with tlie glumes of ric-e. The form and color of the labels on the canisters have long remained unchanged. History. The lii.storv of cassia oil will be found with tliat of Ceylon cinnamon on p. 378. Properties, t'liincse cinnamon oil or cassia oil, when pure, is a mobile liquid, yellowish to tirownish in c-oloi-, and strongly refractive. Its odor is cinnamon-like, the taste Ijurning and intensely sweet, with- out the unpleasant, grating after-taste that is perceptil)]e iu oils adulter- ated witli rosin. Sp. gr. l.O.'i.") — 1.0(5.5. Inasmuch as the specitic gravity of the cinuamic aldehyde and the other constituents of the oil is almost the same, differences in tlie aldehyde content are not revealed by changes in the specific gravity. Cassia oil is opti<-ally inactive ov has but a slight rotatory power either to the right or to the left. It is readily soluble in 1 — 2 p. of 8t> p. c. alcohol. Its Ijehavior toward 70 p. c. alcohol varies in so far as most oils yield clear solutions with 8 parts of tlie solvent, whereas some otherwise good oils produce turbid, opalescent solutions. This peculiar behavior is possibly traceable to zinc cinnamate which is frecpiently present in the oil. The oil boils with partial decomposition between 240—260°; acetic acid is split off. and a viscid residue of (J— 8 p. c. remains. For further details see under Examination. If four drops of cassia, oil. well cooled with ice water, are mixed with a like amount of nitric acid, they unite forming a, crystalline mass. This reaction, wliii-h is mentioned in the German Pliarmaco]ioeia as a reaction of identity, depends on the union of the nitric acid witli the cinnaniic aldehyde to an unstable addition product, which is readily split up into its component parts by water. The reaction cannot be used as a. test of jiurity for even strongly adulterated oils will ]-irodn(/e crystals. In order to carry out the reaction, the oil must be well cooled. 1) lierifht voii S. & Co., Ajir. ISiC!, p. 11; Oct. ISDG, p. m. OjIk of the Laur.nceae. 385 for if the heat of the reaction becomes too great, ouly oil}' products result. The principal constituent of the oil, which supplies a criterion for its valuation, is the cinnamic aldehyde. A good oil contains as much as T-j — 90 p. c. Composition. The principal constituent of cassia oil as well as of cinnamon oil is the cinnamic aldehj'de. The differences in the two oils due to the accompanying constituents were known to the chemists who investigated the Chinese and Ceylon oils during the first half of this century. Blanchefi (1833) e. g. calls attention to the fact that cassia oil has a much more pungent odor than the Ceylon cinnamon oil. Dumas and Peligot^ (1834) also point out differences in the oils. With oils distilled by themselves they came to the conclusion that the cinnamic acid, obtained by the oxidation of the oil, stood in the same relation to the cinnamon oil or cinnamic aldehyde, as benzoic acid does ^ to bitter almond oil or benz-aldehyde. In other words they recognized that cinnamon oil consists essentially of cinnamic aldehyde. The same investigators discovered the interesting, though unstable substance CaHsO . NOsH, which results upon the addition of nitric acid to cinnamic aldehyde in the cold, and which is remarkable on account of its tendency to crystallize. Of other investigations of the same period, those of Mulder s (1840) and of Bertagnini* (1853) may be mentioned. Bertagnini investigated the compounds resulting b.y the action of the acid alkali sulphites upon the aldehyde, the composition of which has only recently been definitely established by Heusler^ (1891). Cinnamic aldehyde, C«Ho . CH : CH . CHO, is a light yellow, strongly refractive liquid with an intensely sweet taste. At low temperatures it sohdifles and melts at — 7.5°.o Sp. gr. 1.064 at 15° (1.0497 at ^).7 Only under greatly diminished pressure does it boil without decom- position: at 128 — 130° under 20 mm. pressure.^ For purposes of identi- fication the phenyl hydrazone, which melts at 168°, is well adapted. ^ The "cassia stearoptene" of Bochleder'o is a crystalline deposit only seldom found in old cassia oil. Its constitution was determined by 1) Lleblg'e AnnaleB, 7, p. 164. S) Zeitschr. f. phys. Chem., 16, p. 24. 2) Ann. de Chim. et Phys., .57, p. 805; ') Liebig's Annalen, 235, p. 18. Abetr. in Liebig's Annalen, 12, p. 24: l::S, sj Berichte, 17, p. 2110. p. 76; 14. p. 50. ") Berichte, 17, p. 575. 3) Liebig's Annalen, .34, p. 147; .Journ. lo) Ber. d. Academ. d. Wissenscli. zu f. prakt. Chem., 15, p. .307; 17, p. :30.3 ; Wien, mathem. phys. KL, 1850, p. 1. 18, p. 885. (Abstr. Chem. Centrbl., 1851, p. 46), and •t) Liebig's Annalen, 85, p. 271. ibid., vol. 12, p. 190. (Abstr. Chem. 5) Berichte, 24, p. 1805. Centrbl.. 1854, p. 701). 25 386 Special Part. Bertram and Kuersteiiijii 189.",, This particular specinaen crystallized out of the last fraction obtained in the rectification of an oil of cassia. In the pure state it consists of well formed, hexagonal, yellow plates which melt at -t.'i— 10°. They have a very persistent, unpleasant odor and are identical with metliyl ortho cumaric aldehyde, GiiHiiOCHs) CH:CH.CHO, a substance that can be obtained synthetically by the condensation of methyl salicylic aldehyde and acet-aldeh.yde. A constituent that has no very favorable influence on the odor and taste of the cassia oil is the cinnamyl acetate which was found in the oil by Schimmel & Oo.^ in 1889. Upon saponifieation of the non-aldehyde constituents of the oil with alcoholic potassa ciunamic alcohol is olitained on the one hand anil acetic acid on the other. The former c-rystallizes from ether in hard, wliite crystals (b. p. 187° at 11 mm.). Cinnamyl ♦ acetate boils Ijetween 18.")— 110° under 11 mm. i)ressure and has an unpleasant odor and a. grating taste. Besides this, small amounts of a second ester seem to be present, viz. the phenyl jiropyl ester of acetic acid. This i-onclusion is drawn from the boiling point of an alci:)hol that accomjianies the ciunamic alcohol after sap(.)niflcntion. On account of the readiness with which ciunamic aldehyde oxidizes, cassia oil always contains free cinnamic acid, but the auKjunt is much less than one might expect from the changeability of the ])ure a,ldehyde. It is present to the extent of about 1 p. c.'^ The free acid has the undesirable property of dissolving the lead of which the canisters are made. A ci-ystaUine sediment observed by HirschsohnJ' in 1891 con- sisteil of lead cinnamate. Subsequently he examined a, number of com- mercial oils and out of twelve samples eleven were found to contain lead. The test for lead is made by sliaking a few dmps of the oil with sulpliuretted hydrijgen water. According to the amount of lead ])resent, the oil is colored red to l:ibn;-k. Foi' medicinal or (iulinary purposes only tlie i-ectified oil, frei' fnmi L.'ad, shdulrt be used. Adulterations and their Detection. Formerly cassia oil was adulterated only with fatty oils, cedar wood oil and gurjun balsam oil. i| .loui-n. r. i>i-iikt. ClieiH., II, .Tl, p. ;n(5. =) Bt-rii-ht Ton S. & Co., Oct. ISS'J, p. 19. 3) Eviileiitl,Y till) cinnamyl acetate largel.v prevents the oxidation a.^ i.s Kliown b.v tlie following experiment. A very olfl oil of cassia containing 77.7 p. c. of aldeli.vde was set aside for a .year in shallow dishes covered with jierforated filter paper. Heat, light and air had free access. .It the end of this ]>eriod the cinnamic acid content had increased from 0.7 p. c. to S..", p. c. Resinification had been I>ut sliglit, for the non- volatile residue (comp. tests), was but slightly greater after the experiment than l:)efore. Under like conditions pnre cinnamic aldehyde w^ould rapidly have been converted into a mass of crystals of cinnamic acid. — (Ber. of >S. & Co., Oct. l.SyO, p. 10.) .i) Pliarm. Zeitschr. f. Rnssland, 80, p, 790, Oils of the Lauraceae. 387 The deteeti(_)n of these adulterants was very simple, since the specific gravity was lowered and the oil was no longer soluble in 8(^) p. c. alcohol. The presence of the oils of cedar wood and g'urjun balsam could furthermore be readily ascertained by their strong laevo-rotation. Less easy of detection was the adulteration with rosin and petroleum which was much practiced in Macao and Hongkong especially during the late eighties. At first c-olophonium only seems to have been used, but inas- much as larger additions of rosin thickened the oil and increased its specific.- gravity, this discrepancy was equalized by the addition of petroleum. Inasmuch as this method of adulteration did not influence the solubility in SO p. c. alcohol any more than the specific gravity, it was not discovered for some time. Detection, however, followed when the addition of rosin became too large. The commercial oils of that period had a veiw unpleasant odor, a dark brown color and the c^ou- sistency of a thi(.'k laccpier. The taste which was but slightly sweetish soon gave way to an unpleasant and persistently grating sensation in the mouth. Upon rectification witli water vapor, as much as 40 p. e. of a resinous mass remained in the still. The distillate separated in two layers : one sank to the bottom of the water, the other fioated on it. The latter consisted, as was found upcjn examination, of petroleum. The demand to be able to detect on a small scale this form of adulteration, led to the distillation test of Schimmel cV: Co.i This test consists in distilling a weighed or measured qnantitj' of the oil and weighing the residual rosin. Fifty gT.iiiis of eassi.-i oil are weif;'li('d in a taivd fr;iftioiiation flask of TOO IX. capacity (fig-. 53, p. 189). A tube 1 in. in length iw .attached as con- den.ser and the oil distilled with the aid of a direct flame. At first water jiasses over with "cracking," tin' thermometer then i-ises rapidl.v to 240° and the bulk of the oil distills betwpcn 240 and 260°. The end of the distillation is indicated by the a]:ipearancc of white fumes arising' from the decomposition of the residue. The thermometer at the same time i-ises to 280 — 290°. Mpon cooling the residue in the flask is weighed. The residue oi a good oil is viscid and tough and constitutes 0—8, at most 10 p. c. of the oil. The residue of an oil adulterated with rosin is hai'd and brittle and correspondingly larger. Instead of weighing the oil, ."lO cc. ca.n be measured in a ]iipette and the distillate be collected in a graduated cylinder. By deducting the number of cc. ol' distillate from .50, the amount of residue can be a.scertained with sufficient accui-acy. The petroleum can be detected in the distillate. The distillate from pure oils forms a clear solution with TO — 80 ]>. o. alcohol. If petroleum is present, 1) Bericht von S. & Co.. Oct. 18S0, p. 15. 388 Special Part. no perlpct solution resultH:^ tlic liquid is tnibid at first, but upon standing- tlie supernatant i)etrolpuni can hf removed and its beliavior toward suliihuric and nitric acids be tested (toinp. p. 201.) Ill order to detert rosin in cassia oil witliout material loss, Gilbert 2 Rug-g-ests that several grains of oil be heated in a watc-hglass in a drying oven at a temperature of 110—120° until of c-onstant weight. According to Gilbert, the determination of the ai-id number also yields useful re.sults for the detection of rosin. An oil which upon distillation yielded . c. alcohol, a freshly prepared solution of lead acetate in 70 ji. c. alcohol, satui'ated at ordinary temperature, is added drop b.v drop to the extent of oue-half the volume of the oil solution. If a ]ireci]>itate is produced, the oil was adulter- ated with rosiii. As little as -j ]i. c. of rosin can be deticted in this way. Aldehyde Assay. Inasmucli as the value of cassia oil depends on its ciniiamic aldehyde content, the aldehyde assaj' is of the greatest importance in deter- mining tlie value f)f the oil. The method worked out by tSchimmel & Co.* is universally recognized ^ and the oil is sold according to the results obtained by it in the principal markets of the world, suc-li a.s Hongkong, London, Hamburg and New York. For the assay a special fla.sk ((.-assia tiask, aldehyde flask, tij;-. 71) of about 100 cc. capacity is used. The neck of the flask is about 13 cm. long, has an Fiff. 71. Vs natiiDiI size. 1) As nlready stated, cassia oil that contains roain as well as petruloiini, is soluble in 80 p. c. alcohol, whereas otherwise pure cassia oil to which petroleum has been added does not form a clear solution with 80 p. c. alcohol, the petroleum separating in the form of oily drops. 2) Chem. Zeitunj>:, 18. p. 1406. 3) Pharm. Zeitschr. f. KnssL, 2*J, p. 255. 4) Bericht von S. I'c Co., Oct. 1890. p. 12. G) In the description of his travels through the cassia districts, Q. Struckmeyer relates that he found the implements for the aldehyde determination according to Schinimel & Co. oti a plantation near Loting-chow in the interior of China. Bericht von S. & Co., Oct. 1896, p. 12. Oils of the Lanrficeaf. 889 inner diameter of is mm., and is calibrated into Vio cc. The neck has a capacity of about 6 cc. Tlie zero mark i.s fixed .shghtly above tlie point where the flask is narrowed into the neck. B.v means of a pipette. 10 cc. of oil are transferred to the flask and an equal volume of iiO p. c. sodium acid sulphite solution is added. The mixture is sliaken and the flask i)laced in a boiling water bath. Alter the solid mass has become liquid more acid sulphite solution is added, the mixture being constantly heated and occasionally shaken, until fully three-fourths of the flask is filled. The solution is heated until no more solid |jarticles are visible and the odor of cinnamic aldeh.yde has disappeared. When the clear oil floats upon the salt solution, flask and contents are allowed to cool and suflicient acid sulphite solution is added to raise the lower hmit of the oily layer to the zero point of the scale. The number of cc. of oil is read off, and b.y deducting this number from ten, the aldehyde content is ascertained. Accurately speaking, percentage by volume a.nd not jiercentage by weight is determined in this maimer. Inasmuch, however, as the specific gravity of the aldeh.yde and the non- aldehyde constituents is almost the same, the two are practicall.v identical. The chemical reactions involved can be explained by means of the following equations (Heusler,i 1891): At first the insoluble aldehyde addition product is formed. CaHs . CH : CH . CHO + NaHSOg = C0H5 . CH : CH . CHO . NaHSOg Cinuamic aldehyde Aeid sulphite of sodium Clnnainal hydroxy sulphunate of solUuiii, When boiled with water, two molecules of this addition product break up into a molecule of cinnamic aldehyde and one of sulpho cinnamal hydroxy sulphonate of .sodium. 2G(jH5 . C;H : (JH . CHO . NaHSOs = CoH, . CH . CH . CHO -|- Cinnamal hydruxj- sulphunate of su-Uuni Olnuaiiiic aMehyile CflH.,CHL> . CH(SOnNa) . CHO . NaHSOa sulpho rionaiiial hydroxy sulphonate of sodium. In order to convert all i:)f the aldehyde into the second compound soluble in water it is necessary to use ati excess (2 mol. ) of sodium acid sulphite. The salts of the sulpho cinnamal hydroxy sulphonic acid are readily soluble in water, and not decomposed by boiling water. They are decomposed by destructive distillation or when heated with caustic soda or sulphuric acid. The aldehyde content of a good cassia oil amounts to at least 75 p. c, and only in rare instances is highei- than 90 p. c. However, oils have been obtained from China which contained only 33—30 p. c. of aldehyde, .vet no adulteration could be detected. According to the Cliinese, these oils were distilled from young leaves, an assertion the correctness of which cainiot be ascertained. i| Berichte, 24, 11. 1X0.": Bericht von S. & Co., April 1890, ]i 390 Special Part. In order to be able to assay oils with but 35 p. e. of aldehyde according to the method given above, it is necessary to use o cc. of oil instead of lo cc. and to make corresponding changes in the calculation. Oils obtained from the different parts of the Cassia Shrub. All parts of the cassia shrub yield oils with a high aldehyde content. i The differences in the specific gravity, though they are but slight, indicate that the non-aldehyde constituents vary somewhat as to com- position. In tlie distillation of the commercial oil only the leaves and twigs are commonly used. The bark and the so-called cassia buds command too higli a price, whereas the flower stalks cannot be obtained in sufficient quantity. However, it may happen occasionally that all of these parts are distilled. 1. Oil from the bai-k, the Cuskih lignea of commerce. Yield 1..") p. c. ; sp. gr. l.()3.j; aldehyde content .S1S.9 p. c. 2. Oil from the cassia buds, the Flore.s cas.sme of commerce. Yield l.() p. c. ; sp. gr. 1.026; aldehyde content 80.4 p. c. Pj. Oil from the stalks of the cassia: buds, 1.040; aldehyde content 92 p. c. 4. Oil from the leaves. Yield 0,.")4 p, c ; content 9:i p. (• '>. Oil from the twigs. Yield 0.2 p, c, ; content !)(.) p. c. (j. Oil from a mixture of leaves, petioles and j-oung twigs. Yield 0,77 p, I-.; sp, gr, l,0.")."i; aldehyde content !•;? p, c. Inasmuch as the commercial oil is distilled from the materials enumerated under No. <>, its properties should correspond with those found and recorded al)ove. The fact that the commercial oils never equal the above in (piality is probably due to the crude method common in (liina, namely the distillation over a free flame, Productiox .\nd CoiiMEROE, ('assia, also kuowTi comnierciallj' as CussiH. Uu;iie;h in order to distinguish it from other cinnninon varieties, is ])roduced in a comparatively limited territory, namely in the provinces Kwaug-si and Kwang-tung. The cassia, distric't lies between the degrees 110 and 112 eastern hmgitude. It is bounded on the north by the S^i-kiang or West river, and extends to the south as far as the 28°;!' Udrthern latitude. The principal plantations are in thi^ vicinity of Tai-wo, Yung and iSihdeong on the t^ang-kiang, also at Loting-chow on the Lintan river. Yield 1,7 p. c, ; sp, gr. sp. gr. l,n.5(i; aldehyile ■jp, gr. 1,04.'.; alilehyde 1) Bericht Tfiii K, & To,, Oct, 1S92, p. 12, Oils of the Laiivaceae. 391 The Tai-wo product i.s preferred in the market. The annual output of cassia varies between 50,000 and 80,000 pieuls or ;^, (100,000 and 4,800,000 k. fJauton and Hongkong are tlie principal niarliets. From the latter point 54,082 piculs were exported during 189(). The distillation is conducted in the district outlined above. As material tor distillation the leaves, petioles and twigs, which result as waste in the production of the Cassia lignea, are used. Whereas the cassia bai-k is transporled down the Si-kiang, the natural water route, to Canton, the oil is conveyed in lead containers over the mountains to Pak-hoi and then by ship to Hongkong. This is done to avoid the high tariff levied at the Likin stations on the way to Canton. The annual production of cassia oil varies between 2,000 and 3,<)00 piculs, or 4,0litii>-i folia. jvAt\ upon distillation (770 dz, to the ton) an oil which has a decided ocloi- of sas.safras." 1) Trommsdorff's Ncues .Journ. der I'harm.. S, II, ji. 10(i, 2) Arohiv (1. Phnrni,, 285, p. .58:!. 3) Bericlit Yon S. & Co., Ot-t., 18S7, |i. :!r,; Apr. ISSN, p. 4r,. i) Prop. Liiiiieiui .Sor. of .\.-S.-W:ilfs. IS'.lT, ]>;ii-t 2, ]i. L'7."); iil.str I'hariii Zt"' +■' p. M-,<). '') Rericht von S. 0^ Co.. .\pr. 1MS7, p. ;1S. Oils of the Lauracene. ' 393 138. Oil from Persea Gratissima. The leaves of Povfea gratmsima Gaertn. (from the botanic-al garden in Genoa) yielded upon distillation 0.5 p. c. of a light greenish oil which closely resembles estragon oil in odor and taste.^ Sp. gr. 0.9607 ; aD= + 1°5<)';' nD at 18.2° = !.. 5164. These data indicated the presence of fairly pure methyl chavicol. Anethol was excluded because of the absence of a sweet taste and because no crystals separated when the oil was exposed to a freezing mixture. An attempt to convert a part of the oil, of which but 10 g. were obtainable, into anethol by means of alcoholic pota.ssa failed on account of an accident. The remaining oil, when oxidized with permanganate, yielded an acid melting at 188° which possessed the properties of -anisic acid, thus indicating methyl chavicol. 139. Oil from Clove Bark. The bark of the Brazilian tree Persea vavyophylhitci Mart. (Dicy- pellium caiyopliyilatuin Nees) was formerly used in the apothecary shops as Cortex ciiryophyllati. It was also known as Cassia caryo- phyllata (Ger. Nelkenrinde, Nelkenziint,^ Nelkencass'ie and Nelkenholz). Upon distillation of the powdered bark, Trommsdorffs (1881) obtained 4 p. c. of a light yellow oil heavier than water which had the odor of cloves. With potassa., soda, and ammonia the oil formed crystalline compounds from which it could be regenerated upon the addition of sulphuric acid. Tliis property as well as odor and density render it probable that this oil. like the oil of cloves, contains eugenol. 140. Oil of Pichurim Beans. The volatile f)il of the cotyledons of Nectandra pichury major Nees and iV. p. minor Nees, the pichurim beans of commerce, was first prepared by Robes* in 1709 and then by Bona.stre-' in 1825. It was examined by Mueller" in 1858. On account of the large amount of starch present he added sulphuric acid to prevent the formation of starch paste and obtained 0.7 p. c. of an oil of greenish-yellow color and tlie characteristic pichurim odor. 1) Beriuht vcn S. i Cik. Oct. 1894, p, 71, 2) The riil from tin- lp;L\'fc*,s of the <'eylon cinnamon \v;is for a time designated as Nelkenzim tol. 3) Tromm,sclorff's .\eues .Journ. d, Pharm,. 23, I, ]>, 7. 4) Berlin. .Jahrlj. d. Pharm.. 5, p, GO. _ 5| Ibidem, 37. ii, IGO: Eepert, f. rt. Pharui,, 1, 21, p, 201, 8) .Journ, f, pral— 170° had an orange odor and seems likewise to hivve been a terpene. Fraction 25.j— 25(j° had a, deep indigo blue- color. Frcjm the highest fractions i:rystaLs of "pichurini Fettsiiure" (Inuric acid) separated. Inasmucli as the piehurim beans have a distinct safrol (jdor, this substance is probably a constituent of the oil. 141. Caparrapi Oil. Accoriling to 15. F. Tapia, i (189H) the oil of Nectniidin ciipamipi is long known in Columbia as capivrrapi oil. The tree is popularly known as duielo, probably on account of the cinnainon-like odor of the bark. The oil is obtained according to a method similnr to that in vogue in this crjuntry for the production of turpentine, and is used as a substitute for copaiba in this country. In commerce the oil is fomid more or less colored in accordance with the tempei-ature employed in the removal of the water. It contains a, monobasic acid, CioHao**:!, which melts at 84. •'i° and which can lie obtained in acrj^stalline form only from the light colored oils. The acid free oil consists in kirge ])aTt of a sesquiterpiene alcohol, C1.5H2.-5OH, called caparrapiol, whi(.-h is converted into caparrapene, Ci.-,Hl>4. by dehyilrating agents. The alcohol as well as the hydrocarbcjn are readilj^ polymerized, espe(.-ially b,y heat, so that in the water distillation about three-fourths of the cjil is resinitied. 142. Guayana Linaloe Oil. The oil from Orotea aiudiitu is des(-ribed together with Mexican linaloi' oil, which see. 143. Ocotea or Laurel Oil from Guayana. An oil designated laurel oil from Denierara (British (luayana) -ivas^ examined liy 8teuhou.se- in 1.S42. According to ('hristison, it is obtained from n s]>ecies of the genus Ocoten. Incisions are made near the root, penetrating the oil (-avities beneath the bark. The exuding oil is a yellowish liquid which has a pleasant terebinthinate odor, sp. gr. ().8()4 at l;i.;5° and boils between 149— l(;2..j°. Upon standing, a mixture of 1) Bull. .Soc. chim., Ill, 10, p. (IBS, 2) Philos. Mag-az. ami .loiini. ijf Science, 20, p. 27H: 2',. ji. 200. Liebin'w .iimalen, 4-t, p. 309: .50, p. 1.5.''). Cump. iilBO Hancock, Hull. iIck sciences, malh. pliys. et chim. Yi\r. 1825. p. 125. .-\bsti-. 'ri-cjnimHiliirft"s .\eues .[oiirn. d. I'hann., l"!, I, ]i. 171. Oils of the Lunracene. 395 oil. alcohol and dilute nitric acid yielded crystals which upon recrystal- lization were obtained in the form (if white, rhombic prisms melting at 150°. The oil. therefore, appears to consist of pinene and the ci-ystals obtained by Stenhouse were probably terpin hydrate although the melting point of this substance lies at 11(3—117° and not at 1.50°. i 14'4. Venezuelan Camphorvtood Oil. Through the kindness of Professor H. H. Kusby,- Fritzsche Bros, of New York (obtained some Yenzuelan camphorwood. the l.iotanical origin of which has not been determined, but which probably belongs to either the genus Nertandrn or Ocotea (Family Lanraceae). The wood, which was in the form of large billets, was rather soft and easily split, has a silky lustre and possesses a faint odor reminding somewhat of borneol. Upon distillation of the comminiited wood, l.l."i p. c of a light yellow oil was obtained that had an unusually high sp. gr., viz. 1.15.5, and '.2. i) Pi'oc. Am. I'harm. Assoc., 29, p. Hi'i. 396 Sppcial Part. As already mentioned under the oils of sweet bireli and wintergreen (p. 331) next to turpentine oil, tlie oil of sassafras was tlie first volatile oil distilled in a primitive fashion in North America. On account of the pleasant aroma, the root bark was chewed by the natives as Pavnme. It was also mixed with smoking tobacco (Raftnesquei ), and added as nronuitic to refreshing beverages and was used as a remedy. On account of its peculiarity, the sassafras tree is said to have attracted the attention of the Spaniards at their first landing in Florida under Ponce de Leon in 1-'12, also under de Soto in 1538. They are said to have regarded it as a kind of cinnamon tree. Afterward the sassafras tree soon came to be regarded as a valual.ile medicinal plant and article of luxurj' of the new world, not only by the Spaniards and French in Florida, but also in Mexico. As late as the first half of this century the bark, leaves and buds were used in the middle and central states as a substitute f<:ir Chinese tea (Lloyd-). As early as 1.">(S2 sassafras w<.)od and bark became known in Germany as a new American drug and wei'e used under the name of LigJium pavcinum. L. floridum, L. xyloimtnithi'uw (Ger. Feiichelbolz).^ In 1610 young plants were brought to England and cultivated.* Bark and wood were apparently first distilled by Angelus Sala in 1020, who mentions that the oil is heavier than water.s Schroeder's Pharmacoptea medieo-chymica, published in Frankfurt-on-the-Main in Kill, is the first pharmacop(jeia that gives directions for the distillation of the oil. whereas the municipal price ordinance of Frankfiu't-on-the-Main of l."i87 alreailj^ enumerates Oleum ligni sfis.safras. Hoffmiann in Halle distilled the oil in 171.") and describes it as being colorless and specifically heavy. 's In 173H Maud, an Englishman, observed the formation of large crystals of sassafras camphor.''' Earl,y examinations of the oil were made by Muschenbroeck, l)y Neumann,** and Ijy Dehne,'' the first thorough orie was made by Grimaux and Ruottei" in ISG'.t. A detailed historic ac(iount of the sassafras tree as a. ilrug-vielding plant was given l:iy .1. IT. Lloyd- in 1808, who, however, does not enter into the history of the ^'olotile oil. Schoepf," wlio was a careful observer 1) Med. Flora cii- .Alniiual n[ the Meil. «) Obsi'i-vatinnes pllYsiro-chymiri. Oliser- Bot. uf the U. S. of N. Am., vol. 3, p. 23.-1. vati.j 1 , p. 3 .H. -J HiKtoricalstndy ofSasaafras. l^havin. ~i Pliil. 'I'rans. of the Uoy. Soc, 8, Review, 1(5, p. 450: rharni. Era, 20, p. ijlis. p. 2 + ;i. :') Doeuniente ziir (>e.schichte iler Phar- S) Ciiyin. ined., viA. 2, pars 3, ]). 248. macie, p. 30, !i| System d. .Mat. meil.. vol. 4, p. 242. ■') Pharmaeosrniihia, p. ."i:!7. lu) Coiiiiit. rend., (is, p. '.I2s, S) Cljtera pli^\'sieo-iiieiIlca. i>. S4. Oils ot tlie LaniHcese. ' 397 and who traveled tlirough the Atlantif states in 178:! and 1784 repeatedly refers to the sassafras tree, but does not mention the oil. Evidently the distillation of the oil did not become an indnstry until the close of the last or the early part of this century. Possibly it was fostered by the growth of the industry in medical specialties ("patent medicines"), as was the case with the oils of sweet birch and wintergreen. The process of distillation seems to have been generally very primitive.! The still consisted of a barrel uitli a perforated bottom, firmly fitted into a conioal iron kettle. The top of the barrel coald be removed to charge the still. It is pi'ovided with an opening for the reception of a tin tube which passes through a barrel of cold water and serves as condenser. In recent years the distillation is conducted in a somewhat more rational manner. The stills, made of -T in. pine planks, are i^-Tt ft. high, about 12 ft. square and strengthened by iron bands. One of the sides is provided with two close fitting doors, an upper one for charging the still, and a lower one for removing the e.Khausted material. The wood is split, or sawed into thin pieces. The steam, generated in a boiler, enters the still at the bottom and the di.stiliat^ is cooled in a coil condenser and collected in a large copper flask of 20 gal. capacity. About 2 in. from the bottom this flask is provided with a stopcock through which the oil is drawn off from time to time. The exhausted wood is dried and used as fuel. Such a still has a capacity for 20,000 lbs. of wood and the distillation of this quantity lasts about 48 — 50 hours. The root bark yields 6—9 p. c. of oil, the woody part of the root less than I p. c. Up to the middle of this century the oil was distilled principally in Pennsylvania, Maryland and Virginia, and Baltimore and Richmond were the principal commercial centers for the oil. At the beginning of the war in 1860, not less than .50,000 lbs. of sassafras oil were sold annually in Baltimore alone (Sharp 2). Since the sixties, considerable quantities of the oil have also been distilled in New .Jersey, New York, Ohio. Indiana, Tennes.see and the New England states, until the practical extinction of the tree rendered the industrj' unprofitable. Peopebties. Sassafras oil is a yellowish or reddish-yellow liquid having the odor of safrol and an aromatic taste. Sp. gr. 1.070—1.080; a^ = + .3 to + 4° ; soluble in all proportions in 90 p. c. alcohol. If, according to the U. S. Pharmacopoeia, .5 drops of oil are mixed with .5 drops of nitric acid, a violent reaction results: the oil is first colored red and is later converted into a red resin (Bonastre-'). 1) Proc. Am. Pharm. Aksoc, 14. p. 211: Am. Druggist 1887, p. 4.5; Xew Remedies. 1883. p. 224: Oil, Paint & Drug Reporter, Sept. 14. 1891: Pharm. .Tourn., Ill, 22, p. 491. 2) Am. .Jour. Ptiarm., .3.J, p. 13. Comp. also W. Procter, ibid. 33, p, 1; 38, p. 484- 3) Comp. p. 400, footnote 2. 398 Special Pnrt. Oils of the Lauraceae. 399 "be a 400 Special Part. Composition. To its principal constituent, the safrol, C10H10O2, the- oil owes its odor as well as its principal properties. This substance was observed by Binder 1 in 1821, it having crystallized out of the oil- The earlier investigators- contented themselves by studjnng the action of chlorine, bromine, etc. on the oil as well as on the safrol. Upon satur- ating the oil with chlorine, then neutralizing the mixture with lime and distilling with water vapor, Faltin ■' observed another constituent of the- (jil, the ordinarj^ camphor. The term safrol was introduced hj Grimaux and Ruotte* (1869) who ascertained its composition to be represented Xij the formula. <-'ioHio02. Thej^ also isolated a hydrocarbon CioHie, b. p. 15.5 — 157°, ami named it safrene. They further observed the presence of a phenol which had the odor of eugenol and produced a green color with ferric (jhloi'ide. The identity of this phenol with eugenol was later established by Pomeranzs (1890). A detailed study of the composition of the oil was made by Power and Kleber^ in 1896. From the air-dried root bark 7.4 p. c. of oil wer& obtained, sp. gr. 1.075, aD = + 3°16'. After most of the safrol had been removed by freezing, the eugenol (benzoyl eugenol, m. p. (59°) was- shaken out with caustic alkali solution. The oil thus deprived of safrol and eugenol was fractionated. Fraction 155 — 160° was found to consist- of pinene (pinene nitrolbenzjdamine, m. p. 123°) ; fraction 160 — 175° contained phellandrene (nitrite). The so-called safrene of Grimaux and Ruotte is, therefore, pinene. From a higher fraction destro camphor (oxime, m. p. 115°) was isolated. The quantitative reduction of the camphor to borneol and the acetydization of the latter showed that camphor was present to the extent of 6.8 p. c. in the oil. Inasmuch as fraction 260 — 270° gave the characteristic sesquiter- pene reaction with sulphuric and glacial acetic acids, the presence of such a hydrocarbon is assumed, though a solid hydrochloride could not be obtained. According to the investigation of Power and Kleber, the composition of sassafras is as follows : 1) Bnchner'8 Hepert. f. d. l*harm., 11, p. .346. 2) Bonastre, 1828, .Tourn. de Pliarm., II, 14, p. 645. Abstr. TroramsdorH's Neues .lournal, 19, I, p. 210; Saint Evre, 1844, Ann. de Chim. et Phys., Ill, 12, p. 107; Conipt. rend., IS, p. 705. Ab.st. Llebig's Annalen, 52, p. 39G. 3} Liebig'e Annalen. 87, p. 376. •1) Compt. rend., 68, p. 928. 5) Monatsh. f. Cheni., 11, p. 101. •5) Phann. Review, 14, p. 101. Oils of the Laiu-ncene. 401 Safrol 80.0 p Pinene ( ^^ ^^ PhellaTidreiiel d-Camphor 6.8 Eugenol 0.5 High boiling substaiioes (sesqui- terpene and residue) JS.O e. 100.;-! Adulteratiox. Sa.s.safras oil is frequently adulterated with camphor oil. A perfec-tly pure article appear.s to be ot rare occurrence. Inasmuch as camphor oil contains all of the constituents found in sassafras oil, the detection of the former is exceedingly difficult, but its presence may be indicated by strong variations in the specific gravity and other physical properties. Under tlie name of artificial sassafras oil, fractions of camphor oil having a specific gravity similar to that of true sas- safras oil are sold. 14.6. Oil of Sassafras Leaves. As far as is known, the oil of sassafras leaves has been prepared but once. Power and Kleber^ obtained upon the distillation of fresh .sassafras leaves 0.02.S p. c. of an oil with a very agreeable odor remind- ing of that of lemons. Sp. gr. 0.872, 'iD = + 6°25'. The low boiling fractions consist of a mixture of pinene (nitrol- benzylamine) and mj'reene. This representative of the olefinic terpenes which have been found e. g. in the oils of bay, hops, origanum and ro.semary, was hydrated according to Bertram's method. The resulting alcohol had the odor and boiling point of linalool. This alcohol was further identified bj' its oxidation product citral and the condensation product of the latter with naphthylamine and pyrotartaric acid. The third terpene identified is phellandrene (nitrite). In addition, the presence of a paraffln melting at 5.8° and of a sesquiterpene was established. Of oxygenated constituents the oil contains citral (citral-/?- naphtho cinchoninic acid) and the two isomeric alcohols linalool and geraniol. These alcohols occur free as well as in the form of acetic and valerianic esters. 147. Cryptocaria Oil. Cryptocaria woschatn Mart, is a tree 10—15 m. high and is known in Brazil by the popular name Nos moscado do Brasil, Brazilian 1) Pharm. Review, li, p. 10.3. 26 402 Special Part. nutmeg'. The ripe fruits are somewhat smaller than nutmegs and liave a, strong aromatie odor reminding- of laurel, sassafras, eajeput and nutmeg. Ten kilos of the poAvdered fruit deprived of their ])ericarp yielded upon distillation 37 g. of volatile oil (Peckolt i). This is a mobile liquid, light yellow in color, of a penetrating, aromatic odor and a burning, spiey taste. Sp. gr. 0.917. It is soluble in 90 p. r. alcohol in all proporticjns. l-tS. Oil of Cryptocaria Pretiosa. The bark of Cryptocaria. pretiosa, Mart.. (Mespilodaphne pretiosa Nees et Mart., Family Laiiraeeae). which is indigenous to northern Brazil on the Rio Negro, has a pleasant aromatic, cinnamon-like odor. Upon distillation the bark yielded l.KJ p. c. of an oil of cinnamon-like odor and a. sp. gr. of 1.118. Although the odor seems to indicate the presence of cinnamic aldehyde, no crystalline addition product was obtained with sodium acid sulphite solution.- 14.9. Oil of Laurel Leaves. Oleiiiri Laiii-i Folioriim. — Lorbeerbliitterol. — Essence (le Laurier. Okigix and Histoky. The laurel, Lauriis nohilis L. is indigenous to Asia Minor, Syria and the Silician Taurus and has been extensively c-ultivated. During classical antiquity it acquired great signiticauce as a symbol of victory but apparently found no other application than as a decorative plant. During the middle ages bark and leaves were used medicinally. The laurel oil of commerce is distilled from the leaves. The yield varies from 1—8 p. i:-. according to the quality of the leaves. Pkopbhties. The oil of the laurel leaves is a light yellow liquid with a pleasant odor, which first reminds of that of eajeput oil, and later becomes sweetish. Sp. gr. 0.920— 0.930 : «d = — lo to — 18° ; 2 — 3 p. of SO p. c. alcohol are re(]uisitp to effect solution. Composition. The oil begins to boil at 158°, the thermometer rising rapidly to 1(58°. This fraction contains pinene (nitrolpiperidine base, m. ]). 118°). Fraction 17()° contains cineol as shown by the hydrobrom addition product. The fractions above 180° had a decided odor of anethf)1.3 Inasmuch, however, as the oil has no sweetish taste, which ought to be the case if anethol were present, this odor seems to indicate methyl chavieol, the isomer of anethol. The oil also c(3ntains small amounts of eugenol (benzoyl eugenol, m. p. 70°).a 1) Phnrm. Review, 14, p. 24S. 3j lierielit von S. &Co., .\pr. ISO'.I, p. 31. -) Bericht. vun S. & Co., ,\pr. 1803, ji. (i3. OHk of the Laiirncene. 403 150. Laurel Oil from Berries. History. Upon boiling and expi-ession of the lanrel berries a yreen mixture of fatty and volatile oil is olitained {Oleum liiurinuin) which is semi-liquid at ordinary temperature. It wms used during antiquity and in older literature is mentioned among the substances employed in the preparation of ointments; also among the aromatics. It was contained in the first edition of the Dispensatorium Noricum of l.jiy. The volatile oil also seems to have been used medicinally. It is also mentioned in the price ordinances of Frankfurt of 1582 as well as in later ones. At present it seems to find little or no practical application and is only now and then prepared for scientific purposes. Tlie yield fi-om the berries is about 1 p. c. Properties. The oil from the berries is somewhat more viscid than that from the leaves; its odor is less agreeable. (.)n account of the lauric acid which it contains, some specimens sohdify at temperatures aljove 0°. Sp. gr. O.tt].") — 0.03."). The angle of rotation of a single oil was found to be — 14° 10'. The same oil was insoluble in 80 p. c. alcohol, but was soluble in ]4 and more parts of 90 p. c. alcohol. COMPOSITION. 1 The lowei' fractions contain the same constituents as the leaf oil (^^'allach,- 181S9). viz. very little pinene (pinene nitrol- l)euzylamine, m. p. 122 — 12;!°) and much cineol (ciueol hydrobromide). Tlie sui)posed laurene of Briihl^ (1888) has revealed itself as a. mixture of the above two constituents. Frartion 2.50°, sp. gr. 0.92.5, w.d^ — "-2°, has the composition ('i,jH24 and is therefore a sesquiterpene (Bias,* 18(55). Another constituent of the oil. the amount of which will vary a,ccording to the duration of the distillation, is lauric acid. It can l)e removed by shaking the oil with lye and melts when pure at 48°. ^ In addition the oil contains ketones and alcoholic constituents which form solid compounds with sodium. Liberated by means of water they form a viscid oil which distills between 71 — 184° under 20 mm. pres.sure. The statement made by Gladstone" that this oil contains eugenol has not been substantiated by the investigations of Bias and Midler. i| The first inveBtis-atloiiR were ciirrieil out by Bontistre, 1X24, .Ji>urn. de Pharin., 10, p. He ; 11, p. y; Abstr. Repert. f. d. Pharm., I, 17, ]). l'.)0; and by Braiidcs, 1S4(>, Archiv d. Pharm., 72, p. 160. 2) Liebig-'s Annalen, 2.^2, p. 97: also .MBller, Berlchte, -Jo, p. 547. 3) Berichte, 21, p. 157. *) lyiebis's Annalen, 184, p. 1. 5) Bias and Muiler, loc. cit, c) .Joiirn. Chera. Soc, II, 2, p. 1. .Alistr. in .lahresli. f. Cheiii., 1K6:!, p, r,ir,. 404 Special Part. Although Gladstone designates his oil as "Bay oil from the berries of Laurus iiobilis," it seems rather probable that he examined genuine baj^ oil which consists largely of eugenol.i 151. Kuro-moji Oil. Oleum Kiiroiiioji.—Kiiromojiol.— Essence de Kiiro moji. Lindera sericea Bl. is a shrub quite generally distributed throughout the mountainous regions of Japan." All parts of the plant contain small amounts of volatile oil, even the wood which is used in the manufacture of tooth-picks. The oil, which was introduced into the market in 1889 by 8chimmel & Co., is obtained from the leaves and young twigs. The distillation is conducted on a small scaJe by farmers who are satisfied to work up the material growing on their farms. Properties. Kuro-moji oil is of a dark j-ellow color and has a flue aromatic, balsamic odor. Sp. gr. 0.890 to 0.90."); «d = — <>°4:'. Composition. According to Kwasnik* (1892) the oil contains two terpenes and two oxj'genated constituents, viz. d-limonene (tetrabromide, m. p. I(l4°), dipentene (tetrabromide, m. p. 124°), terpineol (phenyl- terpinyl urethane, m. p, 109..')°), and 1-carvone (hyrlrosulphide, ra.p. 214). 152. Mountain Laurel Oil. All parts of the Mountain laurel or California bay tree-"^ Uinbellularia califomica Nutt. (Oveodiiphne californici Nees, Tetninthera californica. Hook, et Arn., Californischer Lorbeerhaum) contain volatile oil, especially tlie leaves which yield 2.4° to 4'-' p. c. The oil is of a light yellow color and has a pungent aromatic odor reminding of nutmeg and cardamom. Strongly inhaled it attacks the mucous membrane and causes the flow of tears. The taste is warm and cainphor-like. Sp. gr. 0.9:56 to 0.940. According to Heany" the oil boils between 175 and 24.")° and con- tains a hydrocarbon boiling at 17."°, also an oxygenated constituent called oreodaphnol, b. p. 210°, sp. gr. 0.9G0. StillmannS found in fraction 167—168° a substance of the com- position of the "terpinol" of Wiggers and List,'^ also umbellol, boiling at 21.5—216° and ha,ving the composition GgHioO. 1) Even ranch more i-ecently no difference 5) Berichte. 18. p, fi.SO. hns been made in England between bay 6) Am. .Jonrn. Pharm.. 47, p. 10.5; oil and the oil from laurel or ba.\' berriew. Pharm. .Journ., III. 5, p. 7*,)1. f'omp. e. g. Ashton in ChemiKt and Druggist, t) As shown by Wallach, terpinol is .July 2, 1892. no chemical unit, but a mixture of dipen- 2) Chemist and Druggi.st, 47, p. .502. tene. terpinene, tei-pinolene and terpineol 3) Archly d. Pharm,, 2'AO, p. 205. (Liebig's Annalen, 280, p. 251). 4) Ber. d. pharm. Ges., 6, p. 50. Oils of the Laurnceae. 406 153. Spice"v\rood Oil. All parts of the North American spicewood, sp)(-'e bush or fever bush (Benzoin odovifernm Nees, Lauiv.s benzoin L., Benzoelorheer-Stranch), but especially the bark and the berries contain volatile oil.' The bark is used as a domestic remedy. 1. The oil of the bark and twigs which was introduced into the market as spicewood oil by Fritzsche Bros, in 1S85, has the odor of winter- green, sp. gr. 0.923 and boils between 170—300°. It consists of hydro- carbons and 9 — 10 p. c. of methyl salicylate. By treating 200 g. of oil with caustic soda, 1() g. of salicylic add were obtained. 2. The berries contain 4 — ."i p.. c. of iin aromatic, spicy oil with a camphor-like odor; b. p. 160—270°; sp. gr. 0.850— 0.85."i. 3. The leaves contain about 0.3 p. c. of oil with a very agreeable odor. Sp. gr. 0.888. 154. Tetranthera Oil. The fruits of Tetviinthera, nitrata Nees (Family La.uracene), some- times called citronella fruits, are regarded as a panacea in India. Upon distillation they yield about oJ> p. c. of an oil which has a strong odor resembling that of verbena oil and for this reason has been designated Japanese verbena oil. Sp. gr. 0.890— 0. 890. It boils between 180—240°, and contains in addition to a terpene, citral as principal constituent. 2 155. Oil of Massoy Bark. The botanical origin of the New Guinea bark, from which Schimmel & Co. have since 1888 distilled their massoy bark oil, is not known. Upon comparison of this bark with that of the genuine bark from Massoia. aroniatica Beccari, Holmes 3 (1888) arrived at 'the conclusion that the two were not identical, but that the bark of Schimmel & C!o. was very similar to the Cortex culilabani papuanus of Hanbury's col- lection, the botanical origin of which is also unknown. Wender* (1891), on the other liarid is of a different opinion. He states that according to its anatomical structure, the massoy bark of Schimmel & Co. is un- questionally that of a lauraceae, and that in otlier respects it corresponds best with the bark of Sa.ssafms goesiaiwm or Masnoia aromatica. 1) Beric'ht von S. & Oo.. Oct. ISS.J, p. 27; Oct. 1890, p. 49. 2) Bericht von S. & Co.. Oct. 1S8S, p. 44. T\\e sp. per. O.OSO mentioned in tiie report is evidently due to a printer's error and should be O.SOii. Two inter distillates had the sii. gr. (1.S94 and 0.896 reepectivel.v. 3) Pharm. .lourn.. Ill, I'J, pp. 465 and 761. 4) ZeitBchr. d. allgem. 0.sterr. Apoth. Ver., 29, ji. 2. 4-()(; Siiecinl Part. The mas.soY liark from German Guineti yields upon distillation 6.5— 8 p. e. of a volatile oil of a pleasant clove- and nntmeg-like odor. 8p. gr. 1.04—1.06. CoMPOSiTiox. According- to Schimmel & Co.i the oil consists princi- pall.y of eugenol (75 p. c. ) and safrol. In addition to these substances Woy2 isolated a fraction boiling at 172° in which he supposed he had fonud a new terpene, -massoyene." Wallach» (1800), however, showed that it consisted of a mixture of three terpenes : pinene ( nitrolbenz,yl- amine, m. p. 128° and nitrosopinene. m. p. I:i3°), limonene (nitrol- benzylamine, m. p. !)3°), and dipentene (tetrabromide, m. p. 128°). 156. Oil of Garden Cress. In 1846 Pless* demonstrated that the oils of Lfpidiuin rudprnle L., L. sativum L., and L. ranijiestrp R. Br. are heavier tlmn water and (.■ontnin sulphur. He states that tlie oil is ready formed in the herli l>ut not in the seeds, where it results througii the action i:)f the water. The c'omposition of the oil from garden cress, L. sativum L. was ascertained ))y Hofmann'"' in 1.S74. The herb was collected immediately after flowering and distilled in wooden vats" witli water va.p(n-. The oil being completely dissolved in the aqueinis distillate was extracted by shaking with benzene. The yield was 0.11.", p. i-. The cruile oil was of a light yellow color but became colorless upon rectification. Three- fourths of the oil boiled at 231. ."i", the boiling point of benzyl cyanide. roH.-, . CHo .f'N. The identity of this suljstanc'C was estalilislieil by its conversion into phenjd acetic acid melting at 77°. nnd by the analysis of the silver salt of this acid. The lower fractions contained a. small amount of sulphurated compounds, tlip conii)Osition of which was not determined, (xadamer'^ has recently investigated this oil and found it to lie identical in composition with the oil from Troepoflum luajus. It con- sists principally of benzyl isoc-yauate, ('iiH.-,.('Hl>.X:('S, and small ann:)nnts of benzyl cyanide. The oil is formed l>,v the .action of a ferment on the glucoside glucotropiieolin, KO.SOo.O.Cl : N.('H2.(;'c,H.-,).S.C,iH:iiO.-, + 2Ho(). The fresh herli of Lfjiidiuw latiloliuni L. yields upon distillation an oil which is heavier than water nnd contains snl]iluir. (Sttanlel ^). i| P.tM-ii-hl voii S. * Co., Ocl. isss, |i, 4-2. cop])!-!- vcssel.>< is to lie uic.icli'il. fill- thf '-] .\rchi-\' (1. T'lianii.. lil'S. 1))), i2il ami tis?. riiiiiHT ^\■ill cause ]>artinl dt'cnmiMisitiiin 3) l.icbiK's .VniialcM. U.'s. p ;j4-c; .\iTlii\- of tlie oils witli forinatiim of copjier (I. Pliarin., lii:'.!, p. nil. milpliiilr. -t| Liebiff's .\niKili-ii. ."s. p ;','.l. D Uciichte. 32, ii. 2820: .-Vrc-hiv il. S| P.frii-htc, 7. p. 12'.13. Phariii.. 237, p. .'ills. u) llui'inft- tilt' ilisllllatioii of thi.s ami '^l llisserl. ile AfriMliue nointuU. \'e<>"t^- otlifr Hiilplmi'-rontainiiij;" oils, tlii:" use of laliil. Tultin;;'en 1S(I5. Oi/.s of the CvucUeraf. 407 157. Oil of Thlaspi Arvense. According- to Pless' (1840) this oil is olitained by first niaceratiug- the herb or seed with water and then distilling. It is colorless, possesses a peculiar penetrating odor and leek-like taste, reminding alike of garlic and mustard. If the oil is saturated with ammonia and the product distilled with water, there remains a residue of thiosinamine (m. p. 72°), thus indi- cating the presenc-e of all.yl sulphoe,yanate. This distillate .yielded with platinum chloride the same addition product obtained b,y Wertheini - (1844) from garlic oil. Pless, therefore, regarded it as all.yl sulphide. iSenimlerS (1802), however, has shown that ^Vertheim's conclusions are erroneous, that oil of garlic contains a group of different siilphides, but does not contain all.yl sulphide. The presence of allyl sulphide in the oil of Thlnspi ;irvense L. is, therefore, highly improbable. 158. Oil of Spoonvrort. Oleum Coclileariae. — Lolfelkrautiil. — Essence de Codilearia. Origix axi) Histohy. Spoonwort, Cochleni-ia officinnlis L. grows wild in the neighboi-hood of the coast-line of the northern continents anil in several mountain i-anges of the central European Alps. It is also largel.y cultivated, rpoii distillation the plant yields an oil jios- sessing a faint mustard odor. During the middle ages spoonwort was regarded as a remedy against scurvy. The distilled oil of spoonwort seems to have been known and to liave been used inedicinall.y since the middle of the sixteenth centur,y. This u.se, however, does not appear to have lieen general, for the oil 'is not mentioned in any edition of t'le Dispensatorium Xoricum, neither in the Pliarmacopoea Augustana nor in 8chroeder"s Pharmacopoea medicochymica of Frankfurt-on-t he-Main. It occurs, however, in the municipal ordinance of Frankfurt of l."')H7. Later it oi-cnrs also in inventories of apothecary shops of Braunschweig and Dresilen of 1640 and 1683 respectivel.v. At the beginning of the ei.chteenth century it was distilled by Hoffmann in Halle and described bv him. Preparation. According to (la darner ^ (1808), the dried herb, whicli need not be in blossom, is ma.c-ei-ated with water t(j wliidi powdered white mustard has been added and then distilled. The .yield is about 0.2;) p. c, or more. 1) Liebijj's AiiniilL-n. ."jS. ],. y.f,. i) Apothfker ZeitmiK, i:!, \t. 079: Arch. 2) Liebig's Annalen, 51, ii. 21lS. d. Phanii., 2.37, p. 92. 3) Archiv a. rhanii,. 2,30, p. i-'.i. 408 Spevinl Part. PR0PEHTIE8. Spooiiwoi-t oil is optirall.T active; Gadamer observed the angle 'j.-d = + 5."). 27°. Upf)!! distillation of 42.8 g. tlie following fractions were obtained: 150—154°, G.8 g. ; 154—156°, 12.2 g. ; 15(5—158°, 10.0 g.; 158—162°, 12.0 g.; residne 2 g. The sp. gr. of these fractions varied from 0.!)41 to 0.!)4H; the angle of rotation from + 51.41° to + G2.H7°. COiMPOSiTiON. Simon 1 (lUlO) gives tlie boiUng point of tlie oil at 156 — 159°. He found that it i-ontains sulphnr and yields a thiosin- amine-like derivative with ammonia. Gdeseler^ i-egarded the oil as l^eing free from nitrogen but containing oxj'gen ami pronounced it an 0x3'- sulphide of allyl. Hofmann^ (1869) .showed the oil to have the com- position of secondary butyl iscsulphoeyanate. Frrjm the bruised fresh herb"*- mixed with water he obtained O.081 p. c. of an oil distilling between 158—165°. After repeated fractionation, fraction Kil— 168° upon analj'sis yielded results corresponding with those for butyl mustard oil. Comparison with sjmthetic secondary butyl isosulphocyanate, CH.gCHs. (CH3).CH.N:C:S, revealed the identity of the two. It i.s a colorless hquid, sp. gr. 0.944 at 12°, b. p. 159.5°, and jiossesses the characteristic odor of the oil of spoonwort. When heated with amnioina to 100° it yields a thio-urea-" which melt.s at 188° and is optically active. According to Moreigne," spoonwort oil contains raphanol. Inas- much as the commercial, so-called artificial spoonwort oil is not secondary but isobutyl mustard oil it should not Ije substituted for the natural product in medicinal preparaticjus. 159. Oil from Horse Radish. The investigations of Gadamer'^ have rendered it highly probable that the formation of the oil of the root of Corhlearia nruionii-in L., to which the pungent taste of horse radish is due, is caused by the presence of sinigrhi. When the juicy root is grated, the glucoside is broken up by a ferment present with the formation of mustard oil. When distilled in glass vessels, the root yielils about 0.05 p. c. of oil. The crude oil is light yellow in color and has the consistency of cinnainon oil; the rectified oil is colorless. Hp. gr. 1.01. The odor is 1) Poffsentl. Annalen, .50, p. HTT. ,an nil upon distillation only when white 2) De {.'ochleariti ofHcinjili ejiiBqiic oleo numtartl meal has been ailded. dissertatlo. Korol. 1S57. ,'.) Gadamer, loo. cit. 3) Beriehte, 2, p. 1II2; 7, p. ."OS. 6) See under radish oil, p. 417. •1) AccordiuR- to Sijnon. dry licrl) yields 7) Arehiv d. Pharm., 2^5, p. .577. Oils of the Cmciferae. 409 penetrating, causes tears to flow and cannot be distinguished from that of mustard oil. Like the latter, the oil of hor.se radish causes burning- arid blistering when brought in contact with the skin. Oil of hor.se radish contains sulphur. Based on the results of elementary analy.ses as well as the formation of thiosinamine, Hubatkai (1848) concluded that the oil has the same composition as mustard oil. The statements of Hubatka have later been verified by 8ani.2 "When kept in contact with water in a closed vessel for years, the oil dis- appeared and in its place acicular crj-stals were formed that had a silvery lustre and the odor first of horse radi.sh, then of peppermint and finally of camphor (Einhof,* 1807). 160. Oil of Hedge Garlic. From the roots of AlUiiria officinalis Andr. (Sisymbrium aUiaria Scop., Ger. Lauchhederich), AVertheim* (1811) obtained upon distillation 0.033 p. c. of an oil that could not be distinguished from mustard oil and which yielded thiosinamine melting at 74°. Judging from the odor the herb contains the same constituents as garlic oil. According to Pless" (181G), the oil of the seeds consists of about ')io mustard oil and i/io garlic oil. 161. Oil of Mustard. Oleum Sinapis. — Seiifol. — Essence de Montarde. I Ohi&ix and History. As black nnistard are designated the seeds of several mustard plants Ijelonging to the Cruciferae, viz. Brassicu nigra Koch (Sinapis nigra L. ) and B.juncea Hooker fll. et Thompson [S.juncea L.). B. nigra, belongs to the European- Asiatic flora and is culti- vated in most civilized countries, especially in those of central Europe; whereas B. jvncea, is cultivated on a larger scale in southern Rirssia, India and North America. The largest amount of seeds are used in the manufacture of table mustard, less for medicinal purposes and for the distillation of mustard oil. The first statement which indicates a knowledge of the fact that mustard oil can be obtained by distillation with water, is found in the writings of Porta; another in the writings of the Parisian apothecary Nic. le Febvre. Boerhaave, however, seems to have been the first to jn-epare the volatile mustard oil in 1732 and to have called attention 1) LleliiR's Annalen. +7, p. 1.53. 3i Seiies BerlinischcK .lalirbueh, .5, p. 36.5 2) Aecad. Line., ]S;)2; Ab.str. Berieht *) Llebig's Annalen, 52, p. 52. von S. & Co., Apr. 1 S94-. p. 50. =J Liebig'u Annalen, 5S, p. 3S. 410 Spechil Part. to its propei'ties. That it contiiins sulpliur wiis oliservpil tiy Thibierge of Paris in 1819. Boerhaave and MuiTay observed the great density of the oil: Jul. l^ontenelle determined the .specific gravity in 1824. Un(h)nbte(]]y those wlio prepared mustard oil knew that the volatile oil does not preexist in the seed but is produced by the acticjn of water. Yet the first to call attention to this fact were Glaseri in 182.5, Boutron and Robi(|uet2 in 18:11. and independently of these Faure-^ as well as Guibourt,''' both in 1S81. Shortly after (188;i). Dumas and Pelouze" made the first elementary analysis of the oil and discovered the thio- sinamine. which mustard oil forms with ammonia. Tliat mustard oil is produced by the action of a ferment was noticed l:iy J')Outron and P^rnmyO (iHdO). Tlipy isolateil myrosin by extracting the si'cd with alcohol and obtainnd mustard oil by allowing this substance to act on the acpieous extract of the seed which had previously been extracted with alcohol. Sinigrin or myronate of potassium, was first prepared by Bussy " (1840). He termed the underlying arid nrkle myroniijup and with Roljiquef^ determined its physical constants and its behavior towai'd reagents. Tlie knowledge of the chemical coni]iosition of the oil was advanced by Will" (1M44| and simultaneously by \Yertheimi" who regarded the mustard oil as allyl sulphocyanate. Lmlwig and Langeii in Isiio confirmed the existence of sinigrin and its decom- position by ferment ai'tion into mustard oil. sugar and potiissium acid sul]>hate. This reaction w;is madn more clear by the detailed studies of \\'ill and Koerner i- ( l.S(>! ). Artificial mustard (lil hail been prepared by the action of ,aflyl iodide on potassium sul])hocyanate by Zinini-' in ls."i."i and by Berthelot anil de Lucad* also in lS.")."i. The natural oil was therefore regarded as an ester of thioc,ya,nic acid. ()eser,i3 however, shnweil in ISO.") that aUyl thiocya,nati/ ami natural mustai'il oil ]H}ssess different ]iroperties. Tile true constitution of mustard oil as the ester of the isuthiocy.-inic acid was recognized by liilletei-i" and (ierlichi" in 1.S7.". Thev showed 1) j;ei>crt. r. il. Ph.nnii.. I. l'l'. |i. Hil'. S| .louni. ilc I'lianii., II. L>l3. j,. no. 2) .lelll'li. lie I'hai'iii., |[, 17, ]i. 2'.I4: ui Lieliis's Aimalfll, ."">::, p. 1. Ofitipi-'s M.in-nzin r, I'liai-iii. anil l-;x|)fr. i") Lirliiti's .\uaaleii. .".L>. p. .■,+. Kritik, :-'.(;. ].].. 11+ anil 07, ill 7,1'Usclir. f, I'heniie nad riiarni., 3. Ill .luara. di- I'harai., II. t7. |>. 12'.)'.1; ]>]>. 431), .',77. 21. |i. +i;4. ii.'i l.icliiK-'s .Vaiialcii, li;.-,. p. l'.-i7. -I) .roiini. ilr I'liana., II, 17, p. MCll. i.T| .Idara. f. pi-.akt. I'hcm.. lU. p. .->04 ; ■'"'J .-Villi. lU- Chilli, ct I'liys,. II, .-,:>,, jj. ric'bin'.s .Viuialeli, i,)."i. p. IL'^. 1S1: LiebiK'h ,\aiialeii, tii. p. :1L'4. it) Ciniipt. roiiil.. 41. p. 21. Ill .loiirii. ilf riiariii., II. L'll. pp. 4S i.-| Lifliiji's Annali-ii. l:i4. p. 7. ami 111^: Lipliis'K .\iiiialea. ;!4, p. 2:'.i). lU) Ili-ni-Utc. s. ],ii. 4lU anil SLJO. 7) .l.iiini. (If I'liarm.. II, I'd. j). :!<.); U) Ilpi-ii-htc. N, p, 0,-,ij; LieliiR-'s .imnalen, Lk'liiii's Aiinali'ii, .'14, p. 2"J3, 17s, p, su. Oils of the Cniciferne. 411 tliat by tlip interaction of allyl iodide and potassium sulplio- cyanate, allyl sulphoeyanate is tirst formed and that upon heating this is converted into its isomer, the allyl isosulphocyanate. As an expla- nation of this form of isomerism, Hofmanni in 18(58 had suggested that in tlie true thiocj^anates the carbon is directly united witli the sulphur, but in the iso compounds with the nitrogen. Inasmuch as the possibility was not excluded that by the ferment action (jn sinigrin allyl sulphocyanate may first be formed, Schmidt - allowed this action to take ijlace at low temperature. He ascertained that even at 0° allyl isosulphocyanate is formed and only traces of the normal isomer. The hist uncei-tainty in connection witli the hydrol\'sis of sinigrin was removed by Gailanier'^ (1897). He showed that tlie formula of sinigrin is CioHioNSoKOd and not CioHisNS^KOio as was supposed by Will and Koerner. also that the hydrolysis takes place by the additirjn of the elements of one molecule of water. Phepah.\tion. The mustard which is used in the manufacture of mustard oil is obtained either from UrnsNicn nigi'n K. {Sin;ii>is nignilj.) which is cultivated in Holland, Apulia or the levant, Or more frequentlj' from B. juncea Hook. fll. et Thomson \S. juucea L.), a species wliidi is cultivated on a large scale in Sa.rejita, in the Russian gouvernement Saratow. also in East India. Mustard oil is not contained as such in the seeds, but is formed liy ferment action. Tlie ground mustard seed is deprived of its fatty oil with tlie aid of hyilra.ulic presses. The press-cakes are mixed with tepid water and allowed to undergo ferTueiitatiou, and then distilled witli water vapor. The yield varies between ().."> — 0.75 p. c. of the original seed.-i i| Bcrichte. 1. ]!. 2S. ■ 2) Beik-hte, Id. ji. IsT. 3| Archiv cl. I'hariu., 2;l.". p. 44. -I) Frir the <|uaiititati\'e e.stiniation of niiistai'd oil ia tlir scimI. the method f)f IHeteric-h l llelfenbers'ei- Annalen, 18913. ]». .-{:iil) can be eni])lo,veil : .' r. ol the liriii.sed koimI are allowed to fernient lor two hours at a temperature of fi-om 20 — 2.*)^, when 10 g. of alcohol are added. The flask is conneL-ted with a condenser, the tiil)e of which dips into the receiver containing- 80 cc. of ammonia. The iliKtillation is continued nntil .50 — GO cc. have passed over. To the ammrmlacal liiinid an excess t)f silver nitrate solntion is added, the precipitated silver sulphide is collected on a filter, ^^ashed. dried a7id heated to a red heat. The reduced silver is then weig-hed and its weight multiplied b,y 0.49;iS. The product gives the amount of mustard oil in 5 g. of seed. Cjadamer (Arr-h. d. Pharm., 235, p. ■~)S) has modified thepiocess somewhat. Before the distillation he adds a definite quantity of N'/IO silver nitrate \'. S. known to be in excess to the ammonia. After the distillation, the distillate is ililuted to a definite volume, set aside for 12 hours and filtered through a dry filter into a dry flask. In an aliquot part of the filti-ate, acidulated w\{\\ intric acid, the excess of sil\-er is titrated hack with potassium sulphocyanate. •il2 Sppcinl Part. At a tem]iei-ature fxeef-dina- 70° no fermentation takes place, because the niyrosin is coagulated and rendered inactive. The fermentation is brought about by the albuminoid ferment, myrosin, which acts on the sinigrin in the presence of water with the formation of nuista.rd oil, dextrose and potassium acid sulphate. CioHioNS2K09 + HoU = CSNCyH., + <'aHi20o + KHSO4 Sinlgrln Water Mustard oil Dextrcise Potassium aiid sulpliate. Beside this reaction others take place resulting in tlie formation of nllyl cyanide and carbon disulphide, which are never entirely wanting- in tlie oil. Oonta.ct with the copper of the still, or prolonged rontact with water i-ause the separation of suljihur and the formation of allyl cyanide. C3H,5NC.S + rocess of fornni- tion, a better, yield can be obtained by neutralizing with alkali (when 1) Liebie's Aniialen, ]2.'5, ]). 2T8. 3) Gailamer, loc. cit. 2) Ai-cliiv d. Pharni., 23."i, p. ,^:i. Oi/.s of the Crnciferae. 413 pure siuigriu is used). Au excess of alkali is to be carefully avoided, because it also diuuuislies the yield. Calcium carbonate has also been found serviceable. AVitli mustard meal, however, it is quite different. The addition of calcium carbonate not only is of no advantage, but its presence acts detrimentally. The cause for this has not yet been explained. Possibly the base sinapine, which is contained in the mustard enters into the reaction by being liberated by the calcium carbonate, forming a non-volatile thiosinamine-like compound with the mustard oil.i Composition. Besides small variable amounts of allyl cyanide and carbon disulphide, mustard oil consists almost entirely of allyl mustard oil or allyl isothiocyanate, C.sH.'jNCS. Possibly traces of the isomeric allyl thiocyanate, and higher boiling (polymeric?) unknown compounds are present. ' The chemical reactions of mustard oil are, therefore, largely those of allyl isosulphocyauate which can be found in any chemir-al reference work. Here only those will be mentioned that are necessary to under- stand the tests. For the qua,ntitative determination of allyl isosulphocyauate in mustard oil, its pr(jperty of ff)rming a solid, non-volatile compound with ammonia is utilized, [f to mustard oil an excess of ammonia and alcohol are added, the odor of both mustard oil and ammonia dis- appears, gradually in the cold tiut more rapidly when heated, while crystals of thiosinamine are formed. V f XT XT /NH . C3H5 cr^'^-^^° + ^„ =C-NH2 Mustaril oil Anmiunia Thiosinamine Thiosinamine or allyl thio urea crystallizes in rhombic prisms which melt at 74°, possess a faint leek-like odor and taste, and are readily soluble in water, alcohol and ether. When a small amount of mustard oil is mixed with twice its volume of concentrated sulphuric acid a violent reaction sets in with the formation of carbon oxysulphide,^ sulphur dioxide 3 and allylamine sulphate. The last remains as a faintly colored liquid which sometimes solidifies in the test tube. Artificial mustard oil is obtained hj the interaction of allyl iodide and potassium thiocj'anate in alcoholic solution. Allyl thio- cyanate is first formed which under the influence of heat rearranges itself to the isothiocyanate. 1) Gadainer, loc, cit. ") Archiv a. I'harm., 196. p. 214. 2) Berichte, 1, p. ISa. 41 -t Specinl Part. C3H5I + N(JSK = C'^HoNCS + KI Ally! ludldp I'utassiuiii thloi-yanate Mustard oil I'otassiniii Iciilkle. Mustard oil also results by the dry distillation of potassium ally! sulphate and potassium thif)cyanate. CaHsKWOi + CNSK = O3H5NC.S + K2SO4 i'otassiutii allyl sulpliate Putassliiin ttilccyaiiate Mustard oil I'otassiuni snlidiate. Properties. Mustard oil is a mobile, colorless or yellowish, strongly refractive liquid, which is ojitically inactive and which has a very strong odor causing' tears to flow. When brought in contact with the skin it draws lilisters. The S])eciflc gravity varies in accordance witli the method of preparation between l.OK; and 1.022 and sometimes rises u]j to 1.030. Mustard oil is soluble in 160 — 800 p. of water, and in 10 ]i. of TO p. c. alcohol. With i)0 p. c. alcohol. \'rtth ether, amjd alcohol, benzene and petroleum ether it is miscible in all pro])ortions. It boils principally lietween 14s — 1,")(5° (b. p. of pure allyl isothiocyanate is 150.7°). Exposed to liglit, mustard oil gradually becomes of a reddish-brcjwn color. At the same time a. film, cr)nsisting of a sub- stance composed of carbon^, nitrogen, liydrogen and sulphur, is dept)sited on the inner wall of the bottle. Ex.iJiiNATiON. The German Pharmacopceia contains a .series of tests, that have been taken almost uncha-nged from the V. S. Pharmacopceia of liS90, which generally suttice for the i-liaracterization of a good mustard oil. 1. Tlie sp. gr. is to be l.OlS— 1.021) according- tci the U. S. P., 1.010—1.022 according to the Ph. Ger. A slight variation either way, however, is not sutHcient indication of adulteration, for the reasons mentioned inider Preparation. 2. The requirement of both pharmacopceias that the boiling point is to lie between 14:,S— l.jQo cannot be construed literally inasmuch as allyl isothiocyanate Ijoils at l.'iO.T" (mercury in va])or). Furthermf)re, a sliglit decomposition invariably takes place during the distillation, so that some of the oil distills above 152°. Inasmuch as allyl cyanide is always present, the first fractions cannot have the same specific gravity as the original oil. Large differences in this respect will be accompanied by a lowering of the boiling point of the first fractions and should not be tolei'ated. ^■^. Sulphuric acid test. If to 3 g. of the oil (i g. of sulphuric acid lie gradually added, the liquid being kept cool, the mixture, upon subsequent agitation, will evolve sul])hur dioxide, Imt will remain of a light yellow color, and ,at first pei-fectly clear, beconnng afterwards thick Oils of the Criiciferae. 415 and occasionally crystalline, while the pungent odor of the oil will disappear. In the presence of petroleum, petroleum ether, chloroform or undue amounts of carbon disulphide, the mixture of mustard oil and sulphuric acid is rendered turbid and upon standing forms two layers. Other volatile oils would be rendered dark in color bjr the sulphui-ic acid. -A. Fei-ric chloride test. Diluted with ~> p. of alcohol, mustard oil is not changed bj^ ferric chloride. Adulteration with oil of cloves would be recognized by the production of a bluish-green color. 5. The tliiosinaniine test according to the U. B. P. is to be made as follows : "It a mixture of 3 g. of the oil and 3 g. of alcohol be shaken in a small flask with 6 g. of ammonia water, it will become clear after standing for some hours, or rapidly when warmed to 50° C. (122° F.) and usually deposit with- out becoming eolored, crystals of thiosinamine [allyl-thio-urea, CS .NaHalC.iiHs)]. "To determine the proportion of thiosinamine obtainable from the oil, de- cant the mother-water from the ory,9tals, and evaporate it gradually in a tared capsule, on a water-bath, adding fresh portions only after the ammoniacal odor of each preceding portion has disappeared. Then add the crystals from the flask to those in the capsule, rinsing them out ot the flask with a little alcohol, and heat the capsule on a waterbath uutil its weight remains constant. The amount of thiosinamine thus obtained from 3 g. of the oil should be not less than 3.2,5 g., nor more than 3.5 g. After cooling, thiosinamine forms a lirow^nish, crystalline mass, fusing at 70° C. (158° F.) and having a leek-like, but no pungent, odor. The mass should be soluble in 2 parts of warm water, forming a solution which should not redden blue litnms pajjer, and which possesses a somewhat bitter, not persistent taste." Attention should be called to the fact that, by following tins test, carbon disulphide is included in this estimation since it also unites with ammonia according to the following equation : CS2 + 4NH3 = NHiSCN + (NHilaS Oarbuu disulphide Aininonia Ainiuouiuni sulptiocyanate Aniinoniuiil sulpljide. Inasmuch as the products of the reaction remain behind upon evaporation, the residue may weigh more than 3. -5 g. If this is the case and especially if the residue has the odor of ammonium sulpliide an unwarranted amount of carbon disulphide was probably present. Kremeli (1888) has suggested the use of ammonia of definite strength and to determine the exce,ss with N/2 acid. As j^et no practical test of this method seems to have been made. According to Gadamer^ (1899) mustard oil can be assayed titrimetri- cally acc-ording to a method that is also applicable to spirit of mustard. 1) Phann. Post, 21, p. 828. 2) .irchir d. Phariii., 207, pp. 110, .372. 410 Special Fart. A solution of 2 p. of mustard oil in 98 ]). of alcohol (Spiritus shiapis Ph. (i. ) is first iirepared. 5 cc. of this sjjirit (4.2 g. ) are transfei'red to a 50 ce. measuring flask, and 25 cc. of N/lO silver nitrate V. S. and ."> co. ammonia are added. The flask is well stoi)pered and set aside for 24 hours. The liquid is then diluted to the .50 cc. mark and filtered. 25 cc. of the filtrate, after the addition of 4 cc. of nitric acid and a few drops of ferric chloride T. S., should not requii-e niore than 4.5 cc. and not less than 4.1 cc. of X/10 ammonium sulviho- cyanate to produce a permanent red color. These numbei-s — 4.1 and 4.5— correspond to the requirements of the Ph. G., viz. a content of 92.6 to nearly 100 ]i. c. of allyl mustai'd oil. Griitzneri converts the allyl isothioeyanate into thiosinamine and oxidizes this with sodium peroxide. Tlie resulting sulphuric acid is estimated as barium sulphate, either gravimetrically or volumetrically. DetermIxN'Ation of Carbon Bisulphide in Mustard Oil. For tlie detection of not too small amounts of carbon disulphide. i. e., in case of adulteration, it can be converted into copper ethyl xanthate- and determined quantitatively. 20—25 g. of mustard oil are heated on a water bath while a slow current of air is passed through the oil. The vapors of carbon disulphide are thus carried over, cooled by passing through a condenser and conducted into alcoholic potassa where they are ccjnverted into potassium ethyl xanthate. After the alkaline solution ha,s been neutralized X/10 copper sulphate V. S. is added until a di'O]! produces a reddish-brown color with potassium ferro- cyanide, i. e., until a slight excess of copper sulphate has been added and all potassium ethyl xanthate has been converted into the cuprous salt. From the amount of the consumed copiper solution (1 cc. corresponds to 0.0152 g. of carbon disulphide) the percentage of carbon disulphide present can be ascer- tained. This volumetric process can be supplemeuted by a gravimetric one. The precipitate of cuprous ethyl xanthate can be collected on a filter, waslied, dried and heated to a red heat in a crucible, and the residue of cupric oxide weighed. 1 g. of the oxide corresponds to 1.918 g. of carbon disulphide. Foi- the quantitative estinuition of traces of carbon disulphide whii/h occur in every mustard oil, the metliod of HofmannS can be used a.ccording to which it can be converted into a compound with triethyl plio.sphine, P(C2H.r, )3 + Ci^2, and weighed. 162. Oil of White Mustard. Sinalbin is the glucoside from the wliite inustard (Sinnpis nlba L.) corresponding to the sinigrin from the black mustard. Eobiquet and Boutron-Cliarlard* (1831) first extracted it with boiling alcohol from the seed deprived of its fatty oil. Its properties, including its hydrolysis 1 Archiv. il. Pharm., 237, p. 18.5. 3) Bcrkhte. liS, p. 1732. 2) Zeitsehr. f. anal. Cliem., 21, p. l;i;>. i) .Journ. de Pharm., II, 17, p. 27i>. Oils of the Cruciferae. ' 417 bv myrosin, were examined bj' Will and Laubeuheimer i (1879) and recently by GadamerS (1897). The identity of the white mustard oil with para, hydroxy benzyl isothioeyanate was established by [^alkowslds (1889). Sinalbin mustard oil, C8H4. OHCi] . CH2NCSW, jg ^^^ sparingly volatile with water vapor and for this reason cannot be prepared from white mustard by distillation. It is an oily liquid of a burning taste, wliich draws blisters when in contact with the skin but much slower than ally] mustard oil. The pungent mustard oil odor is noticeable only when heated ; when cold it possesses only a faint anise-like odor. It is soluble in dilute alkalies. It is prepared by the hydrolysis of sinalbin, dextrose and sinapine sulphate resulting as bj'-products. C3oH42N2S20i5 + H2O = C-HtONCvS + C6Hi20e + C16H24N2O5HSO4 .Sinalbin Sinalbin niustartl oil Dextrose Sinapine acid snlphate. Artiiieially it is prepared by the action of carbon disulphide on p-hydroxy benzylamine and by treating the resulting product with mercuric chloride. 163. Oil of Water-cress. The oil of Nasturtium oiScinale L. was examined by Hofmann* in 1874, who extracted the aqueous distillate (600 k.) from 600 k. of fresh herb with petroleum ether. Upon evaporation of the ether he obtained 40 g. (=0.0006 p. c. ) of oil. The oil no longer had the odor of water- cress, -sp. gr. 1.0014 at 18° and distilled between 120 and 280°. The principal fraction came over at 261° and was shown to be the nitrile of phenyl propionic acid, CoHs . CH2 . CH2 . CN. Moreigne found raphanol^ in the oil. 164-, Oil of Radish. The roots and seeds of Raphanus sativus L., (Family Cruciferae) yield upon distillation with water vapor a small amount of a colorless, sulpliuraceous oil, lieavier than water, which po.s8esses the taste but not the odor of the radish." Upon the distillation of the roots of Rapha^nus niger, Moreigne''' obtained besides a small amount of oil, 0.002.5 p. c. of a substance which crystallized in laminae melting at 62°. It was called raphanol 1) Liebig's Annalen, 199, p. 150 «) Pless, Liebig'.s Annalen, 58, p. 40. 2) Archiv a. Pharm., 235, p. 8.3. Comp. also Bertram & Walbaum. .Journ. f. 3) Berichte, 22, p. 2143. prakt. Chem., II, 50, p. 500. *) Berichte, 7, p. 520. T) .Tourn. de Hliarm. et Cliim., VI, 4, p. 5) See under radish oil. 10; Bull. Soc. chim., Ill, 15, p. 797. 27 418 Special Part. or, l;)ecause it possessed the properties of a lactone, raplianolid. It is free from nitrogen and siilplmr, elementary analysis and molecular weight determination indicating the formula C2»H5804.i When boiled with acetic acid anhydride, it yields an acetyl derivative melting at 122—128°. The liquid portion of the oil was found to contain sulphur but was free from nitrogen and did not combine with ammonia. 165. Oil from Mignonette Flo-wers. Upon steam distillation of the fresh tlowers of Reseda odorata L. (Family Resedaeeae) an oil yield of but 0.()()2 [i. c. is obtained. Eemark- able is the strong development of carbon disulphide^ during the process of distillation. The oil is of a. dark color, and solid at ordinary tem- periitnre, having the consistency of orris oil. When greatly diluted it has the odor of fresh mignonette. ^ In order to obtain the oil in a more suitable form for use it is distilled with geraniol (1 k. of geraniol to '>()() k. of flowers), the i)roduct being l>rouglit into the market as "Keseda Geraniol."* 166. Oil from Mignonette Root. The fresli roots yield upon distillation with water vapor O.Oll — (>.0;:')."i p. c. of oil. It is a. light brownisli liquid which has the odor of radish, sp. gr. 1.010—1.084. «d = + 1°30'. It begins to boil at 255° with decomposition. Even under dinunished pressure it does not boil without decomposition. The oil was first exaruined by VoUrath^ in 1871, who recognized its character as that of a mustard oil. His surmise that it was identical with ally] musta-rd oil was, howevei', shown to be errcmeous li^^ Bertram and Walbanm"- (18!)4), who ideutitted it as jihenyl ethyl mustard oil, C6H.,CH2.CH2NrSl. The odor of this substa,n(ie is that of the mignonette root oil. Upon heating with ammonia, the well crystallizing thiourea. NHo.CS.- NH(:2H4C6ll5 is formed, which melts at 187°. If this thicjurea is treated witli .silver nitrate and baryta, water, silver sulphide and phenyl ethyl urea, i-rystallizing in long needles and melting at 111— 112°, are formed. If i)heiiyl ethyl mustard oil is lieated with concentrated hv p. c. of volatile oil, when distilled with super- heated steam about 1 p. c. of oil. Properties. Oil of storax is a light yellow to dark brpwn liquid of a pleasant odor. The specific gravity varies from 0.89 to 1.1, according as the hjnlrocarbons or the cinnamic esters predonunate. It is laevogyrate, aD = — :! to —38°. It boils between 1.50—300° with partial decomposition, cinnamic ac-id remaining behind. Composition. The peculiar odor of the oil, reminding somewhat of petroleum, is due to the presence of styrene, C0H5 . CH : GH2, or phenjd- ethylene ( Simon, ^ 1839). This hydrocarbon boils at 11G°, is optically inactive and can be identified by means of its dibromide, ('oHi'r, ■ (JHBr . - CH2Br. (Comp. p. 103). According to van't Hoffs (18TG), the optical 1) Berlchte, 19, p. 1824. 3) Berichte, 1>. \>. r,. 2) LiebiK's Annalen, 31, p. 26.5. 420 Special Part. activity of the oil is referable to an oxj-genated constituent, the styi-o- camphene, Ci„Hi60 or CioH,sO. The oil also contains more or less of the cinnamates of ethyl, i benzyl, 2 phenyl propj^P and cimiamic alcohols. 1 168. Oil from American Storax. Origin and History. Ocosotl, an aromatic balsam from Mexico and (Jentral America, is one of the drugs from the new world which attracted interest in Europe. In almost all of its properties it clearly resembled the St.yrax liquidus, the storax coming from the levant and Icnown since antiquity. Its origin, like that of the levant article and especially tlint of the other American balsams (Tolu, Peru, Copaiba etc.) was for a long time uncertain and created much confusion. The first description of American storax is found in the works of Monardes, Garcia ab Orto and Matthiolus, wlio lived during the first half of the sixteenth centurj'. LiqnJdambcir styrneifiuum L. (Family Hnina.jnelklaeea.e) is a tree found in the middle and southern United States, in Mexico and Central Ameri(/a. The resinous balsam of the consistence of honey exudes from the splintwood beneath the bark of the trunk and branches. The excretion is either spontaneous or may be caused liy incisions, but occurs abundantly only in hot climates. For this rea.son it enters the market principally from the Central American c-ountries. According to the method of preparation, the balsam varies in appearance and con- sistency. In North America it is known as sweet gum and is used as a chewing gum and in the preparation of popular remedies. ^ The first examination of Amei-ican storax was made by Bonastre* in l.s3() and 1881. Upon distillation of an apparently fresh balsam, he obtained 7 p. c. of oil. Further investigations were made by Proctor" in 1857 arid by Harrison <• in 1S74. Properties and Composition. According to v. Miller," the oil frmii American storax differs from that of the levant by being dextrogyrate (oD = + 1G°33'), and contains styrene (bromide, m. p. 73°) and an opti(_'a]ly active substance having the odor of turpentine oil, which 1) Lieljig's Annalen, 188, p. 184. 2) Liebig's Annalen, 164, p. 1289. 3) Pharm. Rundschau, 13, p. .~)7. i) .Tonrn. de Pharm., II, 16, p. 88; 11, 17. p. 338; Ti-ommsdorff's Neues .lourn. d. Pharm., 21. II, p. 242, and 24, II, p. 236. 5) Am. .Jonrn. Pharm., 2i), p. 261; 38, p. 33.— Proc. Am. Pharm. Assoc, 13, p. 160. 6) Am. .lourn. Pharm., 46, p. 161; Arch. d. Pharm., 206, p. 541. 7) Archiv d. Pharm., 220, p. 648. Oils of the Haiimmelirlaceae. 421 was not further examined. American storax contains the einnaiiiates of cinnamyl (styracin) and phenyl propyl alcoh(_)ls, but not of ethyl and benzyl alcohols. The leaves of the American storax have a peculiar terebinthinate odor. Upon distillation >- they yielded 0.085 p. c. of a mobile oil, which was greenish-yellow; sp. gr. 0.872; wd = — 38° 45'; saponiflcatiou number 5.9; acetyhzation number 25.2. The odor of the oil reminds of the pine needle oils. It probably contains borneol and bornyl acetate in addition to terpenes. 169. Oil from Rasamala Wood. Upon distillation of a wood coming from the Dutch East Indies and designated Rasamala, Schimmel & Co.^ obtained 0.17 p. c. of a volatile oil. At ordinary temperature, this oil is a light brownish, crystalline mass, which melts between 30 — 40° and the odoi- of which reminds alike of cinnamon and rhubarb. The principal constituent of the oil is a crystalline substance which melts at 54 — 55°. It is probably a ketone, since it combines with hj'droxylamine to a crystalline compound melting at 106 — 107°. The other constituents of the oil are liquid. According to a communication by Dr. van Komburgh of Buitenzorg the term Rasamala is not only applied to the genuine but rare rasamala tree, Altingia exeeha. Nor. { Liquid nmhav altingia Bl., Fa.mily Hama melidaceae) but also to different Indian drugs, namelj' to the liquid storax from Liq. orientale (Getah Rasamala) as well as to other fragrant balsams and to the fragrant wood from Canarium microcarpum Willd. ( Kaju Ra ^a mala ) . Whether the oil distilled by Schimmel &. (.'.o. was derived from any one of the above named trees is uncertain. Possibly it may have been the so-called aloe or eagle wood (Ger. Aloeholz) fi-om Aqiiillaria agal- locha Roxb. which is sold in the Indian markets as Kaju lakka and the characteristic rhubai-b-like odor 8 of which corresponds with that of the wood distilled by Schimmel & Co. 170. Oil of Spiraea. Oil from the flowers. In 1835 Pagenstecher* obtained upon distillation of the flowers of Spiraea ulmaria L. a small amount of oil 1) Bericht von S. & Co., Apr. 1898, p. 58. 2) Bericht von S. & Co., Apr. 1892, p. 43. 3) Bericht von .S. & Co.. Apr. 1892, p. 43. According to a recent investigation by Prof. MoHer (Pharm. Post, 18981 aloewood is odorless and developes a peculiar odor only ^vhen burnt. i) Kepert. f. d. Pharm., 49, p. 337. 422 Specinl Part. heavier than water whic'h he gave to Loewigi for examination. Dumas^ (1839), to whom the oil was whown, recognized its .similarity with the salicylic aldehyde obtained from salicin by Piria .shortly before. EttlingS (1839) verified Dnmas' surmi.se by showing that salicylic aldehyde is one of the two or three volatile substances of which the oil is composed. Etthng had obtained a jdeld of 0.2 p. c. of oil upon distniation of the flowers. According to Wicke* (1852) the cultivated variety produces a la.rger yield than the wild plant. The oil is heavier than water and congeals completely at — 18 to — 20°. The investigations of ydmeegans and Gerock" (1892) have shown that besides salicyli(; aldehyde (formerly known as spiroyl hydride, spiraeic acid, salicyl hydride, .spirojdic or spiric ai.-id) the oil also contains methyl salicylate, also traces of heliotropin (itiperonal) and vanillin. Ettling had also found a small amount of white, crystalline matter of a ])early lusti-e (paraffin?) and an oil of tlie conipcjsition CbHs (terpene or .sesquiterpene?). According to Schneegans and Gerock, the flowers do not contain salicylic aldehyde as such, but an unknown sub.stance (not salicin, however, as suppo.sed by Buchner") which is decomposed during the process of distillation l:)y a ferment. In addition to methjd salicylate, the flowers contain free salic.ylic acid. Oil from the roots. The statement of Wieke, that the roots of S[iirae;i uhuaria L. contain salicylic aldehyde, is incorrect. Acconling to Nietzki''' (1M75) the oil consists principally of methyl salicylate with traces of another substance, pi-obably a hydrocarbon. Oil from tlie herb. In the di.stillate from the herb, Wicke has shown the presence of salicylic aldehj'de. According to Wicke the herb of .S'. digitatn, S. lohata, S. filipendula und the flowers of .S". aruiieus yield salicylic aldehyde upon distillation. The herl:) of S. ai-iincus, the lea.ves of .5. Japojiica., the herb and flowers of S. soi-bifolia yield hydrocyanic acid but no salicylic aldehyde. Neither aldehyde nor acid were found in the oil from S. laevigata, S. a.cutifolia,, S. iilmifolin, and .S'. opulifolia. 1) Poggend. Ann.. .36. p. 38.3; Pharm. Centralbl., 183i). p. 1 2<). ^) Liebig's Annalen, 29, p. 306. 3) Liebig's Annalen, 20, p. 300: 3.~, pji. 1, 24. •») Licblg's Annalen, 83, p. 17.5. 5) .Journ. a. Phai-ni. f. Elsass-Lotlir., 19, pp. 3 and 5."i. Abntr. .Jahresb. f Pharni 1892, p. 164. '■') Liebig'8 Annalen. S8, p. 284. T) Archiv d. Pharm., 204, |i. 429. Oils of the Rosaceae. 423 171. Oil (Otto) of Rose. Oleum Rosariim. — Roseiiol. — Essence de Rose. History. Since the earliest periods the charm and fragrance of the rose has led to its appreciation and use. This is shown hy the entire older literature, and of all the flower perfumes that from the rose has always received preference. In Chinese and Sanskrit writings the fragrance of the rose is much praised. Fats and oils saturated with the rose peii'ume have been used since earliest antiquity in perfumery. Thus Aphrodite anointed the dead body of Hector with rose oil. The Greeks and Romans celebi'ated annuallj' a rose festival, at which the graves of the dead were decoi'ated with roses and their tombstones were anointed with rose oil. Of the various flower c-ults that of the roses has been the most eminent since antiquity. The ea.rliest description of the method of preparation of the oil of rose of the ancients is found in the writings of Dioscorides. It was an aromatised fatty oil as were the majority of the rose oils of the middle ages, such as Oleum rostirum, 0. ronatum or O. vosiiceum, etc. Aside from apocryphal Persian and oriental traditions, the earliest definite directions for the preparation of roses and the use of the distil- late is found in the writings of the Arabian historian Ibn Chaldun. He mentions that during the eighth and ninth centuries rose water was an important article of commerce, being carried as far as China and India. In a codex of ceremonies of 946 by the East Roman emperor Constantine VII., Persian rosewater is mentioned a,s a toilet water. At the beginning of tlie tenth century, Nonus Theopha,nes, the physician of emperor Michael VIII. , recommended and used rose water as a medicament. Avenzoar, the physician of the cfilif Ebn Attafii- of Morocco, who lived at the beginning of the twelfth century; also his contemporary, Joannes Actuarius, a physician of Constantinople, used rose water as an ophthalmic, and rose sugar as an internal remedy. During this period, Persia seems to have supplied most of the i-ose water. During the fourteenth century it was also exported from Meso- potamia. After the prime of the levant commerce, the Portuguese and Dutch were the principal carriers of goods between Aden, the ports of the Persian bay, India and the Occident. Rose water constituted one of their principal articles of merchandise. During the tenth century the distillation of roses was introduced into Spain by the Arabs. Throughout the middle ages, the distillation of rose water seems to have Vjeen an important in<]ustry of Persia.. Unless strongly alcoliolic 424 Special Part. wine was used in tiie process, one would expect that in tlie distillation of large amounts of rose water the separation of oil of rose at low temperatures in the form of a butyraeeous mass had l)een noticed at an early date and probabl.y used to perfume fats and fattj^ oils. The first statements concerning rose oil, which possibly refer to the distilled oil, is found in the writings of Mesues, and in the almanac of Harib for the year 961, which mentions the time suitable for the pre- paration of rose water and a rose preserve. In his Compendium aroma- tariorum written about the middle of the fifteenth centurj-, 8aladin of Asculi. the body physician of a prince of Tarentum, describes the distillation of roses for the preparation of rose water and i-ose oil. According to a statement by Langles, distilled rose oil is twice definitely mentioned in Mohammed Achem's history of the great moguls of 1525 to 1667 ; also in the annals of the Mongolian empire written by Manucci, a Venetian physician who lived 40 years in India. Unquestioned mention of the butyraeeous oil of rose is made in 1574 by Hieronymus Eubeus, body physician of Pope Clemens III. ; also in the writings of Porta of the year 1563 and again in 1604. In the apothecary tax-ordinances of AVorms of 1582 and of Frankfurt-on-the-Main of 1587, Oleum ro.sarum veruin is mentioned in the list of distilled oils. About the same time Angelus Snla describes the distillation of rose oil and designa,tes it strikingly as cnndiscente pinguidine, instar upermatis ceti. In his Pharmacopoeia of 1641, Schroeder enumerates the oil under the Olea destillata iisitatoria. Up to the seventeenth century and lieyond, however, Persia ]3rincip- ally seems to have supplied the market with rose water and rose oil. In the course of the century, however, the cultivation of the rose nnd the oil indu.stry spread to India, Arabia. Tunis, Algiers, and Morrocco to the south, also to Asia Minor, Turkey and Bulgaria tci the north. On the island of Chios also considerable rose oil was distilled at the beginning of this century, wliich entered commerce via Smyrna. The cultivation of roses in Bulgaria, which became of such import- ance in later years, was begun about the l.ieginning of the seventeenth century. It seems to about coincide with the founding of Kezanlyk, a city on the southern slope of the Balkan mountains in East Roumelia. It was not until the nineteenth century, however, that the rose industry of Bulgaria became a dangerous competitor of the Persian rose distillation. In recent years Bulgaria, in turn, has found successful competitors in German V and France. Oils of the Rosaceae. 425 Since the fourteenth century, rose water and with it small quantities of rose oil, have been distilled for popular and medicinal use, also for perfumery, in the north European countries, especially in France, Germany and England. The amount of oil, however, was so small that rose oil was mostly bouhgtr from the orient and later from the Balkan states. The cultivation of roses for the purpose of distilling rose oil on a large scale was begun in France about the middle of this century, in Germany in 1883.1 The high price of rose oil and the ease with which it can be adulter- ated seems to have brought about adulteration in Persia in the course of the seventeenth century. Engelbert Kaempfer from Lemgo, who traveled in Persia in the years 1682 to 1684, mentions that rasped sandalwood is added to the roses in the process of distillation. This observation was verified in 1787 by Archibald Keir in Chatra in the Eamgur, whereas Poller observed in Cashmere during the same jear that in this country not sandalwood, but the fragrant Indian grass (Andropogon) is added to the roses for distillation. Aside from its use during antiquity, the use of Andropogon sehoenanthus L. for the purpose of adulteration of rose distillates, dates back more than a century. As a more convenient adulterant, palmarosa oil is more recently used in place of the grass from which it is distilled in India. At an early period oil of rose was used as a perfume and, filled in fancy flasks, became a much sought for article in the bazaars of Coii- stantinople, Smj'rna, the levant and the entire orient. The demand being greater than the supply, both, manufacturers as well as dealers, early learned to increase the supply in a manner profitable to them- selves. The former added palmarosa oil to the roses in the process of distillation, the latter still further diluted it with indifferent oils and spermaceti, the latter being necessary to maintain the proper congealing point. Origin. Only a few of the 7,000 cultivated varieties of roses are used in the production of the oil. For the purpose of distillation, hand- some appearance is of less importance than hardiness and a rich yield of flowers. Both these qualities are possessed by the Rosa dajnaseena Miller, which is cultivated in the Balkan provinces and in recent years also in Germany for the production of rose oil. This variety does not occur wild, but is a product of cultivation and originally may have been a hybrid between R. gallica and R. canina. I) I'harm. Kunflschau, 12, p. 92. •426 Special Part. The Bnlo-arian rose-plant is armed with numerous not strongly recurved prickles. The glabrous, obtuse three paired lateral leaflets and the terminal leaflet are pure bright green, the calyx smooth and slightly primrose. In many cases the ordinarily racemose clu.sters — of as many as twenty- seven flowers — are almost cymes. In the fully expanded' condition the roses attain a maximum width of 7 cm. and, though double, they are nevertheless provided with numerous stamens with large yellow anthers. In many flowers the outer petals are almost white, becoming redder and redder toward the c-enter and under the 7iiost favoralile conditions i-hiefly pure rose-red. 1 i„ 74 Bulgarian Rose Oil Distilling Apparatus In Bulgaria and in Germany the roses are grown in fairly dense licdge.s, about the height of a man. In Bulgaria a white rose. 7^. alba L. is planted to indicate the divisions of the rose fields. It is said to yield an oil of poorer quality wliii;h is richer in stearojitene. In southern Fram-e R. c-entifolia L. is principally cultivated for the production of rose water ;ind rose pomade. It is planted in rows but forms less dense and lower hedges than the Bulgarian. It is uncertain which species of rose was cultivated in the fainous ro.se gardens of Schiras. Possibly it was B. gnllica. the dried petals of which are even to-day expoi'ted from Persiai in large quantities. In India where rose oil distilleries liave existed for two c-enturies in Gazipour on the Ganges and in other places of Bengal, R. dimmscena is likewise u.sed. The (jil distilled there, however, is never pure, but Oils of the Rosaceae. 427 it- ^ o K 428 Special Part. always contains sandalwood oil. An alread.y stated, the roses are generally distilled with sandalwood. Production of BuLCiAEiAN Rose Oil. The rose stills used in Bulgaria are very simple, and are to-day much the same as the ones described by Bauri 30 years ago. The copper still (Lambic) of 110 liters capacity rests on a fire-place built of stone (fig. 74) wliich is heated by wood from the near forests of the Balkan mountains. The conical still is 1.1 ni. high and provided with handles with which it can be removed from the fire-place. The middle diameter of the still is 0.8 m., at the neok it is 0.25 m. The helmet which is 0.3 m. high and which has the form of a toad-stool fits closely to the neck of the body of the still. The joints are made tight with clay and strips of cloth. The helmet is provided with an exit tube which is inclined to tlie ground at an angle of 4.5° and which connects with the condenser tube pro])er. The latter is straight, about as thick as a thumb, 2.5 m. loug and passes through a tub of oak or beech wood filled with water. The cooling water is conveyed by means of a wooden gutter. A number of the.se stills are usually mounted under one shed. Each apparatus is charged with 10 k. of freshly picked roses and 75 1. of water. The distillation is continued until two five liter lla.sks are filled with aqueous distillate. The water remaining in the still is used for the next charge, a pro- ceeding that is irrational inaBmucli as the salts and extractive matter which accumulate cannot be without influence on the delicate perfume. Wlien a sufficient amount of rose water has accumulated, 40 1. are transfei-red to a still and 5 1. are distilled off. This second distillate is at first a white, turbid liquid, which becomes clear ujton standing, the oily constituents separating at the surface. For the .separation of the oil, a, small tunnel-shaped instrument of tin is einployed in Bulgaria. The tube has but a very fine opening through which the water will ])ass but not the semi-congealed oil. Ai.'cording to unreliable and improbable statements 8,000 k. of flowers yield 1 k. of oil in Bulgaria, In all probability a much larger quantity of roses is necessary, though 3, 000 k. of flowers with a sufficient amount of palmarosa oil may yield 1 k. of Bulgai'ian rose oil. After the oil (Bulgarian GiUjag) has received another addition of palmarosa oil, which for this purpose is exposed to the sun in shallow dishes, by the broker, it is transferred to the well known tinned copper flasks {Estn.gnon.s) and is lirought into the market as Bulgarian rose oil. The designation Turkish is no longer correct, for in Turkey no I'o.se oil is distilled. Production of German Rose Oil. The first attempts by Sehiin- mel & Co. to distill rose oil on a large scale were made in 1883. At first RosH cpntitbliii L. from the neighborhooil of Leipzig was used. 1) Neues .fahrbufh fiir Phariiiacie iiiid vorwandte Filcher, '27, p. 1. Abstr. .lahresb. f. Pharm., 1K07. p. K50. Oils of the Rosaceae. 429 In 1888 the Arm obtained a considerable number of rose buslies from Bulgaria which, by skillful treatment were rapidly multiplied. At the present time 35 hectares ( = 86.4 acres) are being cultivated with this rose variety near Miltitz, a station 12 km. from Leipzig on the Thuringian R. E. The detrimental influence of the transportation on the freshly picked roses, made their distillation on the spot a necessity. Now there stands in the midst of the rose plantation a large faetorj' building equipped with the best modern apparatus. The freshly picked roses are at once taken to tiie large copper stills, which have a capacity for 1,-500 k. of roses in addition to the requisite amount of water (flg. 50, p. 81). From 5,000 to 6,000 k. yield 1 k. of oil. It goes without saying that here the crudities of the Bulgarian process are not tolerated. The stills are not heated with direct Are but with steam. For every new charge of roses fresh water is used and the oil is collected in a cascade-like series of Florentine flasks like all other oils. Owing to the greater care exercised, the odor of the German oil is by far superior to that of the Bulgarian oil. Although the stearoptene content is much higher, the intensity of its odor is again as great as that of the latter. A product, similar in intensity of odor and stearoptene content to the Bulgai'ian rose oil, is the rose geraniol of Schimmel & Co. which is made by distilling 2,500 k. of fresh roses with 1 k. of pure geraniol. Pboperties. The commercial Bulgarian rose oil is light yellow in color, and sometimes has a greenish tint. At 21 — 25° it is of the con- sistency of sweet almond oil, has a strong odor of fresh roses, and a pungent, balsamic taste. At about 18 — 21° acicular crystals or shining crystalline laminae separate out, which, on account of their lighter sp. gT. collect in the upper portion of the oil and coat the sur- face with a thin fllm that readily parts when the oil is disturbed. AVhen cooled the oil congeals to a translucent, soft mass, which is again liquifled by the warmth of the hand. The sp. gr. varies as a rule between 0.855—0.870 at 20°. being lowered by a higher stearoptene content. The oil is slightly laevo- gyrate, au = up to — l:°.i On account of the difficultly soluble paraffins which rose oil contains, it yields only turbid mixtures with even very large amounts of 90 p. c. alcohol. The liquid portion, the so-called oleoptene forms a clear solution with 70 p. c. alcohol. The 1) Baur, ^vhose Btatenients, however, are not always reliable (comp. p. -i.SO), found «„ = -(-4°. 430 Special Part. saponification number is 10—17. Rose oil has a slightly acid reaction, its acid number beino- 0.5— :i. For this reason the test of the German PharmacopfBia. that the chloroform-alcoholic solution should not redden blue litmus paper, is untenable. The temperature at which the rose oil begins to congeal, the congealing- point, lies between 15 and 22°, mostly between 17 and 21°. The stearoptene content varies from 10—15 p. e. On account of its larger stearoptene content, German rose oil from Roaa chimnficena Mill, is at ordinary temperature a greenish mass inter- mingled with crystals. The odor is much stronger and more persistent than that of the Bulgarian oil. The congealing point lies l)etween 27 and 37°, the sp. gr. between 0.845—0.855 at 30°; «,;, = + 1 to —1°. The stearoptene content varies between 26 — 34 p. c. An oil distilled in Leipzig from liona eentjfolia L. had the following properties: sp. gr. 0.8727 at 25°; «d = + 0°49'; congealing point + 28 ; saponification number 7.8. According to Du])()nt and Guerlaini. two French oils distilled in 1895 and 189« had the following pro](erties; sp. gr. 0.8225—0.8407 at 30°; ao at 30° = — (5° 45' to — 8° 3' ; .stearoptene content 35 and 20 p. .:■. Coi£PosiTioN. Shortly after the introduction of elementary analysis tlie first combustion of rose oil and its stearoptene was made by 8aus- sure- in 1N20. A second analysis was made by Blanchet-^ in 1.S33. The analysis of the oil merelj' indicated that it contained oxygen, that of the stearoptene that it was a hydrocarbon. Blanchet supposed the latter to be a terpene. CkiHio, whereas Fliickiger^ in 11SG9 first recognized in it a representative of the paraffin series. The vaptor density determination made hj Power ""^ in Fliickiger's laboratory indi- cated the formula riGH3+. Baur," wlio lias made numerous observations on tlie distillation of rose oil in Bulgaria and who made detailed reports in l.S(;7 and 1872, claimed that the odorless stearoptene could be con- verted into fragrant oleoptcne l_\y oxidation, and also tliat the reverse reaction could be made to take place. Later investigations, however, have not confirmed these statements. About the same time (1872) Gladstone'^ examined the li(piiil portion of the oil and found its boilino- 1) Ccimpt. riMul., 123, p. 7.-)0. 5) PlianiiakoKiio.sie, 3i-(l ed., p. 170. 2) Ann. cleChim. et Ph.vH., II, 13, p. 337. nstrated the identity of "reuniol" with citronellol, the i-eduction product of citronellal. 1) .4rchiy (1. Pharra., 22'.J, p. 3.55; also Bericlitu. 24, p. 4205; Poleck, Berichte, 23, p. 3.-).-:i4. -') .Journ. f. prakt. Chem.. 11, 4s, p. 293. 3j Compt. reinl,, 117, p. 177. ■1) Berichte, 20, p. 2708. 5) .Tourn. f. prakt. Chem., II. 49. ji. 185. <'>) As to whether this alcohol is to be desig-nated "g^eraiiiol," the name assigned to it by its discoverer, or "rhodinol,"' the name suffge.sted by Eckart for the impure cOTiipcjund, has given rise to a lively controversy. Without entering npon this dis- cussion, a mere reference to the literature will here be made: H. ICrdmann & Huth; "Zur Kenntniss des llhodinois und CTeraniols." .Jourjl. f. prakt. Chem., II, 53, p. 42; Bertram & Gildemeister : "Ueber Rhodinol und (Teraniol." .Journ. f. prakt. Chem., II, .53. p. 225; A. Hesse: "Uelier die vermeintliche Identitat von Rhodinol und Geraniol." .lourn. f. prakt. Chem.. II, 53, p. 238; H. Erdmann: "Untersuchungen fiber die Be- standtheile des Rosenols und verwandter iltherischer Oele." .Journ. f. prakt. Chem., II, 56, p. 1; Bertram & Gildemeister: "JJie Bestandtheile des Rosenols und verwandter atherischer Oele." .Journ. f. prakt. Chem,, II, 55, p. 506; Th. Poleek : "Zur Rhodinol- frage." .Journ. f. prakt. Chem., II, 56, p. 515; Berichte, 31, p. 29; Bertram & Gilde- meister: "Zur Rhodinolfrage." Berichte, 31, p. 749. 7) .Journ. f. prakt. Chem., II, 50. p. 473. 8) Berichte. 29, p. 922. 432 Special Part. As already stated, the greater portion of rose oil consists of geraniol. If the stearoptene is removed by dissolving the oil in dilute alcohol or by vacuum distillation, there remains an oil which distills under ordinary pressure between 228—232°. When treated Avith carefully dried and very finely powdered calcium chloride, this oil solidifies to a solid mass of geraniol calcium chloride. This is freed from oil by washing with ether, petroleum ether or benzene, and then decomposed with water, yielding chemically pure geraniol.' For the identification of geraniol the well crystallizing diphenji urethane derivative (m. p. 88 — 84°) dis- covered hj Erdmann and Hutli- can be employed. Properties and derivatives of geraniol are described on p. 132. The second alcohol, the 1-eitronellol, is quantitatively of less im- portance. Tiemann and Schmidt ^ estimate the amount in Turkish ro.se oil to be about 20 p. c. For the identification and isolation of citronellol phosphorus trichloride is allowed to act on a well cooled ethereal solution of the alcohols of rose oil. The geraniol is hereby converted partly into geranyl chloride, partly into hj'drocarbons, whereas the citronellol is converted into a citronellyl chlorophosphorous acid, which can be removed from the ethereal solution by shaking with caustic soda solution. The aqueous solution of this citronellyl acid ester is shaken out with ether, saponified with strong caustic soda solution, and the free citronellol distilled with water vapor. The two alcohols, geraniol and citronellol, occur in rose oil princi- pally in the free state and onlj^ in small part as ester. The oleoptene of Bulgarian rose oil contains about 90 p. c. of alcohols (calculated as CioHisO). Normal Bulgarian oil, including the stearoptene, contains on an average 2..5— 3..5 p. c. of ester (calculated as geranyl acetate) ; a sample of German oil contained 3 p. c. According to Dupont and Guerlain-* (1896) the esters deviate polarized light more than the underlying alcohols. The li(|uid portion of a French oil which deviated the ray of polarized light 10° SO' to the left, after saponification had an angle of only — 7° 5.5'. The acids which are probably partly combined with geraniol, partly with citronellol, have not yet been investigated. Dupont and Guei'lain are of the opinion that the esters play an important role in the production of the rose perfume. 1) Bertram & (iiUlemeister, loc. cit. 2) .Tourn. t. prakt. Cheiii., IJ. 53. p. 4.5: also Tiemann & Sclimi(U, Berichte, 29 p. 920; fnrther H. Erdmann, Journ. f. prakt. Chem., II, 56, p. 6. 3) Loc. cit. ■1) Conipt. rend.. 12,3, p. 750. Oils of the Rosaceae. 433 As shown by Fliickigvpi the stearoptene of oil of rose belongs to the series of paraffin hydrocarbons. It is not, however, a sing-le hydro- carbon, but consists of at least two, possibly of a number of homologous paraffins. This is shown by the fact that on proper treat- ment of a large amount of stearoptene, fractions melting at 22° and 40—41° respectively are obtained. 2 The ethyl alcohol found by Eckart results, according to Scliim- mel & Co.,-^ only when the roses have become heated on their way from the fields to the stills and have thus undergone fermentation. Inasmuch as neither geraniol and eitronellol. nor their esters either alone or mixed possess the characteristic houey-like odor of the rose oil, it must be assumed that other substances are present in very small amounts which assist in producing the fine aroma, of the rose. The different odors of the various varieties would seem to indicate chemical differences. Examination. Since the danger of adulteration of as expensive an oil as rose oil is very great, a luimbei" of em]:)irical tests have been suggested by means of which it was supposed tlie presence of foreign additions, especially of palmarosa oil (so-called Turkish geranium oil) could be detected. Th(jugh these tests were never received with much confidence, their value became even more problematic when it was shown that geraniol constituted tlie principal (Constituent of rose oil as well as of palmarosa oil. It is true that some characteristic constituent of the palmarosa oil not contained in rose oil might produce a particular reaction with the proposed reagents and thus betray the presence of the adulterant. A recent investigation, however, of palmarosa oil by Gilde- meister and Stephana' has not been pi-oductive of any result in this direction. In addition, it should be remembered that the Bulgarians subject the palmarosa oil to si)ecial treatment before they use it as adulterant. Thus e. g. bj' shaking the oil with lemon juice and by exposing it to the sun. they try to make the palmarosa oil resemble the rose oil in odor and other properties as far as possible. Besides palmarosa oil, the true geranium oil is used as an adulterant of rose oil. If the adulterfition is at all skillful not only do the numerous suggested color reactions with iodine, sulphuric acid, fuchsin sul- 1) See footnote 4, \\. 4-.30. 2) Bericht von .S. & Co., Oct. ISilO. p. 42.— Eckfivt, Dupont & Ouerlain, loc. cit. 3) Bericht von S. & Co., Oct. 1R92, p. M;. *) ArcliiT fl. Pharm., 2., \i.

    . e. alcohol and the operation repeated until it has become perfectly odorless. As a rule two such treatments of the crnde stearoptene suffice. Test for spermaceti in the stearoptene. .3 — 5 g. of the stearoptene are boiled for a short time with 20 — 25 g. of a 5 p. c. alcoholic solution of potassa. The alcohol is evaporated and the residue treated with hot water. Ujion cooling most of the stearoptene separates as a sohd crystalline mass on the surface. The alkaline solution is removed, the stearoptene melted with some hot water, again allowed to cool, the water again removed, the operation being repeated until the wash water is neutral. The united aqueous liquids are twice extracted with ether in order to remove any suspended stearoptene. The alkaline aqueous solution is then acidified with dilute sulphuric acid and the acid solution extracted again with ether. Upon evaporation, the ether should leave no residue (fatty acids). By way of control, the recovered stearoptene, dried at 90°, is weighed. Allowance should be made for a slight loss resulting from evaporation while di-ying. 1) Chemlker Zeitung, 22, p. 149. 2) Bericht von S. cfe Co., Apr. 1889. p. 436 Special P:irt. The spermaceti content cn-n be determined in a, simpler manner by saponifvino- the separated stearoptene with alcoholic potassa of known strength and titrating- back with N/2 sulphuric acid. The saponification number of spermaceti is 1()8. 8 a p o n i f i c a t i o n. The saponification number of a good commercial oil varies from 10—17, the acid number from O.N— 2.7. Palmarosa oil according to (lildemeister and h^tephani Ikis a saponification number ,,f :5()_5(), the geimine geranium oils 4.")— 100. Adle. Acetylization. In order to make the exanunation of the oil complete, it will often be advisable to ascertain tlie alcohol content Igvraniol and citronellol) by acetylization. The amount present will be inversely proportional to the pci'centage of stearoptene present. Umney2 found 70— 72.ri p. c. (calculated as geraniol) in good rose oil. Palmarosa oil contains 76—02 p. c. of geraniol. ^ As latest adulterant, guaiai- wood oil from BuJne.^ia s/irinieuti. which lias an agreeable tea-rose-like odor, has been employed in Bulgaria. s It (/an lie recognized by the microscopic examination of the form of the crystals of guaiol which sepa.rate from the oil upon cooling. Guaiol forms needle-shaped crystals which are charai-terized by a channel-like middle line. Tlie (-rystnis of the rose oil paraffin are smaller and thinner and possess less sharply cmtlined forms (Dietze*). The ]iositive pre.sence of guaiae wood oil in ro.se oil should be e.stab- lislied by the isolation of guaiol melting at 91°. The new adulterant ini-reases the specific gravity and the optical rotation, and raises the congealing point of the oil; it lowers the saponification number but very little, and upon evaporation leaves a resinous I'esidue.-i 172. Oil of Bitter Almond. Oleum Aniygdalarinii Aiiiararuiii. — Bitteniiaiideliil. — Essence (rAiiiaiules Aiiieres. OEiiiiN ANii History. Pniini.s nmviid.-ihis Stok(»s (Auivgrlnlus com- immis L. ) whii-li belongs to the family of the Ros;ife;w is cultivated in Europe. Asia anil northern Africa, rec-ently ,-ilso in California. In the cour.se of time several cultivated varieties have been formed, which are distinguished by larger or sm.'iller fruits and seeds. The trees which produce the bitter abnond do not reveal any permanent botanical 1) ArchiY il. Phm-m., 2.^-t, p. /IL'lj. -) Clieniist and T)rugj>:ist, +0, ]i. T'.i.j. •■!') Berlo.ht von S. & Co., Oct. IS'.IS, ji. 4:',. *) Siiddcntscho Apoth. Zt'itiii]^-, ."IS, ])p. (',72 ami 6X0. Oi!.out 5(_)— (j(.)° and the mixture set aside for about 12 hours. The oil formed is then distilled over with water vapor. According to tlie directions of Petteiikofei-i (1.SG2) 12 parts of the ground seeds, deprived of their fatty oil, are added to 100—120 parts of f)oiling water while stirring. The niixtnre is kp|it at tins temperature for about 15 — 30 minutes and is then set aside to i.-ooh To the cool mixture 1 part of fresh bitter almond powder, mixed with G— 7 parts of water, is added and allowed to macerate for 12 hours. By treating the larger portion of tlic almond ]iowdHr witli boiling water, a more complete solution of the amygdalin is supposed to be accomplished. In order to hydrolyse the amygdalin of 12 parts of the powder, the emulsin of 1 part will suflfice. During the proCHss of distillation, care is to be exerrised not to allow the vapors of the very poisonous hydrocyanic acid lo escape into tlic room. Not only should good condensation be provideib but thp ri^ceiver should be joined air-tight to the condensei' b.v means of bhiddrr oi- parchment paper. All esoajiing gases should be conducted into the o]ien atmosphere. Inasmuch as benzaldeliyde is rather readil.v soluble in water, especially in such containing .hydrocyanic acid, the bulk of the oil is obtained only after cohobation of the aqueous distillate. The yield of oil from bitter almond seed varies from 0.5 — 0.7 p. c, that from ajiricot .seeds from 0.6 — 1 p. c. 1) Lieblg's Anmileii, 121.'. p. 81. Oih of tbf Rosiieene. ,439 Inasmuch as the hydrocyanic acid is objectionable in many instances, a part of the oil is deprived of this poisonous acid. For this purpose the oil is shaken with milk of lime and ferrous sulphate whereby the liydrocyanic acid is precipitated as calcium ferroeyanide. The unchanged benzaldehyde is rectified by means of water vapor. If the operation has been carefully conducted no trace of hydrocyanic acid remains, as may be shown by the tests described under Examination. In place of the oil deprived of its hydrocyanic acid, the cheaper artificial benzaldehyde is largely used. Inasmuch as the latter article iTsually contains chlorinated products which possess an unpleasant odor and taste, it can be used only in the manufactui-e of the cheaper grades of soap, but not in perfumery and in liquors. Artificial benzaldehyde is made by boiling benzyl chloride with lead or copper nitrate, or by heating benzj'lidene chloride with soda lye oi- milk of lime. Benzaldehyde obtained in this manner can be detected by means of its chlorine con- tent as described on p. 442. Peopehties. Bitter almond oil containing hydrocyanic acid is at first a colorless liquid which later becomes yellow. It is strongly refractive and posesses the well-known odor of bitter almonds. In smelling of the bitter almond oil great care should be exer- i-ised on account of the strongly poisonous hydrocyanic acid. The sp. gr. of the normal oil is 1.045 — 1.06. A higher specific gravity nmy lie due to an abnorrnally high hydrocyanic acid content or of jihenyl oxyaceto-nitrile. (Comp. under Composition on p. 440. ) Freshly prepai-ed oil is neutral. Upon standing it acquires an acid reaction owing to the oxidation of benzaldehyde to benzcjic acid. The oil is optically inactive. In water it is relatively soluble: 1 part of oil requires somewhat over 300 parts of pure water for solution. In water containing hydro- cyanic acid, however, it is more soluble. The oil is soluble in 90 p. e. alcohol in all proportions, of 70 p. c. alcohol it requires 1}^— 2 parts. Nitric acid dissolves bitter almond oil at ordinary temperature without the generation of nitric oxide vapors. Upon distillation of the oil over a direct flame an (jil rich in hydro- cyanic acid comes over first, later a weaker distillate is obtained. On account of the hydrocyanic acid vapors given off, special care must be taken in conducting this operation. The residue contains benzoin which results from the polymerization of the benzaldehyde under the infiuence of the hydrocyanic acid. 440 Specml Part. Bitter almond oil deprived of its hydrocyanic acid, or benzaldehyde, is a colorless, optically inactive liquid; sp. gr. 1.050—1.055; b. p. 179°. It is much more readily acted upon by atmosplieric oxygen than the oil containing hydrocyanic acid, whi(/h seems to act as a preservative. Atmospheric oxygen quite readily oxidizes benzaldehyde to benzoic acid. Compare under Preservation on p. 412. Composition. Bitter almond oil consists of benzaldehyde, hj'dro- cyauic acid and phenyl oxj'aceto-nitrile (benzaldeli,yde cyanhydrin or the nitrile of maiidelic acid). Upon the hydrolysis of amygdalin, benzalde- hyde and hydrocyanic acid i-esult which, upon prolonged contact, unite to form phenyl oxyaceto-nitrile : C6H.5CH(.) + CNH = CeH5CH(0H)CN. IJeuzaldebyde Hyilrocyauir aclil Fbenyl oxyaceto-nitrile. The proof that bittei' ;ilmond oil contains this nitrile was brought by Fileti i in 1818. Upon reduction of bitter almond oil he obtained phenyl ethyl .'iniiue wherea-s a fresh mixture of hydrocyanic acid and benzaldehyde jnelded only methyl amine. Phenyl oxyaceto-nitrile is readily decomposable, breaking u]) into its components when distilled with water vapor or in a vacuum. It must, therefore, be formed after the distillation of the oil. It is formed in large quantities when the oily distillate remains in cinitact witli tlie aqueous distillate containing the hydrocyanic acid for a long time. Inasmucli as the sp. gr. of the nitrile of maudelic (phenyl glycoUii;-) acid is high, viz. 1.124, the density of an oil will nicrease with the amount of nitrile present. Whereas normal oils having a sp. gr. of from 1.052—1.058 contained l.<5— 4 j). c. of liydrocyanie acid, oils having a density of from 1.080— 1.()9(> were found to contain 0—11.4 p. c. of hydrocyanic acid. To further clear up these relations it was observed that the sp. gr. of pure benzaldeh_yde changed from 1.054 to 1.074 when allowed to .stand two days in contact with a 20 ]). c. aqueous solution of hydrocyanic/ acid.^ From tlie above it becomes ajiparent that tlie hydrocyanic acid content of an oil will vary considei-ahly with the metliod of jjreparation. For mediciiinl ])urposes, tlierefore, a ilefinite percentage strength should lie required.'' ExAMiNATio.x. Qualitative test for liydrocyanic acid. In order to distinguish' a bitter almond oil containing hydrocyanic acid h-om one which does not contain this lu-id the following te.st is made use of: 1) (Jazz, ehiin. ital. S, p. +4(i : Be- 2) Kericlit von S, & Co., .\pril lsy3, p. 40. rlclite, 12, Ref. p. 2iMj. 3) Pharjn. ZcMtuiiK, -tl, p. Tsil. Oils of the Itosnceat. 441 10 — 15 droi)S of the oil to be examined are shaken witlj 2 — 3 drops of a strong (or a corresponding amount of dilute) soda, solution. Several drops of ferrous sulphate solution containing some ferric salt are then added, the mixture thoroughly shaken and acidulated with dilute hydrochloric acid. Upon solution of the precipitate of ferrous and ferric oxide a precipitate of Prussian blue i-esults if hydrocyanic acid was present. The reaction is so delicate that even minute traces of hydrocyanic acid can be detected in this way. As.sav of hydrocyanic acid. The best renults are obtained by the g-ravimetric method according to the following directions. 1 g. of oil carefully weighed is dissolved in 10 — 20 g. of alcohol and 10 g. of alcoholic ammonia (free from chlorine) are adcted. After standing for a short time 1 g. of silver nitrate is added and the mixture acidulated with nitric acid. After the liquid has become clear, the silver c.vanide is collected on a dried and weighed filter, carefully washed with water and dried at a temper- ature of 100°. The silver precipitate olitained in this way represents all of the hydrocyanic acid contained in the oil. If the oil is not previously treated with ammonia only the free lij'drocyanic acid is estimated. Tlie ammonia decomposes the phenjd oxyaceto-nitrile.i More convenient is the volumetric method of Vielhaber- liut it is less accurate bei.-anse the end-reaction cannot be recognized with certainty. Liebig's method for the estimation of hydrocyanic ;icid in bitter almond water is not at all applicable to the oil. The following directions are given l;)y Kreniers and Schreiner:"^ 1 g. of oil is carefully weighed in a small Erlenineyer fla.sk, and 10 cc. of a mixture of freshly prepared magnesium hydroxide and several drops of potassium chromate solution are added. Sufficient X/10 silver nitrate V. S. is added with constant shaking until the formation of the red silver chromate indicates the end of the reaction. In order to obtain the percentage of hydrocyanic acid, the number of cc. of the deci-normal solution used are multiplied by 0.0027. The presence of foreign oils can readily lie detected by converting the benzaldeliyde into its sodium acid sulphite addition product and thus separated from the non-aldehyde constituents. In a test tube of fully 100 cc. capacity 5 g. of the oil to be examined and 45 g. of acid sulphite solution are thoroughly shaken. 60 cc. of water are added and the tube placed in hot water. If the oil was pure a clear solution will result, whereas foreign substances will rise to the surface andean be examined. In order to test for nitro-benzene (oil of mirbane), either the original oil or the oil floating on the sulphite solution is dissolved in 20 times its volume of alcohol and the solution diluted with water until it becomes turbid. Zinc and sulphuric acid are then added and the solution .set aside for several hours. The solution is filtered, the alcohol evaporated and the remaining solution 1) Phurm. Review, l-l, p. 196. 2| Arcliir d. Phariii., L'lH, |). 4(is. 442 SiiH-hil Part. boiled with a drop ol' potassium bichromate solutiou. Tlje ])reseiice of aniline, I'esiiltiiig upon the reduction of any nitro-benzeno in tlie origiual oil, will be recognized by the violet color of the solution. Tlie most common adulterant of bitter almond oil, whether deprived of lij'droeyanic aciil or not, is artificial l:>enz;ddehyde. Inasninch as the hitter is almost invariabl.y accompanied In' chlorinated jiroducts the determination of chlorine affords the easiest method of detection in the following maimer : ■ In n, small porcelain ca]isnle, placed within a, larger one of about 20 cm. diametei-, a folded strip of filter ])a])er saturated with oil is placed and ignited. A large beaker of about 2 1. capacity, the iniier surface of which has been moistened with distilled water, is immediately placed over thi' burning oil. The jjroducts of combustion condense on the moistened surface of the beaker and with the aid of a little distilled water ai'c washed on to a ffltei-. The Hltrate should not be rendered turbid, much less yield a precipitate with .silver nitrate T. S. Genuini' oil, i. e., oil jirepared from almonds or a])i-icot seeds nevei' yields a. chlorine reaction. It nia.v be well, however, to make a duplicate test with a. known ]iure oil iuasmnch as the watei' and the utensils emjilo.ved may at times be contaminated with some chlorine. Inasmuch as a beuzaldehy(.le free from chlorine has re'^-ently been brought into the market, the absence of chlorine is by no means a sign of the al)solute purity of an oil. In all cases, howevei', where chlorine is f(jund the presence of artificial benzaldehyde maybe regarded as being established. The presence of alcohol, which is not infrequently found, can be determined in the usual manner. r'RESERVATroN. It a small amount of benzaldehyde be exposed to the air in aii 0])eii dish, crystals are soon formed and after a short time the oil will lie converted into a magma of (•rvstals of benzoic acid. The same eha.nge takes place if the oil is kept in half-filled bottles. Bitter almond oil should, therefore, be kept in well-filled bottles. Ex- periments have shown that the addition of 10 p. c. of alcohol will ac't as a preservative.- If but 5 ]i. c of alcohol are added, the (jxidation will take place even more rajiidly than when undiluted. Bitter almond oil (Containing hydroi;yanic aiad is not as readily oxidized .is the oil free from arid. The hydroc-yanic acid evidently acts in a. manner similar to the alcohol when 10 p. c. are used. 173. Oil of Cherry-laurel. Oleum Laiirocenisi. — Kirsflilorheerol. — Esspiiee de Laurier-Cerise. Origin, History anu Prepakation. Cherry-laurel, I'nuius lauro- nsus L.. which is indigenous to Pei-sia and the Caucasus and which cei i| Bericht voii S. & Co., Apr. IstlO. |i. 129. =) Bericlit von S. & Co.. Apr. ISilo. p. 47. Oils of the Itosnceae. iiS is ciiltiviited in eoiiiitries with a. temperate climate, appears to liave berome known in Europe since the beginning- of tlie sixteenth century. The aqueous distillate from the leaves has been used medicinally since the tirst half of the eighteenth century and its poisonous properties were repeatedlj' observed. The distilled oil is mentioned in medical treatises since 178(). The presence of hydrocyanic acid in the oil was obsei'ved simultaneously by Scluiub and l:iy iSchrader at the beginning of thi.s century. The oil frcjm the leaves closely resembles the oil from bitter almonds bnt has a .slightly different odor. The method of preparation is likewise similar to that of the bitter almonds. The cut leaves are macer;ited with water and the mash set aside. The oil thus formed is distilled with water vapor. The yield is about 0..5 ]i. c. (Umneyi). The oil is fornipd Ijy the hydrolysis of laurocerasin. a glucoside closely related to amygdalin, but n()t identical with it. 2 Being hygro- sco]iic it is not readily obtained in the crystalline state, but results as a thick syrup ru- an amorphous mass upon evaporation of the alcoholic extract. Laurocerasin. (.UhHotNOso is made up of one molecule of amygdalin, CaoHoiXOn, one molecule of amj^gdalic acid, C20H28O13, and six molecules of water. In contact with emulsin, the amygdalin of the laurocerasin is broken u]j into hydrocyanir- acid, benzaldehj'de and grape sugar. The amount of oil ol)tainal)le from the laurocerasin is, therefrjre, much smaller than that obtained from an equal weight of amygdalin. Properties. Oil of cherrydaurel can only be distinguished from bitter almond r)il Ijy its odor. The difference in odor is emphasized by first uniting the benzaldehyde with an acid sulphite. Its other properties agree with those of bitter almond oil. Its sp. gr. is l.o.'iJ: — l.OGd, it is optically inactive and forms a clear solution with 2 parts of To p. c. alccliol. Inasmuch as cherry-laurel oil is very poisonous on account of the hvdrocyanic acid contained therein sufficient reganl should be had for this property in the use of the oil. Composition. Like bitter almond oil, cherry-laurel oil contains benzaldehyde, hydrcx-yanic acid and phenjd oxyaceto-nitrile (Fileti,-'' 1) P'hann. Jouru., Ill, .", p. 7G1. = ) Lehniann (187-t), .\eue.s Kepert. f. fl. Pharm., 2.3, p. 449; and (1885) I'harm. Zeitschr. f. KuskL, 24, pp. P,'jP,, .369, 38.".. 401. — Berk'hte, Is, p. o69 Referate. 3) (iazz. chilli, ital., S, p. 440 : Beric-hte, 12, p. 296. 444 Special Fart. 1878). According to Umneyi (1869) hTdrocyanic acid is present to the extent of 2 p. c. It is probable, liowever, that the percentage varies as in bitter almond oil. According- to Tilden2 (1875), traces of another substance are present, to which the peculiar odor of this oil is probably due. If the oil is shaken with sodium acid sulphite solution, a dark colored oil remains which upon oxidation with (•hromic acid yields benzoic acid. Tilden supposes this substance to be identical with benzyl ali-ohol. Adultekation and Examination. Oil of cherry-laurel is subjected to the same kind of adulteration as bitter almond oil. Tlie tests are the same as those described on p. 440. 174. Oil of Wild Cherry Bark. The bark of the wild cherry, Priiinis virgiuianfi Mill. (P. nevot'wa Ehrh.), which is indigenous to North America, has been used for a long- time by the natives in the preparation of aromatic beverages and household remedies and was made official in the early editions of the U. 8. Pharmacopoeia. That the distillate from tlie bark contains hydrocyanic acid was observed by Procter 3 in 1834. In 1838 he showed that the oil does not preexist in the bark but results by a process similar to that taking- place in the formation of bitter almond oil.* A more detailed examination of the oil was made by Power and Weimar 5 in 1887. The powdered bark when macerated yields 0.2 p. c. of oil, which resembles the oil of bitter almonds, consists largely of benzaldehyde, and contains hydrocyanic acid.*' Sp. gr. 1.04.") — 1.050. According- to Power and Weimar the bark contains no amygdalin, but a substance that behaves like laurocerasiu. The ferment does not consist of emulsiu, at least no emulsin can be isohited according to the usual method. The leaves of the wild c-herry tree also yield an aqueous distillate containing liydi'ocj'anic acid.^ Hydrocyanic acid and benzaldehyde have been obtained from parts of other rosaceous plants. Thus, e. g. from the leaves, bi-anches and seeds of the peach, Prunu.s per.sirn Jess., from the seeds and the fleshv 1) I'harm. .loiu-n.. II. 10, p. 407. s) I'liarm. RuiirLschaii, 5, |>. 203. 2) Pharm. .lourn.. Ill, .''>. p. 761. «i Berlcht von S. & Co., Apr. 1S90, ]). 4S, 3) Amei-ic. .Joiii-n. Pharm., 6, p. S. 7] Pharmacosnosie, Si-d ed., p. 7lj.j. 4) Ibidem, 10, p., 107. Oils of the Lfguniinosai'. 445 ppriearp of the cheiTV, /-•. verasuv L., from the seeds of tlie phini, P. domesticii L., from the bark, leaves, flowers and seeds of P. padns L., from the young leaves and flowers of P. spinovn L. 175. Oil of Copaiba. Oleum Balsaiui CopaiTae.—Copaivabalsamol. — Essence de Baiiine de Copaliii. OriCtIX. Copaiba balsam, which has been used in Europe since the beg'inning of the sixteenth i^eutui-y, is obtained fi-om a number of species of Copaifera (FamiW Leguwiiio.sae) which are indigenous to the territory of the Amazon and its tributaries as far north as Guayana, Venezuela and Columbia. The principal species are Copaifera, officinale L., C. guaianensis Desf., C. coriacea Martins, C. Langsdorffii Desf., C. eonferti- flora. C. ohlongifolia Martins and C. rigida Bentham. Tlie balsam is allowed to flow from the cavity made in the trunk of the ti-ee by means of tin tubes into the vessels used for its transportation. C)ccasionally the trees are so charged with lialsara that the receptacles liurst and the balsam exudes from the vertii::al cracks. Commercially, the balsam is distinguished according to the ports of export. The most important varieties are the Maracaibo balsam (dei-ived princiiially from Copaifera^ officinaJis) and the Para balsam. The latter is more fluid and inasmuch as it yields the larger percentage of oil, abt. GO — 00 p. c., is preferred for distillation. Maracaibo balsam which is more viscid yields upon distillation about 40 p. c. of oil. A like yield was obtained from a Maranhao balsam. Propekties. Copaiba oil from Para or Maracaibo balsam is a colorless, yellowish or brownish liquid possessing the characteristic pepper-like odor of the balsam, and a bitter, grating and persistent taste. Sp. gr. 0.900—0.910: a-o^ — l to —8.")°. The boiling temper- ature lies between 2.50 and 275°. It is not completely soluble in 90 p. c. alcohol. Of absolute alcohol, usually equal parts are requisite to form a clear solution. According to Kremel,i two samples of ])ara oil yielded no saponification number. Dulicre^ examined an oil of unkncjwn r)rigin and of a high specific gravity, viz. 0.9155, and found a saponifi- cation number corresponding to 4 p. c. of sesquiterpene acetate (Ci5H2,oOCOCH3J. After acetyhzation a, saponification number was obtained c:-orresponding to (j.5 — 7.85 p. of acetate. '^ An oil from Maranhao balsam liad the sp. gr. 0..SS9 and "d = — 20°. i| Pharin. Post, 21, p. 822. 2) Ann. de Pharm. (Louvaini. 3, p. ."j.^S; 4, p. 11. 3) Bericht von S. & Co., Oct. ]S9."i, p. 42; Apr. 1898, p. 49. 446 Special Part. Composition. The only known and well defined constituent of eopailia oil is the sesquiterpene caryophyllene, C10H24, which also occurs in oil of cloves. If fraction 250— 270° is treateil according to Wallachi with glacial acetic acid and sulphuric acid, i-aiyophylleue hydrate CisHo.'i.OH is olrtained in handsonje crystals melting at 00°. By the action of phosphorus pentachloride on car^'ophjdlene hy. 215. 2) Bericht von S. & Co., Apr. 189(j, p. 6'J. 3) Catalog-ue of the Nat. Exhib. in Rio, 1866, p. 4S. 4) Bericht von S. & Co.. Apr. 1896, p. 70. 5) Bericht von S. & Co., Oct, 1894, p. 75. 448 Spechil Part. ethyl alcohol and also Kmall amounts of methyl alci.ihol. The latter was identified by its conversion into methyl iodide and into the methyl ester of oxalic acid melting- at 54°. If the leaves were digested for 24 hours at a temperature of ."lO" before being distilled, the first distil- late contained larger ann^unts of ethyl alcohol which, however, was formed during the prrjcess of maceration. i 180. Sappan Leaf Oil. The leaves of (';iennJpini;). snjipan L., a leguminous tree, from which the sap])an wood used for dyeing is obtained, yields according to vnn Eomburgh 0.16 to 0.2 p. (■. of an almost colorless oil, sp. gr. 0.825 at 28°. It is strongly dextrogyrate, aD= + -M°:M)' to +.jO°yO' and boils princii)ally at 170°. The odor is pepper-like, reminding of phel- landrene. With sodium nitrite and glacial acetic acid so large an amount of phellandrene nitrite was obtained, that the bulk of the oil may be regarded as d-phellandrene. Upon distillation of tlie leaves, van Romburgh observed the occurrence of meth,yl alcohol. ^ 181. Oil of Tolu Balsam. Oleum Ualsiiini Toliitani. — Tolubalsamol. — Essence de Baiiiiie de Tolu. Origin and History. Tlie statements made i:)n p. 420 concerniug the origin and preparatic;)n of American storax apply in ueneral to tolu Ijalsam from TnJuifera bal.sainum Mill. It is prepared in the sciuthern states of South America and has been used for a long period, in Europe since the middle of the sixteenth century. Ui)on distillation with water vapor, the solid balsam yields 1..")— 3 p.c. of oil. Slow distillation yields a light oil, whereas rapid distillation with superheated steam yields moiv oil of a higher density. The sp. gr., tlierefore, varies between 0.94.')— l.OO. The oil is slightly laevo- or dpxti-ogyrate, aD = — 0° .")«' to -|-0° .54'. The odor is pleasant, highly aromatic and reminds of hyacintli. Composition. The older, s1 the Leguniiiiosae. 449 much as Bussed (18T(J) has shown the presenc-e of benzoic and cinnaniir esters of benzyl alcohol in the balsam, these esters are ]irobably also contained in the oil. As a matter of fact the oil has a high saponification number (abt. lisd) and from the alkaline saponification liquor crystalline acids (presumably cinnaniii- and benzoic acids) can be precipitated. 182. Oil of Myroxylon Peruiferutn. From the leaves of the leguminous Myroxylon pernifmim L. f.. a tree (/losely related to the Peru balsam tree,- Peckolt'' obtafned a small amount of oil with a faint but pleasant odor and a sp. gr. of 0.874 at 14°. The bark yielded two oils, one having the sp. gr. 1.189 at 1.")°, the other 0.924 at 17°. The oil from the wood had a faint sassafras odor and a sp. gr. of O..S."2 at l-"j°. 183. Oil of Rose Geranium.'^ Oleum (Teraiiii. — (Teraiiiiiiii- or Pelargoiiiiiiniil. — Essence ure is pnssil.ily lihie in color. 4. Spanish oil. Sp. gr. abt. O.S97 : «!, = — 10 to — 11°. Geranyl tiglinate 35 — 42 p. c. As to solubihty this oil differs from the others inasmuch as the solution in 2 — 3 or more parts of 70 p. c. alcohol is rendered turbid by the presence of minute crystals of paraffin which rise to the surface. The separation of oily drops at the l)otttim of thetulie would indicate adulteration with fatty oil. 5. German oil.i This oil has been distilled by way of exjierinient but is not an article of commerce. Yield 0.1(1 ]i. i-. Sp. gr. 0.90(); «D = — 10°. Geranyl tiglinate 27.9 p. c. Of the commercial varieties, the Sj.ianish oil is rated highest. Frendi and African oil are about alike in quality, while the price of Kinmion oil is somewhat lower. The oil is mostly transported in tin cans and often acquires a brownish color and an odor i.if rotten etias. This disagrepal)le odor„ 1) Berlcht vein S. & Co., .\pr. IS',14, p. 3Li. Oils ot the Leguminosae. 451 however, is easily removed by exposing- tlie oil to the air in shallow dishes for several days. As soon as possible the oil should be filled into glass containers. Composition. The principal constituent is geraniol,i CioHigt). which is i-ontained in all commercial varieties of the oil. It can be isolated by treating the saponified and dried oil witii very fine calcium chlori(ie. The addition product is carefully washed with ether and the pure geraniol separated by decomposing the compound with water.^ Besides geraniol, a second alcohol, CiuH^dO, which ha.s been identified as citronellol by Tiemann and Schmidt s has been found in the oil. It occurs to a larger extent in the oil from Keunion. Mixtures of these alcohols have been described as "Rhodinol de Pelargonium" by Barbier and BouveaultJ' and as "Reuniol" by Hesse.-'' The percentage of geraniol and citronellol in the various commercial varieties has been determined by Tiemann and Schmidt:-^ The Spanisli oil contains 70 p. c. of alcohols, of which (>.") p. c. are geraniol and y5 p. c. citronellol. The African oil contains 75 p. c. alcohols of which 80 p. c. is geraniol and 20 p. c. citronellol. The Reunion oil contains 80 p. c. of equal parts of geraniol and citronellol. In all of these oils the citronellol is a mixture of the dextro- and laevogyrate modifications. The lower fractions of the oil contain a third alcohol, in all probability linalool. (Barbiei- and Bouveault).^ The acids which were separated from the lye after saponification boiled between 100 and 210°, and in part solidified. The sohd acid melted at 04 — 6.")°. Its silver salt and its dibromide melting at 87° identify it as tiglinic acid." The licjuid acid mixture ajjparently consists of valerianic, butyric " and acetic ^ acids. Jeancard and Satie* have found that the a,mount of free acid in geranium oil increases when the oil is kept in ])ai-tly filled bottles. An oil which originally showed an acid number of 56, after two months standing had increased to 66.78. The same authors also made a comparative examination of the different commensal varieties of the oil. 1) .Jahresb. d. Chem., 1S79, p. 942. -') .Joiirn. f. prakt. Cheni., II, 49, p. 191. 3) Beric-hte, 29. p. 924. 4j Conipt. rend.. 119, pp. 2S1 & .384. = 1 .Journ. f. prakt. Chem., II, .TO, p. 472: .-5.3, p. 2.3S. 6) Compt. rend., 119, p. 281. T) Bericht von S. & Co., Apr. 1H94, p. .31. It would be of interest to reexamine the af|iieoi]s distillate of Pelargonium roseum in order to ascertain whether or not the pelargonic aeid of Pless (1846) (Liebig-'s Annalen, .59, p. .j4), may reveal itself as a mixture. 8) Bull. Soc. ehim. Ill, 23, p. 37. -t52 Specinl Fart. C-reraniol :iii(l citroucllnl ;ire C(iiit:iine(l in tlic nil liotli free and combined with aiids. The fsters of eitronellol ai'f more .strongly optically active than the alcohol. If geranium oil is saponified with alcoholic ])0tassa the angle of rotation is less aftei- the sayioniiii-ation than liefore.i Of minor constitnimts 1-menthone remains to be mentioned. It was identified by Flatan and Liibbe^ liy means of the semicarbazone melting at 170..')°. In the highe.st fractions a crystalline substance melting at (i3" has lieen found whi(-li resembles the stearoptene from oil of rose. Juilging fi-om the behavior of the oil to 70 ]). c alcohol, this paraffin occurs in largest am(.)unts in the Spanish variet.y. AnuLTERATiON AND P]xAiNn.\ATiox. Geranium oil is adulterated with turi)entine (.)il, cedar wood oil and fatty oils, all of which can be recog- nized by their insolubility in 7n p. c. ah.'ohol. Fatty oil remains liehind upon distillation with water vapcn- anil can lie detected without ditticulfy. 184. Oil of Garden Nasturtium. The odor of the leaves of TrupM^olum rnnjus L. (Family Ti-op;ieohi- i-e:ie) having an odor .similar to that of the cress, induced Hofmann'^ in lcS74 to examine the oil. HOO k. of flowering herb and unripe seeils were distilled with water vapor. The aqueous di.stillate was shaken with benzene and u]ion evapioration of the benzene 7."> g. (^().02.'i p. c. ) of oil were obtained. The oil boiled l)etween IGO — ;{00° leaving a not inconsiderable residue. Only the fir.st fractions contained sulphur and had an unpleasant odor, the others not. The l.iulk of the oil' distilled at about 2."U.0°. This fraction was a. liquid of strong refractive power, sp. gi-, l.lJl-Kj at 18°, and when acted upon with caustic potassa gave off large quantities of anmionia. Analysis showed it to be the nitrile of phenyl acetic acid. The principal constituent of the oil, therefore, is the same as that of Lf^piiliniii s;itiviiiii L. The same substance was found in the lower and higlier fi-actions of the oil together with a hydrocarbon not farther investigated. Quite different results were obtained recently by (.iadamer.^ He prepared the oil by extracting the juice from the comnunuted herb with ether, also by distilling the carefully comminuted herb and extracting the aqueous distillate with ether. 4 k. of herb yielded 1.8 '■: of a 1) Ooiiipt. reiiil.. ll'.l, p. L'Sl. 3) Berichtf, 7, p. 51S. = } liiill. Soc. fhiiii., III. 1'.), ].. 7S8. ii Avfliiv (1. Phariu., 2:!7. p. 111. Oils of the Ervthroxrhicene. 4-53 brownish (/olorfd oil the (;ress-lilre odor of which becaaut) especially marked when warmeiL Witli ammonia tlie oil yields almost quanti- tatively benzyl thiourea melting- at 102°, thus sliowin^i- that the oil c-onsists almost entirelj' of benz^i mustard oil. Tliis mustard oil owes its orifrin to the decomposition of a giucoside, the glucotropaeolin, C14H18KNS2O1) + xHoO by means of a ferment. Inasmuch as the giucoside and ferment are contained in separate cells, the formation of the benzyl mustard oil takes place only when the cell walls are ruptured and both substances can act on each other. If the cell wall is not destroyed before distillation, the ferment is rendered inactive by the heat before it can act (in the gluc-oside. This is then decomposed during the process of distillation with the formation of the nitrile of phenyl acetic a(nd (benzyl cyanide). If it is assumed that Hofmann did not sntticieTitly comminute his crude material, the results obtained by him are explained. 185. Oil of Coca Leaves. The presence of an oil in the coca leaves was hrst oliserved in 1860 by Niemann 1 and Lessen. 2 The leaves of Erythroxylon coca Lam. var. spiiicenniim Brck. (Fannly ErytJiroxyhiceac) contain va.riahle amounts of oil according to their development. Van Komburgh'^ obtained from young, undeveloped leaves 0.1:! p. c, from fully developed leaves only O.dG p. c. of oil. It consisted principally of methyl salicylate with small amounts of acetone and methyl alcohol. 186. Oil of Guaiac Wood. Oleiiiu Ligni (i(na.jaci. — (Tiiajakliolziil. — Essence de Bois (Ta'iac. Origix and Prepar.4ti(jx. Iiulupsi:i t^ni-jiiif'uti Lor. is, according to drisebach,-'^ a tree 40 — 60 feet in height, lielonging to the faTuily Zygophyllaceae, and is indigenous to the Argentine province of Gran ('haco about half way up the Rio Berjemo. The wood, very .similar to the ordinary guaiac wood from (runjiicuiii officinalis L., occurs since tlie year 1892 as Palo liakaino in commerce. It is exceedinglj- solid and tenacious, and is colored greenisli blue on exposure to the air, which allows of drawing the conclusion that guaiac resin is present. By distil- M De foliis Erythi-Dxyli, Dis.^jertatio. Oiitriiiseii 1860. ^) Ueber die Blatter von Erytliroxylon Coca l^am., Dissert atu.in, r»ottinp:eii 1S61!. 3) Rer. dee trav. cllim. des Pay.s Bas, 1.3, p. 42.5. — S'LandH Plantentuin te Buiten zorg-. 1894, p. 4«.— Berieiit vou S. & Co., Oct. 18'.).=), p. 47: Ajir. 1896. p. 7.5. *) Abhandl, d. Ivi'iniffl. Oes. d. WiKsenscii. zii Oottinsen. \ol. 24. p. 75. 454: Speciiil Part. lation tlie wcjod yields 5 — (> p. c. of oil, whirli was first prepared by Sciiiniiuel & Co.i and brought into eoinraerce as oil of guaiac wood.- Propehtibs. Oil of g-uaia(; wood is a viscous, heavy oil, which at ordinary temperature graduallj^ solidifies to a cry.stalliiie mass. When it has solidified, it does not melt again until between 40 and 51)°, The odor of the (jil is very pleasant, being violet- and tea-like. The specifie gravity lies between O.iX;,"') and 0.07") at 'M)°. the angle of rotation is — () to —7° at :^0°, The oil is soluble in 70 p, c alcohol. The saponifieation number found of an oil was 3.9, the ester number '2A and the acid number l.-t.-' (JoMPOsiTiox. The crystalline constituent of the oil is guaiac alcohol or guaiol ( Wallach-i ), a sesquiterpene hydrate CioHiibO, Guaiol is an odorless body, crystallizing in large transparent prisms, and melting at 91°.'^ It lioils under ordinary pressure at 288°, under 10 mm. pressure at 148°. Its scilution in cliloroform is laevogyrate. With dehydrating agents a hydrocarbon rir>H24 is formed, accompanied by an intensely' blue substance. On boiling guaiol with acetic acid an- hydride a. liquid acetyl compound is produced which boils at 153° under a pressure of 10 mm. The 0(hjriferous constitiient of the oil has not yet been investigatecJ. The oil is used in the perfume industry for the purpose of ])roducing a tea-rose odor. Recently it is bi'ing employed in F>ulgaria .as .-m adulterant for oil of ro.se (p. 4;!()). 187. Japanese Oil of Pepper. The fruit of XiuithoxyJum pippi-itjini D. C. (Family Itut;ire;ie) known as PipfT jnponicuni or Snnslio (Japanese), yields upon distillation '■ with water 3.1(5 ]). c. of a yellowish oil of a pleasant odor reminding of lemon. Sp. gr. 0.973; b. p. 1(50—230°. The oil was investigated b^^ 8tenhouse" in 1857, who established the presence of a terpene boiling at 1()2", xanthoxylene (pinene or camphene?), as well as a cry.stalline body ("loHc.Oi. The main con- stituent of the oil is citral," ('mHioO. 1) r.frioht vnn S. & Co., A|n-. 1S92. \t. 42; .\]iv. IsilM, p. H2 : .\pi- ISilS p ofj . Oct. IS'.lS, i>, HO. ■J) The (Hllfiful nalliu "('liaiii|iaca oil" was later glveii to thi.s s.-nnc oil althousli it liaK not the slightest resemblance to the ffenuine chanipai-a oil from Michflia rliaiiip.-U'-i I (lierloht von S. & ('o., Apr. 189H, p. .3:!. I ^M rHetze, vSrHlcTeutsche Apoth. ZeitunR-, HS, \t. (JSO. ■I) Llebia'B .\nnalen. 270, p. 'i'J'i. s) The (Icsisnation chanipacnl ((iK^miker-Zeitung- Kepert., IT, p. HI) for thi.s aleohol is of course hh little jnstifleil as the name chamiiaca oil for the oil. ") Berlcht von S. & T'o., Oct. IS'.IO, ),. 4!l. 7| I'harm. .lourn.. I, 17, p. 19, — Liebig's ,\nnali-n, 104, p. 236. 0;7.S' of the RntacfHP. 455 188. Oil of Xanthoxylum Hatniltonianum. The seeds of Xanthoxylum hamiltonianuin^ jdeld according to Helbmg2 y ,s4__5 p ,. of volatile oil of the sp. gT. ().84(). It is colorless and has a pleasant persistent odor, i-emiiiding of a mixture of geranium ■and bergamot oils. 189. Oil of Rue. Oleum Rutae.—Rauteiiol. — Essence tie Rue. Ori«i!\' and Histohy. Garden rue, Rutu gniveolens L., belonging to the family Rutaceae, is indigenous to the Mediterranean countries and is cultivated in different countries having a moderate climate. It contains aliout 0.()(j p. c. of volatile oil, which gives to the plant a peculiar aromatic odor and taste which gave rise to its use as a kitchen spice. In ancient times the plant was employed as a remedy, especially for scurvy and snake bites. The first mention of oil of rue (although possibljr of the fatty oil) is found in Saladin's writings. Gesner distilled the oil about the middle of the sixteenth centurj" and the same is mentioned in the price ordi- nances of the cities of Berlin for the year l.~)74 and of Fi-ankfurt for the year 1582, and in the Dispensatorium Noricum of the year 1.589. The yield of volatile oil from rue was first determined by Cartheuser in the beginning of the eighteenth century. The oil was investigated by Neumann and Mtilil in Rostock in the year 1811, ^ by Will in the year 1840,* Cahours in 1845, ^ Gerhard in 1848, e Williams in 1858, f Hallwachs in 1859,8 Harbordt in 1862, » Giesecke in 1870^0 and Gorup- Besaiiez and Grimm in 1871. ^i Properties. Oil of rue is a colorless to yellow liquid of an intensive pjersistent rue odor, which is pleasant only when greatly diluted. Its specific gravity is lower than that of all known volatile oils and lies between 0.8/5>i and 0.840. Oil of rue is slightly dextrogyrate ( «L, = -\-<)°V^' to + 2° 10' ) and s^lidifles at a low temperature. Its solidi- fication point lies between + 8 and + 10°. '^ During the distillation very little passes over up to 2(_)0°, the largest portion boils fi'oni 1) Erodia traxinifoliii was lally «) Ltebig's Annalen, 67. p. 242. given a.s the source of this oi' T) Liebig's Annalen, 107. p. .374. 2) .Jahresb. f. Phaim., ISSi, 57: S) Liebig's Annalen, 11.3, p. 107. and- 1888, p. 128. <>) Liebig's Annalen, 12.3, p. 298. 3) Trommsdorff's .rourn. d. Pharni., lo) Zeitschr. tiir Chemie, 13, p. 428. 20, II, p. 29. ^^) Liebig's Annalen, 157, p. 275. .Vdidterants may also be separated from the methyl nonyl ket(ine by the bisulphite method described under ( 'om]i(isition and then identified as such. 1) Pharm. .Toilril., I II, 2.-), p. 1044. i) Zeitsclir. f. riieiliie, 18, p. 42K. -'I Liebig's Annalen. I.jT. ]!. 27.". s ) .rom'ii. do ['harm, et ('liiiii. \ I, 10. p. 2.5,"->. ■-!) LieliiR's .iniialcn. 107, ji. :!74. "i Plinrni. .Idhvii.. Ill, 2.1, p. 1044. Oils of the RutiU-eRP. 457 190. Boronia Oil. All oil clistilledi in Victoria (Australia) from Boroniri polygalifoUa (Family Eutaeeae) had a sweet odor, reminding of estmiicm and some- what of rue. Specific gravity 0.8;59 (!); an = + 10°. Upon fractional distillation of the oil, there came over from 150 — ITO'^ 31 p. c, from 170—180° 88 ]>. c, from 180—190° 1." p. c, and above 190° IG p. c. 191. Oil of Buchu Leaves. Oleum Buccn Folionim. — Biicciiblatterol.- Essence de Fenilles de Biico. Obigix .\ni) History. The genus Ihirosma belonging to the family Rat:n-eae is distributed in southern Africa in various species. The resin- and oil-containing leaves of these shrubs appear to have been used for a long time by the natives as a medicine. In the year 1820 the leaves were brought from Capetown through London into the European market (Reece^). Since the latter twenties they have been maile official in most of the pharmacopteias. In commerce, round and long buchu leaves are distinguished: the first are the leaves of Baronwii hetulina Bartl., and B. crenulata L., the second those oi B. .seiTatifoIia. Willd. The latter a,re sometimes adulterated with the leaves of Enijilpiii-um serrulatum Ait.** The volatile oil of buchu was prepared in 1827 by Brandes.* It was investigated by Fliickiger in 1880, by Spica in 18H4, li^' Shinioyama ill 1888 and by Bialobrzeski in 189(J. From the leaves of Baro.suui hf'tulina there are obtained liy distillation 1.8 — 2 ]>. c. of oil/' frcjin which separate even at ordiiiar.y tem])erature crystals of diosphenol. The liquid portion .separated from this has the sp. gr. 0.9.")7 — 0.97 at l.~)°. The density of a normal oil which had been warmed to 27° in oixler to diss{.)lve all the diosphenol, was 0.91:?. The leiives of JSaro.sma serr;itif/lia yield only O.H — 1 p. r. The oil, poor in diosphenol and liquid at the ordinary temiiera,ture, has the .sp. gr. 0.914— 0.9()1 at 15°. (_)il of buclin leaves is dark in color and has a strong I'amphor- and mint-like odor a-nd a, bitter, cooling taste. 1) Imperial Institute .lounujl, 2, ]j. .^(12; Pii.irm. .roiini., .".7, p. 1'.)<.I. •J| .Monthly (iazette of Health, London, Fell. 1.821. p. 7Vl9. 3) Prantl's Lehrbuch Jei' Botanik, von Fenl. Pax, p. 3.36; Pharniaeocraphin, p. 110. i) .4rchiv der Pharm., 22, p. 229. = ) Bei-ieht von S. & Co., Apr. ls!»l. p. (', ; Pharni. .iourn.. Ill, 2."), p. Tilfl. 45H SiwiaJ Part. C'OMPOsiTiox.i Tlip stPHTopteiie crystallizing from oil of buchn leavps in the cold is a phenol of the formula CioHiaOa. Diosphenol, as the body has been called, melts at H2°, boils under 14- mm. pressure at 112°. under ordinary atmospheric pressure at 2:i-2° with partial decom- position, and is optii/ally inactive. With ferric cldoride it gives a dark -green color reaction. Besides its properties as a phenol, diosphenol shows the behavior of an aldeliyde as it reacts with hydroxylamine and phenyl hydrazine. Opposed to the suppositi(jn that ;ni aldehyde group is present in diosphenol is the fact that by the action of alcoh(ili(; potas.sa and heat an acid CioHisOs + H^O. diolic a.cid m. p. 00°. is pro- duced, whereas from an aldehyde CioHiuOl' the acid C]oHio<-)3 and the alcohol C10H1KO2 woulil be expected. Upon reduction di<.)sphenol yields diolafcohol, C'aiiHisOs, cry.stals melting iit l.jO" ; upon oxidation with moist silver oxide or permanganate, a licjuid acid OiuHieOs results. The remaining constituents of the oil boil lower than diosphenol. In the first ]jortion is contained a hydrocarbon (a(iHi.s of the boiling- point 174 to 176° (at 11 mm. from ().5— 67°). This hydrocarbon forms a nidljile, strongly active liquid (.)f a pinene-like odor. Sp. gr. 0.8647: [«]D= + <;i>°4()'. The fraction boiling from 206—200° consists of a slightly laevo- gyrate ketone ( ['/]d = — 6° 12') Ch.HisO, wliich possesses a pure pe]iper- mint-like odor. With hydroxylainine it yields a viscous oxime. .slightly dextrogyrate a,nd boiling between 134— 1;-5.^° under a pressure of 15 mm. The ketone is probably identical with laevogyrate menthone. as its reaction with bromine also indicates, with which it forms an oily com- pound of the composition CioHi7BrOBr:>. 192. Oil of Empleurum Serrulatum. The leaves of Einjjlmruiii spi-rulatuin Ait., which are now and then mixed in with the long buchn leaves, contain (.).64 p. c. of volatile oil,- the odor, of which reminds of rue and is quite different fri)m that of buchn leaves. Sp. gr. O.04(;4. It boils between 200 and 28."i°, for the greater part lietween 220 and 2;!0°. From this fraction a crystalline compound is obtained by treating with sodium bisulphite, which seems to indicate the presence of methyl nonjd ketone, the main constituent of oil of rue. 1) Fliiclds-i'r CISNO), riliiriii. .Tdiii-ti., III. 11, i)|i. 174 mid -JIO — Spicn (ISS.T) Ciazetta chilli, ital., 1.". p. l'.>.^. ; .Vhstr. .Inhrt-sli. f. Clieiii.. 1 s8.>. i>. ni;.— Shimoyuiiia (ISSSl, Arcliir. d. Phnnii.. 226. ji. 4ii:!._Bial.>lirzeBki (189iD. Pliarm. Zeitschi-. f. Ritssl.. ri.", pji. +01, 417. 4.3;i, 44'.:i.— Kc.iidaki.w (Islliil, .Jiiuni. (. prakt. ( liem., U, 7,4, p. 438. '') Pliarni. .loiirn.. Ill, 2.", ji. 7'.)il. Oil.s of the Rutiti-ene. 459 193. Oil of Jaborandi Leaves. Oleum Folioruin Jaborandi. — Jaborandiblatterijl. — Essence de Feiiilles de Jaborandi. The genuine jaborandi leaves from PiloCciriius jnliornmli Holmes i (Family Rutaceae) yield upon distillation 0.2 — 1.1 p. (/. of volatile oil,^ the yield depending upon the freshness of the material. It ha.s a strong- odor reminding somewhat of rue and a mild, fruity taste. Hp. gr. O.BfSri — 0.89."); 6!u= 4- 3°2."')'. It dissolves in 2 parts of 80 p. c. alcohol to a clear solution. It boils from 180 — 200° and sometimes solidities on cooling. By fractionation a hydrocarbon called piloca.rpene (Hardy 3) (sp. gr. 0.852 at 18°, [«]d= + 1.21°) can be isolated, which forms with hydrochloric acid a solid dihydrochloride. According to this, piloearpene appears to be dipentene accompanied liy small amounts of an optically active substance. Kleber* lias also found methyl nonyl ket(jne and homologous ketones. The fractions boiling above 200° solidify in the cold and contain a compound melting at 27 — 28° wliich is evidently a hydrocarbon as it is capable of taking up considei'able amounts of bromine in petroleum other solution and probably belongs to the oleflnic series.^ Jaborandi bark contains but very little volatile oil. 194. Oil of Angostura Bark. Oririx and Properties. The genuine angostura bark from CusjMiia trifolhitn Engl. (Galipra cusparia St. Hil., G. officinalis Hancock) (Family Rutacene) cc)ming from Venezuela and the upper Orinoco districts, yields by distillation with steam l.."i" — 1.9" p. c. of volatile oil of an aromatic odor and taste. It is slightly yellow at first, but later becomes much darker. Sp. gr. 0.93 — 0.9<3; angle of rotation «d = — 36° to —50°. CoMPOSiTiox. Aci-ording to an extensive investigaticni hj Beckurts and TroegerS the sesquiterpene alcohol, gali])ol, CiriHaiiO, is the aromatic principle of angostura oil. It boils between 200 and 270°. has the 1) Pharm. .Joiirn., -J."), jjp. .522, 5H!). 2 1 Berieht von S. & Co., Apr. 1H8S, p. 44 3) Bull. Soc. chim., II, 24, p. 497: Abstr. Chem. Centralbl., TsJlJ, p. 70. *) Private communicHtion. = ) Berieht von S & Co., Apr. 1899, p. 28. 0) Berieht von S. & f'o.. Apr. 1S90, p. 47. 7; .Joiu-n. fie Pharni. et Chim., IV, 2('i. p. 130: Abstr. .Jahre.sb. il. Pharm., 1877, \>. 17S. ») Archiv (I. Pharm., 2.H.T. pp. 518 and 6:^4; ibid., 23(i, p. ■■!'.I2. — Comp. also Beckurts & Nehring-, ArLhi\- il. Pharm., 229, p. 012: also Herzos, iljiil., 14:^, ]i. 14(3. 4-60 SiiPi'inI P;irt. sp. gi-. of ().'.)270 at 20° and is optically inactive. The hinhly unstable alcohol when heated splits oft' water, and is contained in the oil to the extent of about 14 ]>. c. A prominent constituent of the oil is cadinene f'-i-jHo^, which is the cause of the laevogyrate rotation; it wa,s characterized by its crystal- line hydrochloric acid addition product. Besides the laevogyrate cadinene a,nd the inactive alcohol there is contained in angostura oil an inactive sesquiterpene, called galipene. Tills boils at 255—260° and has the sp. gr. ().!)12 at 19°. It forms liquid, easily decomposed com])ounds witli the hydrohalogens. A terpene is found in small amounts in angostura oil, whidi appears to be pinene. 195. Toddalia Oil. Toddalhi iimleatn Pers. (Family Rut:ii:eH.e) is a shrul) which gr(.iws wild in the .Xilgiri mountains (India) and which is there called wild orange tree. All preparatiou. For the production of lemon oil the nmchine IS useless for two reasons. First, the irregular form of the lemon Ill-events all parts of the rind from coming in contact with tlie sponges, and secoml, tlie lenuai oil thus obtained is green and is, therefore, not marketable as such. The lemon oil sometimes prepared with the nnicliines is used for adulterating bergamot oil. The Eruplle ,'i jiii/uer is an instrument euqiloyed in Nice for the ]ireparation of the oil. It consists of a. bowl, provided with upright ln-ass needles, which is prolonged into a tube at the bottom. The fruit liricked by the needles allows its oil to run into the bowd and collect in the tube from which it is tilled into ves.sels. 1) .^rcliiv d, Pharm., 227, |i. Km.-,. =) Boriclit von S. & (_;>.. \\fun,tiei- of ?,'.uiil,erof fruits in tiiousanda Number of trees Nuiuher ui fiuits in tliousands Lombardy 755 144 1 4,960 5 ,.509 -P,-2(I3 11,760 343,730 2,666,693 4,.3.59,20'j 187,797 39 12,045 1,4.52 320 1,478 70,-136 541,634 .544,3.50 14,649 21.242 1,210 409,652 17,842 16.486 19,873 1.34,913 1,031.116 6,-z43,1.58 40,786 1,918 1.56 15,777 237 819 2,411 23,022 193,588 1,661,994 " 3,-237 3,3-50 12 38,7.50 4(50 7,59 1,370 13,482 ] ,02.3,450 318,779 18,132 83 0.2 9,131 4 29 79 1,029 179,784 57,043 69! 25,347 i 1,366 5.53,352 70,811 19,448 33,003 492,125 4,721.2.59 10,921,143 246,715 2,040 162 ijijjuria .Marken and Clmbria Tuscany 36,9.53 1,693 1,168 3,969 South. Adriatic- 94,486 South. .Vlediter- ranian region.. Sicily .Sardinia 915,(I0S 2,263,385- 18,580 Total 1 7,729,747 1.186,408 7,9.36.-278 1,903,159 1,418,544 247,875 17,084,,569 3,337,44.3: 464 SppfinI Fart. If 800 fruits iir(^ calenlated to a double liundred weig-lit the year 1S!)(3 would give tlie followiuji' result: Tot;il iH-odiictioTi 3,;!a7,44:i,<)()0 fi-iiits Total exj)ort ■2.n7-2,3V,0 double liiiTidi-prt weightsCr/ fS()(t])ieces 1,H9T,S,S8,()0() " Rpiiimn for Ilaliau C(jii.snii]i]ti(jii iridiisivt:' of tlie essence inaiiiifactiive ] ,489,ri;")o,()(J0 fruits Among the cousuruei-s in 18!)0 the most prominent are the United States aud tJanada with nearl.y oO percent of the total exports. Then follows Austria-Hune■aI•^• with about 20 percent. Great Britain with about 14 ]iercent, Russia, with percent and Germany with about 5 per(/ent. The total export of Ijergamcit, lemon and orange essences of the individual I'enters of jjroductirjn during the last two years was as folhjws : 1807 Kxport from Messina 500,788 k. having a value of 7,5T(),61iS lire Reggio 87, (»!)."( " " *' l,:{(10,4:2.j ■■ " Catania 12,016 " '■ " ll'0,l()O " " Palermo 72,l!);t '■ " " 721.1.".:( " Tot;d essence export ls!)7... 732,002 k. having a value of 9,718.356 lire 1S9N ExjKjrt from Messina 524,099 k. having a value of (),813,2.S7 lire " Keggio 85,069 " ' " 1,440,117 " " Catania 0,306 " " " 82,758 " " " Palermo 51,759 " " '■ 072,807 " Total essence export 1898... 067,293 k. having a value of 9,015,039 lire During the last 10 years the essence export amounted to; lfi89 277,599 k. having a value of 4,200,25s lire 1890 301,879 " " '■ 5,056,214 " 1«91 264,151) ■■ " " 4,954,055 ■■ 1892 359,378 " '■ " 5,543 358 •■ 1893 588,334 " ■• ■' 9,350,814 " 1894 066,740 " " •' 8,308,148 " l'^"'' 554,191 '• •• " 8^081^870 " 1896 514,007 " " ■' 7,579.424 " 1897 732,092 " '■ " 9,719,13:! " 1898 607,293 - " ■• 9!oi5",083 " The manufacture of the I'SseiK'es produced by expression is almost entirely carried on in Talaluia and 8icily. The only exception is the preparation of the West Indian limette oil at Montserrat. It is true that now and then sanqiles of expressed essences from the AVest Indies and from Florida appear, but one cannot yet speak of a TV ''^ The Districts of Production of ORANGE-, LEMON -AND BERGAIVIOT- ESSENCES IN Southern Italy, Scale 1: 1100 000. Legend: (Calabria.) D Districts of Bergamot. Essence of Lemon. Essence of Bergamot . Essence of Orange. >K IteJlannilair KQomoiers. .^.^n. Hi^K - roods . -Jlaibvads. — — JStnoLJtailroad. , Taltyj^j^nph Cables. tli^M'Twuees. ^±ti==jL Legend: (Sicily.) Essence of Orang e. Essence of Lemon ■with regard to its optical rotation. + 59° - -t- 61° + 61° - + 63° + 63° - + 64° 2 + 63° - + 67° Ea.st o±* GTeon^\'i^l^ FrmU'd bv F. A.BrookhaiiS, Loipzitf, Oils of the Rutnvfae. 465 manufacture in tliese places. It is liardly to be expected tliat one will arise, as the hig:li wages there paid cannot compete with the low wages of Italy. The preparation of expres.sed agrumen oils formerly conducted on a small scale appears to liave been entirely given up. The districts of production can be seen on the accompanying map. which was prepared in 1896 by a representative of the firm of Schimmel ct T'o. BergauKjts are only cultivated in Talabria. The principal center for the oil is Keggio. Lemons and oranges are planted on the continent as well as in Sicily. In Calabria lemon oil is made in the same places as liergainot oil. In Sicily the principal productive centers of lemon oil are in the provinces of Messina, ("atania, Syracuse and Palermo. The oils from the different districts often show quite important variations in their optical rotation. The angle of rotation of the Calabrian oils lies between +50 and +62°:!()'. In Sicily the principal places of production, arranged a.ceording to the angle of rotation of their oils are as follows ; «r]^4-59° to + ()1°. Messina and vicinity, Nizza di Sicilia. aj,= + Ql° to +G:',°. Acireale, S. Teresa di Riva, Scaletta. S. Lucia, Patti, S. Agata, S. Stefano. '/u=+68° to -\-(')-i:°. Catania, Giarre, Giardini, Acireale, Leutini. «£, ^ + 64° to +67°. Barcellona, Siracusa. In the province of Palermo the pla(;es colored yellow on the mapi produce only fruit but no rjil, the manufacture of which is restricted to the immediate vicinity of Palermo to which the fruit is transported. The angle of rotation of the rjils there produced lies between +.'59° and + 61°; rotations of +61 to 68° are very rare. 196. Oil of Lemon. Oleum t'itri.—Citroiienol.— Essence de Citron. Pkopekties. Oil of lemon is a light yellow liquid of the pleasant odor of fresh lemons and an aromatic, mild, somewhat bitter after-taste. Sp. gr. O.fS.'pfS — ().8()1. The angle of rotation lies as a rule between 60 and ()1:° at 20°. i Oils with a rotatory power oi +64 to 67° are rare.^ 1) It will be well to make the rotation determinations for lemon oil at 20° or to reduce to 20° by calculation, for the same reason as that given under orange oil (remai-k 6 on page 471). If the rotation is determined at a temperature below 20°, 9 minutes are to be subtracted from the result found for every degree of temperature below 20°. On condut-ting the investigation at a temperature above 20°, 8.2 minutes are, however, to be added for every degree in temperature in order to find the .ingle of rotation for +20°. 2) The oiI.s obtained in the vicinity of Siracusa and Barcellona (Sicily) distinguish themselves by a high rotatory power. The lemon oils from the province of Palermo are the weakest in rotatory power (+.^9 to 61°). Compare with above. 30 ■i06 SpeeiaJ Part. The fiUTTiniy iiiid ve<2,etal3le wax-like eonstitueiits present often prevent the (;lear solubility of lemon oil in 90 p. e. alcohol. Rectified oil requires about 5 p. of 00 p. c. alcohol to form a clear solution. Absolute alcohol, ether, chloroform, benzol and ani^d alcohol dissolve lemon oil in all proportions. The solutions in carbon di.sulphide and in benzene are usually somewhat cloudv on account of a little water contained in the oil. Oil of lemon, like all essential oils oljtained Ijy expression, gives on standing a more or less crystalline deposit. Ina.smncli as rectified and distilled oils decompose rap)idly and have a.n unpleasant, peneti-ating' odor, it is irrational to rectify a. lemon oil. Oil of lemon is rapidly changed by the action of light and air. It loses its color and a. thic-k, brown deposit separates. At the same time the specific gravity and the solubility in 90 percent alcohol increa.se. This is the same phenomenon that can be observi:-!] with old, jKjorly kept turpentine oil. Preservation. Oil of leiur)n is to be ke]it in carefully dosed vessels, filled to the neck, in tlie dark and in a cool place. C'oMPOsiTiON. Although a large number of investigators have worked on oil of lemon since the first quarter of the present century, its compo- sition is for all that not yet satisfactorily cleared up; A critical examination of the rather extensive literature, i the details of which cannot here l)e i-onsidered, shows that a p.-irt of the oils investigat'ed wt're a.dulterated with turpentine oil. This is not surprising, as it is only now possible, bj' means of the recent proof- that lenu:)u oil contahis no pinene, to distinguish pure lemon oil from that adulter- ated with turpentine oil. Kven by the first analy.ses of the oil its small annnuit of oxygen was recMignized. Home c^hemists, however, went so far as to declare it free from oxygen and consisting only of hydrocarbons. This nnstake arose from the fact that rectified oils were mostly used in the investi- gation, in which the much higher boiling oxygenized compounds remained in the residue of the fiask. 1) SausBure (1820). Ann. ile Chini. et Pliys., II. 13, p. 262; LiebiR's Annalen. 3, p. 157. — Dumas (1S33), Ann. rie Chini. et Phys,. II, 52, p. 45; Liebig's Annalen, (>. p. 255, and ibid., 9, p. 61. — Blanchet & Sell (1.S33), Liebig's Annalen, 6, p. 318.— Sonbeiran & Capitalne (1840), .Tourn. de Pharni., II, 26, p. 1; Liebig's Annalen, 34, p. 317.— Gerhardt (18431, Conipt. rend., 17, p. 314.— Berthelol (1853), Ann, de Chim', et Phys., Ill, 37, p. 233; ibid. 3S, p. 44; ibid., 40, p. 36.— Liebig's Annalen, 88, p. 346. — Oppenlieiin (1872), Berichte, 5, p. 628. — Lafont (1S87), Bull. Soc chim., II 48, p 777, and 49, p. 17. 2) P.erioht von 8. & Co., Apr. 1897, p. 19; Oct. 1897, p. 22. Oils of the RutacfiUfi. 467 In reality about ')io of the oil consist of hydrocarbons, of which dextrogyrate limonene (Wallach,i ISNol, (tetrabromide, ni. p. 124— 125°) is the most important. Tilden- (1877) has called attention to tlie fact that this terpene is contained in a far less pure state in lemon oil than in orange oil. By the oxidation of tlie limonene fraction designated by him as "citrene" he obtained paratoluic and terephthalic acids, two acids which do not result by the oxidation of the c-orresponding fi'actions from orange oil. "Gitrene" behaves likewise different than limonene when treated with concentrated sulphuric acid. Besides resinous polymerization products some eymene is formed. It does not follow, however, that cymene is contained in the original oil. It is much more likely that the cymene resulted fi'om a second tei"pene by the action of sulphuric a.(_;id. As a matter of fact neither cymene nor pseudo-cumene '^ have np to the present been found in lemon oil which had not been treated with sulphuric acid.''^ Tlie reason for the differences between "citrene" and limonene may probably be found in yjart in tlie presence of phellandrene in lemon oil. This terpene lias only recently been discovered in the oil and recognized as such by its nitrite melting at 102°. ' The behavior of the fraction boiling below 170° observed by Wallach''' can in all probability be also traced to pliellandrene. This fraction gave no solid addition product by direct bromination " but after heating from 2.50 — 270° it readil.y yielded dipentene tetrabromide. Although the terpenes make up by far the greater part of the lemon oil, the odor is largely due to the comparatively small amount of oxygenated compounds. The constituent of greatest imjiortance as to odor is eitral, CioHieO, an aldehyde, which was found by Bertram in oil of lemon in 188H.''' The amount of the eitral is estimated at 7 — 10 percent. Besides eitral lemon oil (/ontains a second aldehyde, citronellal. When coudeused with pyrotartaric add and /S-naphthylamine this yields 1} Liebig'H Annalen. 227, p. 2!I0. 2) Pharm. Joiirn., Ill, 8, ii. 190: 9, p. 0.54. 3) Bonchardat & Lafont {.lourn. rte Pharm., V, 27, p. 49) found, after treating citrene with sulphui-ie acid, yjseudo-cumene bcHideR cymene. They seem to consider these substances as preexisting in lemon oil. i) Bericht von S. & Co., CJct. 1S97, p. 23. s) Wallach, loc. cit. 6) Oliveri claims to have obtained a tetrabromide of the melting point .81° from the fraction of lemon oil boiling at 170 to 170.5° (Gazz. chim. ital., 21, I, p. 318; Berichte 24, p. 024, P.ef.). 7) Bericht von S. & Co., Oct. 1888, p. 17. 468 , Special Part. according- to Docbner'' i.-itroiiellal :-iiaplitho einchoiiiuii- acid, in. ]). 225°. Appai-entlj^ tlie statements of La dell 2 wl:o investig-ated so-called terpeiie- free lemon oil, refer a,lso to citrouellal. He isolated by fractionation a dextrogyrate body C-ioHisO boiling at 206°. Tildens in 1877 described as a constituent of lemon oil a dextro- gyrate substance of the composition OioHisO, boiling a little above 20(1°, which, with the (^xcejition of its rotatory power, agreed in its principal properties with "terpinol." Tt is probable that Tilden also had citronellal under consideration. Barbier and Bouveault,-^ how- ever, deny the presence of (Itronellal in lemon oil. According tci Umney and iSwintouS gerau.yl acetate is also contained in the lemon oils from Messina and Palermo. They removed from so-called concentrated lemon oil, i. e. from the high boiling tractions rich in oxygen, the aldehyde with hot bisulphite solution, and saponified the non-aldehydes. From the alkaline solution acetic acid was separated and from the oil a, fraction was obtained wdiich combined with calcium chloride to form a solid compijund, which yielded citral on oxidation, and consequently consisted of geraniol, which must have existed originally in the oil as acetic ester. From Palermo lemon oil, besides geraniol, a fraction of the properties of 1-linalool was isolated. Umney and Swinton are of the opinion that the differences in odor which exist between the lemon oils from Palermo and Messina can be attributed to a different ratic) of tlie quantities of citi'al and citronellal, as wcdl as to the pi'esence of linalyl ai-etate in the Palermo oil. A sesquiterpene, Ci.-;H24, of the boiling point 240 — 242° is contained according to Oliveri {lor. fit.) in the highest boiling fractions of lemon oil. The statements found in liti'rature" referring to the so-called lemon camphor or citraptene, the non-volatile constituent of lemon oil, vary so much both as to composition and properties (m. ]i. from 4.j — 144°) that the body must at present be considered as a. mixture of different sub.stances. Adulter.vtio.x a\t) Ex.vmixatiox. Turpentine oil, the adulterant mostly employed, can be readily detected by means of the ]iolarisco])e. 1] ArchiY a. Pluirai., 2:i2, p. 6SS; riorichtc, 27, p. :^r■,•2. 2) Pharni. .Joiirn., Ill, 2i, p. ."iSO. 3) Footnote 2 on p. 4(57: coiiip. alsii Wrisiit, .huirn. Chcm. Si>c., II, 12, pp. 2 and 317; Bcriflite, (i, ]). 1320. •1) (.'oDipt. rend., 122, ]>. 8.". C} Pharni. .Tonrn., 01. pi;i. I'.lfi and 870. S) .Mnider (1SH!I), r.iebis'.s Annalen, HI, p. 60. — P,orthel.it. lor. cit.— Tilden & Beck (ISOOl, .Journ. C'lieni. Soc, ."7. p. 32S ; Berichte, 23, p. .".00, Kef. — Crisnier (1891), Bull. Sric. chilli., Ill, (.), 11. 30: liericlite, 24. p. 6(11, Ref. Oil.-i of the Rutaceae. 4(59 as it decreases the rotatory power of the lemon oil to a considerable extent. In order to determine approximately the amount of the addition, it must first be determined whether French or American turpentine had been employed. As turpentine oil (pinene) boils lower than the constituents of normal lemon oil, it is to be sought for in the fraction wdrich distills over first. The lemon oil to be investigated is therefoi-e fractionated several times and the rotatory power of the frai-tion boiling at about KiO— 165° detei-mined. If the first distillate finally Ijecomes laevogyrate, French turpentine oil is under consideration, but if it remains slightly dextrogyrate, American turpentine oil has been employed. For the approximate ralculation of the amount of turpentine oil from the rotatory powei', the mean angle of rotation — ;i()" for French and + 6° for American turpentine oil may lie taken. A lemon oil consisting of half turpentine oil would rotate in a 100 + 60°+— ;!0° mm. tube in the one case ^^ ^= + l.j°, ;ind in the other case According to this it is not difficult to calculate the approximate amount of the addition, providing that it is known wliether this addition was French or American turpentine oil. Detection of Turpentine oil in the presence of orange oil. Lemon ouud solul)le in water, ("itronelhil. however, dof'.s not ]ios.sess this propertjs and its double salt .separating partly in the oily and pnrtly in the aqueous layer makes an accurate reading impossible. 1) Berlcht von S. * Co., Oct. tS'.M5, p. 8(1. 2) GaKz. clUTii. Ital., 27, II. |i. 2.~>. 3) Chemist & Unigsist, ."i3, pii. l'2(). li'.li;, '.U'.i ; 54, pp. 4!)."i, .'i+.'i. ■t| See Solilaini anil Bertc'. Roll, chini. I',arni.. ys. p. .Tai : P.erielite voii S. & t'o., Apr, UIOO. p. 2-2. Oils of the Riitaceae. 471 Grarnett i tried to conrei't the cildehydes by reduction witli sodium into alcohols, and determine these by acetylizatiou. Unfortunately, as thorough examinations have shown, the reduction does not take place quantitatively and the results are therefore useless. 2 WaltherS has published a method for the estimation of citral in lemon oil liy treating the latter in alcoholic solution with hj^droxylaniine hydrochloride and S(3dinm bicarlionate and then titrating back the excess of hydroxylamine. Schimmel & Co.-* have tested the method and found that the results are too high. Parry' has based a method on the formation of citralidene cyanacetic acid. From 20U cc. of oil 175 cc. are distilled off under 1-5 mm. pressure. 10 cc. of tlie residue are shaken in a cassia flask with .jg. of cyanacetic acid and ."1 g. of sodium iiydrate in 80 cc. of water. The part insoluble in water is read off on the scale. No determinations were made rjn known mixtures of citral and terpenes, so that the accuracy of the method is unknown. 197. Oil of Sweet Orange. Oleinii Aiiraiitii Diilcis. — Siisses Pomeranzenscliiileiiol. Siisses Oraiigensclialenol. A])felsiiiensclialeii<)l. — Essence d'Oraiige Portiiijal. Properties. Oil of orange is a yellow to yellowish-brown liquid of a characteristic orange odor and a mild, aromatic, not bitter taste. Specific gravity 0.848—0.852; '/.d = +9(j to +98° at 20°." On account of the presence of wax-like, non-volatile sul)Stances of unknown crjmposition, which partly separate on standing for some time, the oil as a rule does not form a clear solution with 00 p. c. alcohol. It begins to boil at 175° ; up to 180° nine-tenths distill over. The rectified oil is colorless ; its sji.gr. is somewhat lower, the rotatorj' power slightly higher tlian that of the original oil. Rectified orange oil is kept with difficulty, it deteriorates rapidly and acquires thereby a .stale, OTatin"' odor. 1) Chomist and DrugsiMt, 48, p. .599. 2) Bericlit von S. & Co.. Oct. 1896, p. a2. 3) Pharui. Centralh., 40, p. 621. J.) Bericht von .S. & C(j.. .\pr. 1!)()0, p. 2c. 5) Chemi.st & Druff;?ist, .IB, p. .876. f J ) Since the angle of rotation of orange oil, like that of lemon oil, varies greatly with changes in temperature, decreasing with an increase in temperature, it is neces- .sar.y, in oider to obtain conipariible numbers, to ascertain accurately the temperature and to reduce the result to 20° by calculation. As the difference in the angle of rotation between -|-10° and +20° is 14.5 minutes and between +20° and 80° it is 1.3,2 minutes for one degree of change in temperature, the reduction to 20° is made by deducting 14.5 minutes for each degree in temperature, when the polarization was eflfected at a temperature below 20°. If the detet-mination was made at a temjjerature above 20°, 18.2 minutes are to be added to the number found in order to find the angle of rotation for +20°. 472 Specinl Part. Composition. Ornuye oil consists, as Wallachi (1881) has shown, of at lea.st 90 p. c. of d-liinonene (dihydroehloride, in. p. 5(t° (Soubeiran and Capitaine,2 1840), tetrabromide, m. ]>. 104— K).")" i). On this aci:onnt, fspeciallj as othor hydrocarbons are completely absent, it is well suited for the jireparatiou of this terpene in a pure state. The absence of pinene is of iniportiim-e for the detection of adulteration with turpentine ciil. (Jf oxyjj-enated compounds, aldehydes are present in orange oil. By shaking with sodium bisulphite solution crystals of a double compound are formed, whii-li can be isolated by filtration and pressing; by decom- posing with soda an oil is obtainefl which is purified by steam distillation. A part of tlus boils at 224—228° and consists of citral (Semmler,^ 1891). The lower Ijoiling fraction contains likewise a,n aldehyde, the comjjosition (jf which has not yet been determined. The as.sertion made by Wright'^ in 1878 that r)il of orange peel contains 0.8 percent of a body boiling at 212 — 218° identical with the somewhat mystic myristicol (CioHmO) of the oil of nutmeg, is too little supported by facts. Th(.' most recent and not yet completed investigation of orange oil is that of Flatau and Labbe." The.y obtained b.y shaking orange oil with bisulphite solution a double compound, which yielded besides traces of i.-itronellal, ;i sm.dl amount of a new aldehyde that had a very characteristic orange odor. In addition an acid of possibly twenty-one carbon atoms was isolated. Like the acid, its ethyl ester is difticultly soluble in alcohol and can be precipitated by this solvent from the residue of the oil after 9.") p. c. have been distilled off. When purified it melts at 64—6.")° and has a pleasant and characteilstic orange odor. Further communications on this ester are promised. Parry suspects the presence of the methyl ester of anthranilic acid in sweet orange oil. This observation is confirmed by Schimmel \- C'O.t who have definitely shown its presence. Of the nature of the orange oil stearoptene, which finds its way into the oil by expressing the peel of the fruit and which remains in the residue when the oil is rectified, nothing is known. M I.iebis'" Annalen, 227, p. 2S;). Cdiuii. -t) ('hern. Ne\vn, 27, ],. 2G(l- Bei-iehte also Volckel (1S41), ibid , :i'J, p. 120; uiid C, ]>. 148. Wrisht & Piesse (1871), Clieni. \uws, 24. =1 I3nll. Soi'. cliim.. Ill, in, p. am. p. ! + "• 15) Chemist & DniRKist, .">(;. p. 4(>2 -') I.iebig's Aiinalen, :^^. p. :n<.l. 7) BericlU vnii S. & Co., Apr. 1900, 3) liericlile. 24, p. 202. p. la. Oils of the Rutaceiw. 473 ExAiiiXATioN. On aceomit of the low speeifli- gravity and the extraordinarilj' lai'ge rotatory power of orange oil, all kinds of foreign additions can be readily and accurately detected, as there is no adulterant l)y which these two properties would not he changed. Formerly, when the polariscope was not so generally used as it is to-day the oil was greatly adulterated with tui-pentine and sometimes even with lemon oil. Kecently ' the terpenes remaining from the manufacture of terpene-free lemon oil are used to an enormous extent in Messina for the adulteration of orange oil. For the detection of turpentine oil the lowest boiling portions of the oil are repeatedly fractionated by employing a dephlegmator, and the pinene may then be recognized b}^ its boiling point, as well as by its rotatory power (strongly laevogyrate with French and slightlj' dextro- gyrate with American turpentine oil ) . Should such a test be considered as not conclusive, the pinene must V)e converted into pinene nitroso- (■hloride and into the i:-haracteristic pinene nitrolbenzyla.mine or nitrol- piperidine ba.se. 198. Oil of Bitter Orange. Oleum .Vuraiitii Amari. — Bittcres Pomeranzeiisclialeiiol. — Essence d'Orange Bignrade. The oil of bitter orange, which plays only a. subordinate role in commerce in i-omparison with oil of sweet orange, differs from this mainl}' in its bitter taste. The rotator}' power ^ is sometimes slightly lower and varies from + 92° to -|- !)8°. All other properties are the saine as those of the sweet oil. and it is impossible to distinguish between the two oils in any other manner than by their odor and ta.ste. 199. Oil of Bergainot. Oleum Bergamottae. — Berg-amottill. — Essence de Berg-amotte. Propekties. oil of bergamot is a lirownisli-yellow or lioney-colored licjuid often colored green by the presence of copper. 3 It has a bitter taste aiid a very pleasant odor. iSpeeiflc gravity 0.882— 0.88G. The angle of rotation, which on account of the dark color of the oil can mostly be determined only in a '>0 or '20 mm. tube, varies from +H to + 20°. i| liericht von S. & Co., Oct. 1S'.)9, p. 2,j. 3) Ibidem, .Apr. 188!), p. 16. 2) Bericht von S. & Co., ,ipr. 1896, p. 29. 474 Special Part. The oil yields a clear solution with about )i to % volume of 90 p. c. alcohol and the solution does not become turbid on the addition of more alcohol. All oils do not dissolve clearl.y in HO p. c. alcohol. Many, and especially those of a high ester content, often give turbid mixtures, from which fatty globules separate on the bottom by standing. The reason for this phenomenon has not yet been determined, but can probably be sought in the wax-like constituents, which get into the oil by expressing tlie peel. This non-volatile substance, which partly separates as a deposit when the oil is kept for some time, consists principally of bergaptene. It remains in the residue when the oil is eva])orated on a water bath or by rectification; it amounts to h — 6 p. c. Rectified oil of bergamot is colorless and has a lower specific gravity (0.870— (».8M0) as well as a slightly higher rotatory ])ower than the original oil. The rectified oil is as a rtile less valualile, because during the steam distillation part of tlie ester is always decomposed. The amotmt of ester present is a uieasure of the value of Ijergamot oil, i. e. the oil is the better, the more linalyl acetate it contains. The average content in ester varies somewhat in different years; it tistially amounts to between ;i() and 4t) percent, but sometimes ri.ses as high as 4.J percent. Even within the limits of the same liarvesting period great variations occur. The oils obtained at the beginning of the harvest from less ripe fruit (.-ontafn less (down to •!() percent linalyl ai-etate); with increasing ripeness the ester content increases, for which reason the oil ex]5resse(l from ripe fruit is the best. Composition. As early as 1840 Soubeiran and Capita.ine' called attention to the presence of different terpenes in bergamot oil. AVa.llach^ showed in 1884 that d-limonene was contained in the fraction boiling from 17."i— 180°. When he heated tlie fraction of the oil Ixiiling from 180 — liH)°, which, indeed, absorbed bromine but yielded no solid bronude, to a higher temperature, high boiling condensation products were formed, and on again fractionating, the portion going over up to 190° gave dipentene tetrabromide melting at 124 — 12.j°. It does not follow fi-om this, whether the dijientene detected in this manner is to be considered as an original constituent of the oil, or whether it lias l)een produced by heating the fraction 180—190° whicli no doubt contained linalool. Likewise, the observation made by Semmler and Tiemann ■' in 1892 according to which the oil boiling 17° higher than the limonene fraction 1) Lieliig's Aiinalen. M.T, p. 31:!. 3) Berichte. UTi, |i. ns2. -') Liebig's .\nTiMleii. L'liT, ]). 2'.M). Oils of the Rutaceae. 475 yielded dipentene tetra.bromide cannot be considered as a proof of the presence of dipentene in berganiot oil. Our knowledge of the most inipoi-tant constituent as far as the odor of the bergamot oil is concerned, is due to two investigatirjns, published at nearly the same time, by Semmler and Tiemaiini and by Berti-am and Walbaum.^ Bj^ these investigations it was shown that the principal carrier of the bergamot odor is tlie acetic ester of 1-lhialool. In addition to this ester, free 1-linalool and possiblj^ substances not yet isolated take part in the formation of the aroma. The properties and derivatives of linalool and linalyl acetate have been described on pp. 128— i;il. Charabot* has uiade a comparative study of the oils of bergamot from the green and tlie ripe fruit. The oil frcjm the green fruit had a sp. gr. of 0.882 at 14°. «d = + 14°:58'; 0,289 p. c. of free acid, 33.8 p. c. of hualyl acetate. 13.0 p. c-. of linalool, and .5.0 p. c. of bergaptene. The oil from the ripe fruit had a sp. gr. of 0.883, «i, = + 20° 30', 0.283 p. (,'. of acid, 37.3 p. c, of ester. .').9 p. c. of linalool and o.-j p. c. of bergaptene. He draws the conclusion that in ripening the original linalool is changed to the ester and that during this process some of the linalool is dehydrated with the formation of terpenes. The bergaptene contained in the oil to the extent of about .j percent is completely odorless. A wliole series of investigations has been carried out on this compound."* Pomeranz'^ in 1891 succeeded in clearing up its constitution. Bergaptene C12H8O4 forms soft, whit-e. satin-like, tasteless needles, which are odorless at ordinary temperature, but on heating give off aromatic vapors and melt at 188°. Bergaptene is the monomethyl ether of a dioxycumarin which is traceable to phloro- gluein. By treating with methyl iodide and alcoholic potassa metli,yl bergaptenic acid and its metliyl ester result. According to this bergap- tene is the inner anhydride of bergaptenic acid. Examination. The determination of the purity of berga.mot oil is not difficult because adulterations of all kinds change the physii/al constants to a considerable extent. As the syjeciflc gravity of pure oils 11 BtTichtf, 2,5, |j. 11S2. = ) .Journ. f. prakt. Chein., II, 4.''i, p. 602. 3) Bull. Soo. ehim. Ill, 21, p, 1083, i> Jlulder (1839), Lieljig'.s Annalen, 31, p, 70,— f)hme fl839), Ibirl., 31, p. 320.— Fraiike, Dis.sertation, Erlangen, 1880. — Gotk'froy (1881), Zeitschr. d. allgi»m. iKsterr. Apoth, Ver., 1'.), p, 1; Cheui, Centralbl.. 1881, p. .372. — Tilden & IJeck (IS'.it)}. .Toui-n. Chein. Soc, 'jl . p. 323; f:hem. Centralbl., 1S!)0, I, p. 71!). — CriKmer (1801), Bull. Soc. (■him.. Ill, 0, p. 30; Cheui. Centralbl., 1891, II, p. 379. S) .Mnnatsh. f. Che)n., 12, p. 379: 14, p. 28. 476 Special Part. varies witliiii the coinparativel.y narrow limits of 0.882— (.».(S86, the addition of turpentine oil,i lemon oil, orange oil, as well as distilled bergamot oil ijroduce a, decrease, fatty oil, c-edar wood oil or g-urjiui balsam oil an inc^rease in tlie densit^y. A pa-rt of these adulterants wonld also clumge the angle (jf rotati(jn which lies lietween +8 and + 20° with pure oils. The solubility determination with 90 percent alcohol gives with bergamot oil results of only slight value, as by it only very extensive adulterations can be recognized. Only a pai-t of pure bergamot oils, as already mentioned, are soluble in 80 percent alcohol. If a bergamot oil dissolves to a clear solution in this solvent it is free from fatty oil, turpentine oil and orange oil. If, however, it d(_)es not dissolve, this may be due either to an adulterant, for instance, fatty oil, or also to the presence of large quantities of bergaptene or wax-like constituents. The detection of fatty oil is effected l)y weighing the residue left liy evaporating the oil at 100°, which with normal oil amounts to -j — 6 p. e. Abont 5 g. of oil (weighed accurately to 1 eg.) are weighed off in a glasi* or poi-celaiii disli aud heated on a waterbath until that which remains has lost all odor of bergamot oil. Aftei- cooling, the dish, )ire\-iouKly tared, is weighed with Hie residue. If this amounts to more than (i p. c. of tin- oil used, tatty oil is pre.s<'nt. E)ach additional |iercent rc)ireseuts one percent of • adulterant. Thus e. g. a bergamot oil adultci-ated with 5 percent of olive oil will leave a residue of from 10 to 11 ]i. c. In the oils adulterated with turpentine oil, orange oil or distilled berga.mot oil the residue will in certain cases amount to ccjnsideralily less than ."i or (J percetit. The determinatic;)n of the residue is of special importain?e as fatty oil gives a high saponification number and may therefore ea,sily iiive rise to mistakes. Ester (Jontknt. The , p. :i.-,) the evaporation residue on saponification sives numbers which correspond to an amount of 2 p. c. of linalyl acetate, this number ought by riRht to be deducted from the result found, 'rhis is, however, not done, as the method would thereby be only made unnecessarily complex-. 3) An oil obtained in Messina by distillation from the exiiressed bersamot peel Oils of the Rntaceae. 477 200. Oil of Cedro. The oil offered in commerce under tlie name of cedro oil or cedrate oil is nothing more than a mixture of lemon oil and other oils. Genuine (;edro oil, obtained by expression from the rind of Citrus medial Risso (Cedro ordiniirio, Cedrntier ordinaire), is a .yellow liquid of a pleasant odor reminding of citi'al or lemon oil. In physical as well as chemical behavior cedro oil differs but little from lemon oil. Its specific gravity is 0.871 at 15°, an — +67°S'.i Upon distillation the larger part of the oil passes over from 177 to 220°. By boiling with an alcoholic solution of /5-naphthylamine and pyrotartaric acid eitry]-/5'-naphtho-cinclioninic acid was obtained in yellow crystalline leaflets, melting at 197—200°, by which the presence of eitral in cedro oil was shown. 301. Oil of Limette. Oleum Liiiiettae. — Liniettol. — Essence de Limette. Two oils coming from different plants and of entirely different properties are designated by the common name of limette oil ^ which according to their source may be called West Indian and Italian limette oils. West Indian Limette Oil. The West Indian hmette or lime. Citrus medica L., var. acida Brandis,^ is cultivated on Montserrat, Dominica, Jamaica and Trinidad on account of its acid juice, com- mercially known as lime juice. The oil obtained from the peel of the fruit by expression (oil of limette) is of a golden yellow color and can hardly be distinguished from a good lemon oil by its odor, if the greater intensity of the limette oil is not considered. vSp. gr. 0.873* at 29° to 0.882 at 15°; «D = + 35 to + 38°. The most important constituent of the oil is eitral. Entirely different from the expressed oil is the distilled oil which is obtained as a by-product in the evaporation of the juice and is known in commerce under the name of oil of limes. Its odor is unpleasant, terebinthinate, and no longer reminds of eitral. Probably this aldehj'de posse.SHfcfl an eMter content, of 011I5' 12 p. c. (.sp. ffr. 0..S6.'). Two oils distilled from the peel ol lallen unripe bergamot fruit contained 6.3 and 23.5 p. c. of ester isp. si'. 0.S68 and 0.889). (Bericht von S. & Co., Oct. 1894, p. 15.). 1) Bericht Ton S. & Co., Oct. 1895, p. 18. 2) Arch. d. Pharm., 233, p. 174. 3) Bulletin of Miscellaneou.'i Information, Royal Gardens Kew, 1894, p. 113. *) Pharm. .Jouni., Ill, 15, p. .'S22. 478 Special Part. is completely destroyed by the boiling of the acid liquid. Sp. gr. 0.8051 — 0.8()8;2 r/D = 4-38°."')2'. It boils between ITo and 220°. Italian Limette Oil. 2 The fruit of the South European limette, Citi'UN Ihnetta. Risso (Citrus limettn vulgaris, Lima dukis. Limn di Spagi]^ dole, Limettier ordinaire) distinguishes itself from that of the West Indian by its sweet juice. The oil obtained by expression from the peel is of a brcjwnish-yellow color, has an odor reminding strongly of l)ergamot oil. and forms a yellow deposit in considerable amounts on .standing. Sp. gr. 0.872; «D = +.58° 19'; saponifieation number 75. The composition of the Italian limette oil is very similar to that of bergamot oil, only the limette oil contains more limonene and less linalyl acetiite. The linKjnene is the dextrogyr.-ite modiflcation (d.d =-- +S1°45', .sp. •j:y. 0.848) and yields a dihydrochlorideS melting at 50°, a.s well as a, tetrabromide melting at 105°. In the oil investigated by (jihlemeister 26.:! p. c. of linalyl in-etate were present (b. p. 101—103° at 13 mm., sp. gr. 0.898, «d = —9° 52'). After saponification with alkali, acetic acid was found in the alkaline solntion, while from the oil 1-linalool (b. p. 88.3 — S9.5° at 13 mm.. sp. gr. 0.870, ["-Jd = — 20° 7') was separated by fractional distillation. From it citral was formed on oxidation.* Linalool is present in the oil ])artly in the fi'ee state, partly as acetic aciil ester. The limettin which separates from the oil on standing melts according- to Tildens at 121—122°. It has the composition C6H3(0CH3)2 . C3HO2 and yields on melting with potassa, besides acetic acid, phloroglucin. 202. Oil of Limette Leaves. The oil of the leaves from Citrus liuietta contains according to Watts'' (1892) an inactive terpene, boiling at 176—177°, which yields with hydrochloric acid a crystalline hydrochloride melting at 49 — 50° 1) Phnrm. .Jonrn.. Ill, 14, p. 100.5. 2) Gildemeister, loo. cit. 3) The same dihydi-ochloride was obtained by de I^nca in ISiiO (Conipt. rend., 51, p. 258) from the terpene bollinp: at 180° of an oil, which is deslRiiated as coming from Citrus lumia. but Avhich in all probabillt.v was Itahan limette oil. Conip. Gildemeister. loc. cit. i) To which compound the "Limettsiiure," (-'iiHiOe obtained by Vohl in 1,S53 upon the oxidation of the oil (Archlv d. Pharm., 124, p. IG) owes its origin, is uncertain. = ) .Jonrn. Chem. Soc, 61, p. .844; also Tilden & Beck, .Journ. Chem. Soc, 57, p. H23. «) .Tourn, Chem. Soc, 49, p. 31 C. Oils of the Entareae. 479 and is, therefore, dipeiitene or limonene. Fractiou 220 — 230° yielded upon oxidation with cliromie acid, acetic acid and pelargonic acid, on account of wliicli it is considered as methyl nonyl ketone. 203. Oil of Mandarins. Oleum Ulandariiiae. — M'andafineiuU. — Essence de Mandarines. Okig-in. The peel of the pleasant tasting fruit of Citrus madurensis Loui-eiro ^ Ivuown as mandarins contains a very pleasant smelling oil, which is obtained like the oils of the other agrumen fruits, by expression. Properties. Mandarin oil is a golden yellow liquid with a slight bluish fluorescence, which becomes more prominent when the oil is diluted with alcohol. The odor, although similar to that of lemon oil, is more pleasant and distinctlj^ different from it. Sp. gr. 0.8.")4 — O.S.jS; ao = +65 to +75°. Two mandarin oils^ distilled in Porto Alegre (Brazil) had the following properties: Sp. gr. 0.8515 and 0.8510; angle of rotation + 74° 16' at 17° and +71° 20' at 10°. Both oils were distinguished Ijy a Ijeautiful blue fluorescence. Composition. The oil beg;an to boil at 175° and all except a small residue went over up to 179°. The fraction boiling at 175 — 177° («D^ + 7<;°15') gave on broraination in glacial acetic acid solution a tetrabromide melting at 101 — 105° (Gildemeister and Stephan,^ 1897). By conducting hydrochloric acid into the same fraction dipentene dihydrochloride, m. p. 19°, resulted (de Luca,-i= 1857). According to this the greater part of the mandarin oil consists of d-limonene. If the portion which did not distill over up to 177° be treated with bisulphite solution, an addition product is obtained, from which an oil is separated b,y alkali. This behaves like a mixture of citral and dtronellal when condensed with pyrotartaric acid and jJ-naphthylamine. The melting point of the naphtho-cinchoninic acid formed is not constant. At 197° (the melting point of the pure citral compound) the body begins to run together, but does not melt completely until 222° (melting point of the citronellal compound 225°). The positive identi- fication of these two aldehydes in the oil has, therefore, not yet been made. 1) According to de Lucca (see footnote 4) the mandarin is obtained from (Jftrus bi,^aradia sinensis and C. b. myrtifolia, according- to Sawer (Odoro^rapiiia. vol. 1, p. 74) and v. Millier (Select Extra-Tropical Plants, 9th ed., p. 120) however, from Citrus nobilis Lonreiro. 2) Bericht von S. & Co., Apr. 1896, p. 68. 3) Archiv d. Pharm., 23.5, p. ."iSS. *) Compt. rend., 4~>, p. 904. ■ 4-SU SppcinJ I'nrt. Ac'iorrlino- to Flatau and Labbt'i the expressed mandarin oil con- tains tlie same estev, difficultl.y solnlile in alcoliol, as does orange oil (comp. page 472). 304. Oil of Grape Fruit. The fniit of CifruK dcniniimn L., known as sluiddock or grape frnit, contains in its peel a small anionnt of volatile oil, uhich can be obtained by expression or by distillation. An oil- expresse) .Touni. d. Plinrni. 11, 11, |i. r,2'.t. 2| Berioht von S. & Cd., A]ir. IS',14, p. 27. M .Tourii. d. riiariii. II, 1-t, p. 4'.h;. Oils of the Rutnceae. 4:81 of paraffin colleL-t on the surface. The ale(.)holi(; solution of neroli oil Jistinguislies itself by a beautiful violet-blue fiuoreseeui-e, which becomes especially prominent when some alcohol is poured in a layer above the oil. On strongly cooling, the oil becotnes turl)id on account of the separation of parattin. At times it even solidifies ti) a butter-like mass. Tlie saponification number of good oils lies between 20 and 52. corresponding to an amount of 7 — 18 percent of linaljd acetate. Oils with a saponification nunibei- liigher than 55 are su.spicious. Details are mentioned under Examination. in order to ascertain the properties of oils which were undoubtedly genuine, fresh orange l)lossoms which were partly preserved with salt, partly with sea water, for transportation, were distilled by the firm of Schiinmel & Co.i and about 0.1 percent of oil obtained which possessed the following properties : No. Specific trravity "■\) Sap. number Behavior in a freeziiiff mi.xtiire 1. 2. 3. 4. 0.887 0.881 0.87(5 0.872 inactive — (I ='.-.2' — 0° 40' 21 21 solirjifies to n bntter-lilie mass. ] viscous, but not beeoniinK solid. The rotatoi'y power of No. 2 could n(.)t be determined on account of its dai-k color. Xos. '■'> and 4 are distillates of the same shipment of blossoms. Xo. 4 cc)nsists only of the oil wliii-h separated directly in the receiver on distillation. Its preparation corresponds to the method usually eniplrjyed in southern France, where orange blossom oil is obtained as a by-product in the manufacture of oi'ange blossom water. No. 8 is a normal ]iro(luct, i. e. .a mixture of oil seiiarating at once and that obtained by cohobation fi-om the water. The oils obtnineil by these two Tiiethods differ but slightl.)'. Of still greater im]iortance for the determination of tlie constants of pure commer(;ial oils than these experiments with ])i-eserved blossoms, are the distillations of fresh material by Charaliot and Fillet- in southern France. The oils distilled in May l8i)H in ('amies and Antibes behaved as follows: The sri. gr. was between ().N720 and 0.8757, the i| Bericht von S. & Co., Oct. 18ill, p. 26: Oct. ISiJ-t, p. -H). 3) Bull. Soc. chim., II, l',i, p. y^'i'-i. 81 4.S2 Special Part. ;ni,ulp (if rotation, «[,, between +1.42° and +4.00°. 1 pnrt of the oil dissolved in l.:i to l.ij parts of St) p. c idcoliol at 20°. The amount of ester (Ci()Hi7<-)C(jr'H3) present was 1;').4— IN.O p. r. Some interesting q\iantit;ttive distillations wvre made bj- Jean Gras in Cavmes during the last harvest (1899). Ho samples were distilled at different periods thi-onghout the harvest. The yield imnvases as the season advances, from 0.80 to 1.2:! p. c 2.") nf the '40 sam]iles were investigated by Hcliimmel & V.oA No marked differences were n<.)ted. The sp. gr. varied from 0.',!. p. ano: Hee also ErdmaniL, Beriehte, 32. p. 1213. •1) .Joiii-ii. lie Pharni., 14, p. 497; Trommsdort'f'H Xeiies .Journ. d. Pharm., I'.l, 1, ji. 227. Oils of the Rutaceae. 48S paraftius which occur in ahiiost all oils obtained from blossoms and in the pure state is i/onipletely odorless and tasteless. Its melting pi.nnt is ."^.j".! Inasmui-h as the decomposition of the paraffin is wliolly improbable, the assertion by Plisson- (1829) that the amount of the stearoptene in the oil decreases with age, evidently rests on a wrong observation. Examination. The most common and most dangerous adulterants are the oils of bergamot and petitgrain. As these for the greater part possess the same con>stituents as oil of neroli — linalool and linalyl acetate — tlie detection of small amounts is impossible. Larger additions cause an inci-ease in the specific gravity and the amount of esters, which in pure neroli oil is 7 — IS percent (sapoiiiflcation number 20 — 52), in bergamot oil H~> — 4."i p. c. (s. n. 100— l:iO), in petitgrain oil 88 — 85 p. c. (,s. n. 110—245). Orange flower oils whi(;li show a saponification number higher than 55 are tlierefore to be rejected as suspicious. Tlie propei-ty of neroli oil to separate paraffin in a freezing mixture has been employed as a test, which is not wholly irrational, as the addition of paraffin free oils might decrease the relative amount of paraffin to such an extent that a separation no longer takes place on cooling. It must, however, be remembered in employing this test that scjme unadulterated oils may in certain cases be poor in paraffin. When, for instance, at the time of the harvest a large amount of Ijlossoms is to be quickly distilled, it happens, that the distillation is not carried on to its comi)lete exhaustion and that a smaller amount of the difficultly volatile paraffin gets into the oil. For the rest it is necessai'y in testing to depend on the comparison of the physical properties with those of good oils, especially of the odor. 206. Oil of Neroli Portugal. Oleiini Aiirantii Floniiii Diilce. — Siisses Oi"ang'eiil)Uitlieii(51. — Essence de Neroli PortuffaU Oil of sweet rjrange blossoms, Nfroli Puj-tugal. i. e. the oil distilled from the blossoms of the sweet orange does not occur at all in commerce in a pure sta-te. The goods sold under the above designation are always a mixture of different aurantiaceous oils. An oil distilled in fTermany from the fresh blossoms of the sweet orange Citrus Hurantiuin Kisso, had entirely different properties from 1) Pharniacop^raphia, 2nd eil., ji. 127. -} .Jonrn. ile Phariii., II, 1.5, p. l.>2. 484 Special Part. that proriired fi-om sontlifni France. ^ The blrissoms used for tlie distiUatiou were transported from southern Spain in ir(jii easlvet.s from wliich tlie air was pumped out after liaving been filled. ().1.">4 p. c. of oil was obtained having- the sp. gr. O.I-iO:! and the angle of rotation «d^ + 1<)°8'. 207. Oil of Petitgrain. Oleiiiii Petltgraiii. — Petitgriiiiidl. — EssiMice dc Petit-itraiii. Orkhn and Preparation. Petitgrain oil is obtained fr(jni the leaves, twigs and immature fruit of the bitter orange, Citrus higtirndia Risso, by distillation with water. Former!,)' the oil was prin(;ipally produced in southern France, until towanl the end of the seventies Frencli c(jlonists ])egan the distillation in Pa,raguay. The poor (juality of the oils there produced in the beginning iin])roved in tlie course of the years to such an extent tliat the South American oil is now generally preferred (jn a.ccount of its greater reliability a,nd unifornuty to the often adidterated Fr(Jiich pi-odur-t. The market for the Paraguay oil is Asuncion; the ])riiicip;U ])lace i)f distillation is said to be the little town of Yagn;iron.-' Properties. The odor- of petitgrain oil is similar to that of neroli, but far less delicate, the taste is aronuitic and somewhat Ijitter. the color yellowish. 8p. gr. ().S,S7— o.Ooo. It turns the polarized ray of light either slightly to the right, or to the left; «d = + :!'4;!' to —\°-2-2'. The oil is solulile to a clear solutioii in 2 parts of so p. r. alcohol. Sa])onitication number 110 — 24.'i = :is — s.") ]>. c. of lin^dvl acetate. Eight different petitgrain oils recently distilled fi'om tlie leaves of the bitter orange by Charabot and Pillet^ in Cannes, had the following liroperties: Sp. gr. 0.801 0—0. ,s!);U ; «i, = — .'"11*' to — (i°l.j'. Soluble in 1 — 1.1 parts of SO p. c. alcohol. The amounts of ester varied from ."iF."— (i!t.(; p. c. It may be i-emai'ked. that oils with so strong a rotatorv power as these liavi' not yi't been met in c(jmmerce. Moreover, as a general rule, petitgrain oil is not ilistilleil exclusively from the leaves, but a.lso from the unri]:)c fi-uit, lj\- whidi tin- deviations of the commercial oils are explained. ^o^rP()SITIOx. Semmler and Tiemann+ in 181)2 fractionated petit- grain oil under l."i mm. jnvssure. The first jiortions contained a l| Bci-ii'lit Ydl] S. & Co., Ort. ISS'.l, p. jis. :',) Bull. S<.f. ctiliii., Ill, 21, |>. 73. -') Cliciiilst and Drusnist. r,l, ji. 110. M Bi-rirlite, ij.l, p. list;. Oils of thp Rutiiveae. 485 liydroi/arlioii which was rerogiiized as linioneue. The main fraction, amounting- to 70 p. c. of the crude oil, i^ontained oxygen, boiled from 102—106° and had the sp. gr. 0.8988 at 20°. The composition <;or- responded to the formula CasHaoOa. By treatment with potassa the oil was decomposed to acetic acid and linalool (aurantiol) and consisted tlierefore of linalyl acetate. According- to Passyi linalool is not the only alcohol ('kiHisO contained in petitgrain oil, but also gera.niol in the free state as well as in the ff)rm of the acetic acid ester. Besides the bodies named other oxygenized, not yet isolated com- pounds are pi-eseut in the oil, which take part in developing the S]:iecific petitgrain odor. The amount of esters, linalyl acetate and geranyl acetate, varies between 40 and S.") p. c. and usually amounts to about TA) p. c. Tlie last fractions of the petitgrain oil contain a. sesquiterpene. Charabot and Pillet^ hnve recently shown that only the petitgrain oils distilleil frrmi the leaves and twigs contain no limouene, so that the occasional presence of ddimonene comes from the ai-i.-ompaujing small fruit in the distillation. According to the authors na,med, petit- grain oil (from the leaves) contains about TO — 1~> p. c. of 1-liualool and 10 — l.j p. I-. of geraniol, as well as small amounts of a sesquiterpene. Adulteration and Examination. Petitgrain oil is adulterated with orange oil, lemon oil and turpentine oil. These additions are readily recognized by the lowering- of the specifi(- gravity, decrease in the saponification number l'.l. 3) Bericht von S. & Co.. Oct. IS'IO, p. 59. 2| Bull. Soo. (-hiiiJ., Ill, 21, T'. "+• 48C) Special Part. SOS. Oil of West Indian Sandalwood. Oleum Sautali ex India Occidentali. — Westiiidisfhes Saiidelliolziil. — Essence de Itois de Santal des Indes Occideiitales. The botani(.'al wouree of the West Indian santalwood was unknown until I'ecently. Througli a study of tlie wood and the leaves Holmes, Kirkhy and Petersen came to tlie conclusion, that the plant must belong- to the family of the Eutacear, ami Ijv no means be clas.sed with the ta.mily of the Sant;ilacfne.'^ More than this couhl not be a,srei-tained on account of the want of blossoms. In compliance with a request by E. M. Holmes of London, Scbinmiel & Co. tiimlly succeeded in 18118 in otitaining flowering- branches of the tree from Puerto Cabello in Venezuela, frcjni whence the wood is lirought into commerce. In the investigation Holmes i:-ame to the conclusion, that the plant belongeil to the family of the Rutaceae. He believed it to be a representative of a hitherto unknown genus and named it Schinuuelia oleifpra.- Later, however, he agreed witli Urban of Berlin, who determined the plant as ^l7;i,r;-;.s- lial.samifera L. The mistake \va,s caused by the fact, that the genus Ajiiyi-Ls has hitherto been classed by the English l)otanists with the fninily of the Buispiaceap. while in Germany, and according to Holmes" view with perfect riglit, it is classed with the Ihitaceae. Now, as no species of the Kutaeeae in English botanic-al literature corresponded t(.i the descri]ition of the ^^'est Indian sandalwood jdant. Holmes had considered it as a. new spei.-ies. The wood, which has no simil.-irity with the East Indian samlal- wooil, consists of sticks from a thumb to an arm in thii-kness. It is white and haril and covered with a gray bark. The anatonucal build of the wood has been studied and described by Petersen and Kirkby. The well c(jmminuted wood yiehls upon distillation I..") — ;(.."> p. c. of. a thick, viscous oil of a weak not pleasant odor. The sp. gr. lies lietween 0.9(50 and 0.9G7, the angle i)f rotation between +24 and +2'.)^. Of the com])osition of the West Indian sandalwood oil nothing is known. 209. Oil of Myrrh. Oleniu Myirhae. — Myrrlienol. —Essence de Myrrlie. Obkjin and History. Myrrh is the dried up emulsiondike juice, originally contained in the pareiichyma of the bark, of .several species of the genus Connniplioia whii-h belongs to the family of the Bursn-acfat'. 1) Fhai-iii. .roiini.. III. ir,, ])]>. 7.",. si>l jiiid 100.~>. -) Phunn. .Toui-n.. (52. i)i>. .':!. 1M7 .-nid 2l>.-'.. Oils of the Bursevaceae. 487 These shrubs yrow partly wild, and are partly cultivated in the coast districts of the Red Sea especially on the iSouiali coast oF East Africa, and appear to flourish in many parts of Arabia as far as Pei'sia. The distilled oil of nij'rrh was well known to Eyff, Cordus and Gesner. In the driii;' and spice ordinances it is first mentioned in those of the city of Frankfurt-on-the-Main of 15S7, avui taken up in the Dispensatoriuui Noricum of l."i89. Observations on the methods of preparation and yield were made in the course of the eig-hteenth century by Hoffmann, Neuma-nn, Spiel- mann, Thielebein, and later by Braeonnot, Pelletier and Brandes. The ofiicinal (Ph. G. III.) or Heraljol myrrh is derived from Coin- mipliom abyssiiiicn Eiiyl. and C. schimpi^vi Enul. from southerii Arabia, anil the coast districts of Somali-land. It can be distinguished from cither varieties in that the extract made with petroleum ether is colored red hj bromine vapors. This color reaction is also peculiar to the volatile oil which is obtained by distillation in yields of 2..") — S. p. c. Properties. Oil of myrrh is a thick fluid, of a yellow to greenish color and has a strong myrrh odor. Sp. gr. 0.988— 1.007. K<")hleri^ in LsOO found a density of only 0.9(524 at 17.5° due jiossibly to the fact that in the preparation on a small scale the heavier parts are likely to remain in the resin and only the lighter oil comes over. Angle of rotation «l)= — (57° al' (Kohler) to — 90°. Gladstone^ observed in a. 10 inch (2."'i cm.) tube a rotation of —136. Oil of myrrh boils according to Kohler from 220 — 325°, according to Tucholka« (1897) from 2(30—280°. It dissoh-es to a dear solution in 10 parts of 90 p. c. alcohol. Composition. Of the constituents of oil of myrrh not one lu^s been isolated and identified. An elementary analysis made by Ruickhold Avhich had yielded numbers nearly corresponding with the formula C10H14O, induced Fliickiger* (1S7(5) to investigate the oil for carvone. It was found, however, that this body is not cDutained in oil of myrrh. Bisabol Oil of Myrrh. ' Bisabol, or Bissabol myrrh comes from the interior of the Somali-lands and according to Holmes is ideutic-al with the opopanax (.see this) now occurring in commerce. It does not give the color-reaction with bromine vapors as described for Herabol mvrrh. 11 ArchU' d. Pharm., 22S, p. 291. 41 Korichte, !), ]p. 471. 2) .foui-n. Chem. Soc, 17, |i. 1. =1 Arcliiv d. I'harm., L'H.", \>. 28<:i. 0) Archiv d. Pharm., 2;).", p. 21)S. 488 Special Part. If (i drops of the petroleum etlitT extract of I'.isabol iiiyrili (1:].",) are mixed with 3 cc. of filacial acetic aoid and tliis liquid poui'ed iti a layer on to]) of 8 cc. of coEicentrated snlplinric acid, a rose colored zone is formed at the place of contact of the two layers, and in a short time the entire acetic acid layer will become ]]ink. Herabol myrrh gives under the same conditions only a very slight pink coloration to the acetic acid layer. The zone of contact of the two liquids is green. Oil of Bisaljol inyrrli is mobile and light yellow. 8]). ,(_lf^ii(Jr()n knlhl Ivunth). In the collection of ('hinese di'ugs it is (;onini(inly designated as myrrh and has probably been often mistake!! for this. According to Holmes it may probtibly be the myrrh of the 8cri])ture,s. Upon distillation o]jopauax yields — K) ]i. c of oil of a greenish- yellow color and a. jileasant balsamic odor. It ri\sinifles readily c)n ex- posure to air. Sp. gr. 0.S70— O.OOo ; '/d = — H> to —12°.-" It dissolves to a clear solution in an equal pai't of 00 ]i. c. alcohiil. Oil of opopanax boils with decomposition between 2."0 and •'!()0° (P)aur.'' iNb.j). The carrier of the characteristic odor is found in the lower boiling portions, t Kecently Knitb' has made an investigation of undoubtedly genuine oil. The oil was prepared b,y shaking out the alcoholic solution of the 1) Phanii. Jmirn., Ill, 21, p. .S3S ; ■2r>, p. ."lOO: t;i. ],. .-.o."). -O .Vii oil lU.stllled in the laboi-ator.r ot Schimniel t^c Cii,. was pi-iibalily iilit,'uni'il tfimi tlie u!e^»resin of anottier plant. Yield l>.7 p. c; sp. o-r. o.spl; '/.d ^ + iL*- HiV 3) .iiTli. il. Pliarm., 13.S3. p. 2:1.-. J) BcriL-ht von S. & Co., Apr. Isild, p. 8+. 5 .\rcliiv (1. Pliarm.. 2^7, p. O.'C. Oils of the BiiTfieraceae. 489 ivhiin with petroleum ether. AVith bisulphite solution a brownish mass was separated, which on sulilimation g'ave white (/olorless needles melt- ing at I:-?:-! — 1:-54°. The body corresponded with the formula CaoHioO? and was called oponal. The oil itself, when distilleil under diminished pressure gave at first colorless distillate having the odor of lovage oil and later a blue distillate came over. Crj'stals of oponal separated in the neck of the retort. 211. Oil of Olibanum (Frankincense). Ok'Lim Olibaiii. — Weihraneliol. —Essence d'Oliban. History. The distilled oil of olihamim was known to Valerius (_'ordus. but was seldom mentioned in literature. In the treatises on distillation of the sixteenth i-entury frankincense is mentioned as one of the many constituents used in the distillation of the complex balsams. Oil of frankincense is first found as Oleum thnvis in the drug orcUnances of the city of Berlin for 1574, and of Fra.nkfurt-(ra-the-Main for 1587 ; further in the Dispensatorium XoricuTU of the year 15cS9. The older investigations of fraidviueeuse as to content of volatile oil as well as the properties of the oil were mostly made in connection witli like investigations of oil of myrrh of whii-h the more important liave been mentioned on p. 4-S7. Ohic+ix Axn Preparation. Franlvincense is (jbtained from Boswfllin c;ii-terii Birdw. and other species of the geiuis I'o.swellin (Family Buvsevacpae) in Homali-land and in south-eastern Arabia. If the bark (jf the frankincense tree is rut. a white emulsion oozes out, which solidifies after some time and then forms yellow graiuiles (tears or drops) which are separated from the tree trunks or picked up from the ground. Frankincense yields upon distillation with steam :! — H p. e. of volatile oil. It is c-olorless or yellowish and has a pleasant balsamic and slightly lemon-like odor. Sp. gr. ().H75— ().,S,S5 ; '/-d =—11° to— 17° (Stenhouse.i 1840). CoMPOsiTiox. (hi of olilianum, consisting for tlie greater part of terpenes, when distilled comes over principally aliout 102°. i After fractionating several times a laevogyrate hydrocarljon of the formula CioHio is obtained, which boils at 157 to IGO". It yields witli h^rdro- chloric acid a monohydrochloride melting at 127° (Kurbatow,- 1874); with amvl nitrite and hydrochloric acid a nitrosochloride melting at 1) LiebiK's Annalen, Ji.", p. ;J0<;. 2) Liobig's Aniiulfn, \~a, p. 1. 490 ^ Special Fart. 100—101°. Till' Itittei- when boiled with alcoholic potassa is readily converted into nitroso pinene CmHasNO meltinji' at 13U°, from which it Follows, that the terpene boilinf;- at 157 to 1(30° (the olibene of Km-batow) is 1-pinene (Wallacli.t 1889). The fraction boilin^i- between 177 and 179° yields on broniination dipentene tetrabromide.^ The second constitnent of the oil is therefore dipentene. As oil of olibanum gives with sodium nitrite and glacial acetic acid the phellandrene reaction, phellandrene is the third terpene con- tained in the oil.- The o.\ygenized fractions bnilin.n' above 17."° liave not ,^■et lieen carefully investigated. 212. Oil of Elemi. Oleum Elemi. — Elemiol. — Essence d'Elemi. History. Elemi is a dried up resin juice, comparable with turpen- tine, of a nundier of different trees belonging- to the family of the Biij-f^ernce/ie. At the jirespiit time elenn resin conips mainl.v froin the Philip])ines. especiall.v frcjm Luzon. Besides this, now and then Centi-al American, Brazilian, West African and other varieties occur in the market. The distilled elemi oil was first mentioned in the ordinance of Frankfurt-on-t he-Ma in of 1.">M7 and included in the Pharnmi-opoea Augustana of Kil:-!, likewise in the Frankfurt Pharniai-opoeia of 1G49. The first determination of the .yield of volatile oil was made fiy Neumann about 17H0; Bonastre in 182;'> and Manjeau in 1824 relocated the experiment. Origin and Preparation. The Manila, elend I'xclusivel.v used f(n"the preparation of elemi oil consists of a thick, turpentine-like, white mass endosing- many small fragments of bark. On kee])ing fen- some time it takes on a wax-like a])])ea.rani-e on the exterior, due to drying out. by which the outer la.ver becomes of a yellow color and loses its odor. When treated with 90 p. c. alc-ohol in the cold a, part dissolves, while a ci-ystalline residui' renmins. From the .solution prepared l)y boiling, needle-shaped crystals of amvrin .separate in large (juantity on cooling- ( Vesterberii-.3 1S87). 1) Ijiebig-'s .\nnnlen, 2.^2, ii. 1()0. 2) Observation made in tlie lalnn-atoi-y (if Schininiel ^: Co. 3) nerichte. 20, \>. 1242, Oils of the Burseraceae. 49] The botanical source of the Manila elemi is not definitely known: it is. however, supposed that its source is a species of C;ni;irium. Neither Cmmriuin coimnunt' L. the resin of which forms a dry mass.i nor Cann- riuni muelleri need be considered in discussing the source of Manila elenii, as the tui-pentine of the lattei' plant c-ontains a.ccording to Maiden, 2 (18!»2) no crystalline constituents, and its solutions deposit no crystals on evaporation. Up to 30 p. c. of oil are obtained from Manila elemi l:)y distillation. Properties. Oil of elemi is colorless or pale yellow and has a decided phellandrene odor. The- specific gravity of the oil prepared on a large scale lies between 0.87 and 0.01. Distilled on a small scale terpenes principally come over. Hence the specifie gravit,y is fonnrl to be lower, as for instance by Flii(;kiger3 who determined 0.860. Manila elemi oil is optically' dextrogyrate;* vd ^ + H° 3'. With sodium nitrite and glacial acetic acid it gives a strong phellandrene reaction. Composition. The fraction of the oil boiling below 17.">° contains according to Wallach" (1888) d-phellandrene. In fraction 175 — 180° dipentene is present to such an extent that it is very well suited for the preparation of dipentene derivatives. The dipentene was identified by means of the tetrabromide m. p. 12.")°. and by the nitrosochloride and its conversion into carvoxime melting at d-i°. The elemi (ill investigated by Deville^ in 1840 also contained dipentene, as it yielded a solid h.ydrochloride. Besides these terpenes and polyterpenes elenu oil also contains ox.ygenized ]iroduets, which readily split off water, even when distilled by themselves, Imt especially when distilled with potassium acid sulphate. 3 In the preparation of the (jil on a large scale a portion was obtained which sank in water. This boiled in a vacuum of 10 mm. pressure between 158 and 1(13°, tlie main portion from 100—101°. Under ordinary atmospheric pressure this fraction boiled at 270 — 280°, was optically inactive and had the sp. gr. 1.043 at 15°. Upon oxidation with potassium permanganate an acid of the melting point 170° was 1) Pharmacosraphia Indica, vol. 1. p. :^21 . 2) Pharni. .Touni., Ill, 23, p. la. 31 PharmacoKQosie, ."Srcl ed , p. SH. i) An oil examined by Devilie in ls+'.) (Liebig's .\nnalen, 71. p. :i?)H) was stronai.v laevog-.rrate and probablj' obtained from a different variety of elemi. Comp. also Stenhouse. Liebig'H Annalen, 36 p. f.tii. &) Liebig's Annalen. 2411. p. 23.-!; 2.12. p. 102. fi) Liebig's Annalen. 71, i). .S.5.3. •192 Special Part. obtained, the .silver salt of wiiic-li, staljle toward light, after l)eiiio- purified by reerystallizatiou from boiling water, was analysed, 29. 5H p. c. of silver being found. i The composition of the acid, which no doubt rejjreseuts the direct oxidation product of an oxygenized compound h;is not yet been determined. 213. Oil of Conima Resin. The resin known under tlie name of conima. resin or Hyawa gum from Ti-ic;i< hppt;ijihyU;i Aubl. is use. Guayana linaloe wood came for the tirst time to Marseille in the seventies where it was used for making the oil. The oil is distilled in Cayenne itself only sin(;e 18t).'i. ()Biuii\.-t On account of the great simila.i'ity of their physical .-ind chemical properties the oils from the wood of entii-ely iliftVrent trees nre designated by the common name of linaloe oil. The Mexicnu linaloewood, called in .Mexico LiiX'">J'>i' or Limilufi, txXfit) lioin dt' citron ilc .l/ex;V/!7c comes from Bursev:). cleljibechinmi Toiss. belonging to the fnmily of linr cr.-ircue. and probably also from Ihn-Kcrn nlocxyloii Eu;iler { I'JInjiIiriiiin nioexylon Schiede, Aniyi-is liu:i]. O.".. 3| .\lso .spelled liffnnloe. 2) LiebiK's Aiiiinleii, Ise, ).. 2.-,:',. .1. | phann. .lo\n-ii., Ill, is, p. \:V2. Oils of the Bursemmae. 493 Upon distillation, which is carried on in a primitive manner by native Indians in the province of Guerrero, south from the capital of Mexico, the wood of old trunks is said to give a yielil of li) — 12 ]>. c. of oil. Wood distilled in Europe gave only 7 — 9 p. c. of oil. The lin aloe wood from French Guayana. or Cayenne linaloewood is called bj' the natives Likriri. by the French colonists Bois df rose im'ile. It is further designated as Z?o;.s <:le to e ffiiielli^, liois jauiie, Boik de citron de C'tiyeniw. (JMre jaune or Copahu. The botanical source has not yet l)een definitely determined, but according to Moeller'' Ocotea caudata Mez., a tree belonging to the Lanracene may. with considerable probability, be considerd as its source. The wood is hard and heavy, readily cleavable, on fresh surfaces yellow, on older ones of a, reddish color. It is exported from Cayenne in logs ileprived of bark, the size of which indicate enormous trees. Properties. Although both oils are in general very similar, differences do exist, especially in the specific gravity and optii-al rotatory power. The liTialoe oil (.>f conimerce is almost exclusively the Mexican. This is a c(jlorless to yellowish liquid of pleasant linalool odor.^ Sp. gr. O.ST.I to (.).y9,"J; «d = — 5 to — 12°; saponification number 1 — 10. With two and more parts of 70 p. c. alcohol the oil yields a clear solution. Cayenne linaloe oil can be readily distinguished from the former by its odor. 8p. gr. 0.870— O.SSO ; «d = — lo° to —20°. Its solubility is the same as that of tlie Mexica.n oil. Composition. Linaloe oil consists almost entirely of an alcohol CioHisC). bnt slightly, have 1) Phai-m. Post, 2'.X Xo». 46—48. 2| The odor, which iw iiwuall.v described as lennni- nr rot^e-like, has not the sliahte.st resemblance either to that of rose or that of lemon. 3| Compt. rend., 92, p- V-^x : -'4. p. 7.BS; Ann. de Chi)]!, et Phy.s.. \. L'.~i. ]>. 427. J.) Beiichte, 24. p. 207. 5) Compt. renil., 114, ]>. 1574; 110. ii. .SS.'!. 6) Compt. rend., 121, p. Kis. 4!i4 Special Part. lieeii found by Schiminel et (?o.i in the oil. Tliey are geraniol and metlij'l heptenone, which so often accompanies tlie aliphatic terpene alcohols. According to Barbier and Bouveault^ linaloe oil contains also 3 percent of a sesi]uiterpene, 0.1 percent of a monatomic and a like amount of a diatomic tei'pene. Examination. The adulteration of linaloe oil witli fatty oil. whic-h has been observed several times, can be readily determined by its insolubility in TO p. c. alcohol, by the inci'ease in the specific gravity and bv the high sa]ionifli-ation number. 215. Oil of Cedrela Wood. About 12 different s]:)ecies of the genus Cedrvhi I Fa,mily Meliiirene) indigenous to America, yield a pleasantly odorous wood, which is used foi- making ciga.r and sugar boxes. It is incorrectly called cedar wood ^'olatile oils have been distilled from a. numljer of these wf}ods, the botanical sources of which are unknown. 1. t'cdrela wood from (Jorinto (Nicaragua).-^ Yield 2.;i pt. c. Yellow oil of the sji. gr. 0.9(IG and the angle of rotation an = — 17°23'. 2. (Jedrela wooil from Cuba.^ Yield l.T-'i p. c. Slightlj' yellow oil (if the sp. gr. 0.923 and the angle of rotation «ij = + l,S°(/. It contains large amounts of cadinene, the laevogyrate hydrochloriile of which, melting at 118° was prepared. :i. Cedrela wood from La Plata. « Yield U..">0 p. c. Optically inactive oil of a light blue color and the sp. gr. O.02H. 4. Cedrela wood from Punta Arenas (Costa Eica).^ Yield 3. (Hi p. c. Light blue oil, boiling from 203—270°. Sp. gr. 0.91.j; «D = — .J°5;:i'. Consists principally of cadinene, as was shown by the preparation of the dihydrochloride melting at ll.S°. •"5. Cedrela wood from Cedrela bnisiliensi.s (Cedrehi odornt;i\j.'l) from Porto Alegre.^ From the sawdust, of this wood only 0..") p. c. of a light blue oil of the sp. gr. 0.9348 and the angle of rotation '^D = — 0°22' were obtained. The oil may perhaps be identical with the La. Plata cedrela wood oil mentioned above. 216. Oil of Senega Root. The senega belonging to eastern North America, Polygnla aenegn L, (Family Polygnlncene) contains according to Renters in its root 0.25 1) Bi'i-icht von S. & Co., Apr. 1S92, 3) Bericht yon 8. & I'o., Apr. 1,S92, p. 41. p. 24; Oct. ls;)4. p. ;!.-). -i) Bericht von S. & Co., Apr. ISOu! p. I>9. = ) Conipt. rend., 121, ]>. KJS. 5) Archiv d. Phariii., 227, \\. 313. Oils of the EuphoThiaceiie. 49S tc.) 0.83 p. I-. oi volatile oil, which consists of a mixture of methyl salicylate and an ester of valerianic acid. Quite a number of other species of the genus roIy — 3 p. c. of volatile oil. Propertiks. Cascarilla oil is yellow to greenish and has a slight aromatic- odor and taste. Sp. gr. O.iSiX) — ().!)2.'5; f/D^ + 2 to +5°. In Oti p. c. alcohol it is readily soluble. Composition. Of the but incompletel}^ investigated oil not a single constituent has been definitely determined. Vtilckel'i in 1840 separated the oil hj frai;'tionatiou with water vapor into two portions. The first part was mobile, boiled at 173°, had the sp. gr. 0,(SG2 and was almost free from oxygen. The oil wliich distilled over later was viscous and c-ontained oxygen. According to Gladstone-' (18G4) the oil consists of two hydrocarbons, of which the one has a lemondike odor, boils at 172°, and is probably dipentene (Briihl," 1888). The second hvdro- i-arbon is described as being similar to c-a,lamus oil and is probably a sesquiterpene. 1) Rec. fles trav. chim. des Pays-Bas., 18, p. 421. 2) Compt. rend., 119, p. 802; .loiini. de Pharm., V, .51), pp. 96, 1SS, 4:53: VI. 8, p. ."j"? . 3J Termed Ijetulawe by Schnee^ans in 1896 (.lournal der Pharinacie von ElBatss f^othi'ingell. 28, p. 17). -)•) Liebig:-s .\nnalen, 35, p. 807; comp. Trotnrasdorff, TroiiiniHdorff' s Xeue^; .Joni-Ti. d. I'haim., 26, II, p. 186. 5) .lonrn. C'hem. Sue, 17, ]:i. 1. C) Berichte, 21, p. 1.52. 496 Sppcinl Part. 218. Oil of Stillingia. The puro-ative root of Stilliiigin silvnticn I. Miill. (Family Eiiplior- hhiceiK^) iiidiseiious to North Amerii'a. from Yirg-inia to Fhji'ida., ii.nd westward to Kansas a.iin goes over a1 l(i()'. With dilute acids it yields terpin hydrate According to tins the i)rincipal constituent of oil of mastiche appeai-s to be d-pinenc 220. Oil of Chios Turpentine. (Jhios tm-[)cntine, already known to the ani;ients,-i is obtaineil by making incisions in the ti'Uidc of Pist.-iri.-i tt^i-fhiiitlni.s L. (Family .!;),•(- 1) Amer. .Jcurii. I'harni., .'7. |). ."i^ll. ■-) Bericht vcii S. t'^- c,,.. .\]ir. Is'.C!, p, lu. s) Archiv (1. Phariii.. L'19. p. lie. 1) Chins turpentiiu' is tin-' Ti/ifi'.y'ln^- i,f Tlieni)lii-.-istus ami tin- rtol^ii'^il,,^ ,,f ,,thi-r authiirs. From this (h'sisiiaticn tlu> word "Tiirpfiirine." at pivseiil used for tlie resinous juii-L- of the cliflVrrnt sprrirs of /'/(uix. is .l.-riveil. Fliiukiffer & Hanhiiry. rharmaco- ffrapliia, jj. lOtl. Oih of the Anacardiacene. 49T CHrdmcHae) widely di.stiibuteil in the orient, especially in the island of Chios. Chios turpentine has the consistenev of the ordinary turpentine of the conifers and like it consists of a mixture of resin and volatile oil. Upon distillation with steam about 14 p. c. of oil are obtanied from this turpentine. The oil has a pleasant, mild, turpentine-like odor, wliich reminds somewhat of mace and of camphor. iSp. gr. 0.868 — 0.809; '/.D= + 12°0'i to +l<)°4."i'.2 When treated with sodium the oil boils at l.")7° and has, as shown by an elementary analysis, the composition of a hydrocarbon CioHie. The distillate saturated with liydrcichloric acid yielded a solid compound. ^ From this it follows without a doubt that Chios turpentine oil, like ordinary turpentine oil, consists for the greater part of pineue. 221. Oil of Schinus. Ohigix. Schimis inoUe L. indigenous to South America, is often planted in southern Europe on account of its fine feathei-y leaves and fragrant j'ellow clusters of blossoms. The aromatic berries serve for the preparation of a wine-like lirink. They taste at first sweet, later spicy and at last sharply pepperish and are used quite extensivel.y in Greece in place of pepper. In odor they are similar to elemi, but also remind of pepper and juniper and yield upon distillation 3.35^ to ~^.^2 p. e.*' of volatile oil. Properties. ■ A mobile oil, having the (jdor of phellandreue ; sp. gr. 0.8.50; «u = -f40°4' at 17°. soluble in :5.:5 and more parts of 90 p. c. alcohol. Composition. By conducting hydrochloric acid into the lowest boiling fractions Spica-'' in 1S84 obtained a. solid monohydrochloride melting at Vl~)°, the formation of which (/an probably be traced to pinene. A nitrosochloride could be obtaineil in only very small quanti- ties from a fraction boiling xny to 170° of an oil investigated by Gilde- meister and Stephan," from whicli it follows, that only a small part of the oil estimated, at most % p. c. can consist of pinene. The largest amount boils from 170—171° («rj = + f. The sijecitlc aroma, ])eculiar to wine and cognac is produced by the ethereal fusel oil. It is also called oil of (;ogaac (Ger. DrnsenoL Weinheerol, M^'einol) and is a product of the fermentation actioii of wine yeast. For this reason it is principally found in the yeast deposited from the wine on the bottom after com- pletion of the fermentation. The wine itself contains only minute amoimts of it in solution, namely 1 part of oil in 10,000 pai'ts. For the preparation of oil of cognac either the residues (liquid wine yeast) remaining in the barrels after removing the clear wine, are distilled, or the yeast cakes remaining after expressiim iif the liquid are utilized. The distillation is conducted in a. very primitive manner in the wine ilistricts. Formerly a liarrel, lined with lead and provided with a ron- denser, the (contents of which were heated with ilirect steam, served as distilhng a])paratus,- According to a. more recent description,-^ ordinary whiskey stills are used, which are heated hj tire and provided with a stirring arrange- ment to prevent the burning of the yeast. Before the distillation additions of various kinds are sometimes made to the yeast mixed with water, the purposes oi which are not clearly understood. According]to Rautert^ to .">() k. of le(\s 2."iO g. of sulphuric acid are added, by which the mass is said to liecinue more fluid. In the Palatinate to^a mixture of 1 part of lees with 5 parts of water, 2 p. c. of freshly slacked Jli me, 1 p. c. of potassa and 1 p. c. of salt are added. 1) .N'itrosucarvacrol melts at l."i3°. 3) (.'humi.st and Druggist, 50, p. 18;5. -) Diiigl. iHilyti'fhn. .Joiirn., 148, p. 71. Oils of the Vit^icrae. ■ 499 The oil collected in the receiver floats ou to]5 of the alcohol con- taining water, from whicli liquid still further amounts of oil can be obtained by cohobation. The yield of cognac oil from yeast cakes is given as ().0;i(j — 0,()(;6 p. c. Hchimmel & Co. obtained, however, from the wine yeasts from the Rhine and Palatinate 0.07— 0.12 p. c. of cognac oil. Propekties. The crude cognac oil, usuallj' colored green by copper, contains large amounts of free fatty acid, which, because odorless, may be I'onsidered as a worthles.s constituent. For purification the oil is first freed fi-om i:-o])per by shaking with tartaric acid s(jlution, then freed from fatty acids bj^ treatment with soda solution, and in this condition forms the second quality (jf cognac oil. The finest quality is prepai-ed Ijy the rectification of the oil so purified. In this process a part of the slightly odorous esters of the higher fatty acids are kept back, on account of which the distillate of course becomes stronger. The physical pi-operties of these three varieties, the crude, purified and rectified oil, are of course different. As, however, the observation material at hand is insuflicient, general means of differentiation cannot at present be given. Oil of cognac pos.sesses a stupifying odor, which is unpleasant and even offensive in the undiluted state. Often an empyreumatic odor is perceptable, due to careless preparation. The specific gravity of diffei-ent crude cognac oils coming from the Moselle, from Tyrol, from the Rhenish Palatinate and the Eheingau varied between 0.87.") and O.H8.5.'' Opticallj' they were slightly laevo- or dextrogyrate, 2 " Amyl alcohol 190. 1>1 " Furfurol | ., i ,, .. Bases f Pleasant suielliTig oil of wiiip^ 7.01 " xicetie acid Traces. Butyric acid Isobntylene glycol 2.10 " Glycerin l.:3S ■■ In the investigation of another cognac. Ordonueau-' in 1S8(J found 218 g. of normal butyl alcohol in a hectoliter, and considered this as the ehai'acteristic ]3roduct of the fermentation of the elliptical yeast. Later, however, it was found, that the cognac investigated by Ordon- neau had ])robably Vieen prejiared from a wine, whiili had contained the Biii'illus Imtrricus, and the presence of the butyl alcohol, whii?h does not form under normal conditions is to be traced to this sonrc-e. From these investigations it follows, that the cogiurc oil, wlnm it is obtahied in the manner de.scrilied above, is far from containing all of tlie constituents of cogna.i-. It is therefore never possible to obtain with such a,n (jil a ])roduct that can be comi)ared to a. genuine cognac prepared by distillation from wine. C) Liebiff'.s .Innalen, l.-)7, p. 204. 2| Ibid., 11. 270. 3) Ciiinpt. rend., lo.", p. 1019. ■t) Probably identical with the eof^Miac oil obtained I'roin yeu.st. 5) Conipt. rend., 102. p. 217: lonip. also riaiidon i: Morin, Compt. reud., 104, p. 1 nil) : further Sell. .Vrbeiten aus ileni Ic.-iis. Oesundheitsamte. (i, p. y^.*^. Oils of tlip Mnlvaceae. "lOl Examination'. The tests are at present restricted ti) the deterniiiia- tion of a possible presence of alcohol. For this purpose a certain quantity of cognac oil is shaken in a graduated cylinder with an equal volume of water or glycerin. The presence of alcohol is shown hj an inc-rease in the water or gl.ycerin layer. 223. Oil of Linden Flowers. (_)il of linden flowers is pi-epared by treating the water obtained by distilling fresli linden flowers with common salt and shaking out with ether. On evaporating the ether 0.088 p. c. of oil remain. Oil of linden flowers is colorless, very fluid, (juite volatile and possesses the odor of the fresh flowei-s in a high degree. It is soluble in all proportions in ether and alcohol (Wiuckleri). 224. Oil of Ambrette Seeds. Oleiiin Abelinosclii Seininis.—Moschuskornerol.— Essence de (Jraiiies d'Ambrette. Hibiscus nljflmoschus L., (Abelniosvhus mosclmtus Moench), (Family Malvaceae), jdelds the ambrette seeds, formerly officinal in the German Pharmacopoeia, and no longer used in medicine, but which are still employed in perfumery. The herb-like plant is indigenous to India, but has lately been cultivated in Java and in the West Indies (Martinique). The oil was flrst prepared by 8chimmel & Co.- in 18S7. Upon distillation of the comminuted ambrette seeds a yield of 0.2 p. c. of oil is obtained. Furfurol has been isolated from the distillation water. ■* Oil of ambrette seeds is solid at ordinary temperature; it begins to solidify at about 30—35° and has an agreeable, musk-like odor. 8p. gi'. about 0.900 at 25—35°. The oil is inactive or only slightly dextro- gyrate. This property can be used to advantage, when it is required to distinguish the mixtures witli cedar or copaiba balsam oil found in commerce, from genuine oil. The compound wdiich causes the solidification of the oil is a fatty acid, most probablj^ palmitic acid. As the result, the oil has a high saponification number lying between 180 and 200. 225. Oil of Tea. By extracting dried tea leaves, Thea chinen.si.s h. (Family Theaeeae). with ether, 0.0— 0. 08 p. c. of a citron-yellow extract, solidifying on 1) Pbarmaceut. Centralblatt, 1837, p. 781. 2) Bericht von S. & Co., Oct. 1887, p. .y van Roniburgli^ by the dis- tillation of fresh fermented tea leaves. The yield was only O.OOG p. fi. The (jil .'ippears to be formed during the fermentation, pi-oliably by the decorapositi(.)n of a —l'A° ( 74(.) Tnm. pressure), of a penetrating fusel-like oilor, strongly reminding of tea, is obtained. Its ]jrincipal con.stituent is an alcohol of the formula ToHioO, the acetic acid ester of which boils at H>i)—H>~)° . Oxidation with potassium biidii-oniate converts the alcohol into an oil of the composition and the properties of butyric acid. By heating the alcohol with hydrochloric acid in a sealed tube to l()t)°, a chloride boiling at 120° is formed. The fraction of r)il of tea which on distillation passes over between 220—22."')° is methyl salicylate. The ])resence of metlijd alcohol lb. p. 0()°. nitro metlivl meta-phenylene- diamine compound and oxalic acid metliyl ester, m. p. 51° ) in the aqueous distillate was shown. This is, however, not a. product of fermentation, but is. as vail Romburgh had previously shown, a constituent of the fresh, unfermented tea leaves. 236. Oil of Borneo Camphor. OrKtIN and PuEiWHATroN.s The Borneo-camphoT- tree. Di\v(>h:ihiuop» ;irom;itic!i Gfirtn., is a large and beautiful tree, indigenous to the north- western coast of 1-inmatra and to northern Borneo. In the cavities and cracks rjf tlie wr)od of old trees is found the valuable Bcirneo camplior. also called Baros ca.mphcir. Sunuxtra ca.niphor. or Malay carnphor. It is used by the Malays for the embalming of the dead and for ritualistic pur- poses, and well paiil for. Besides the camphor, the trees contain also a volatile oil. which is obtained, eithei- by tapping the tree or by the distillation of the wood. 1) PoggemliirlTs .\iiiialen dcr Phvsik. 43. ]r IGH; Liebig's .Viinali'ii. 2.S. p. :-!14. 2) A^erwlag oinlreiit tlen Stiiat van S'Laads I'lanteatniii le lUiitenzorg-. IS'.l.*., p. ll'.(, and ISill), p. Iijlj; Berii-hte von S. & Co., .\pr. IS'.IT, p. 42, and .\i)r. l.S',)S, p. r,3. 3) For History set' nnder camphor oil. ]>, ;-!7o. Oils of the Di]iteroc;ir])acpae. '^tO'-'> Properties. Oil of Borneo camphor is a liquid, sometiiues colored green by copper, of the sp, gr. (.).8S2— 0.9()9 (Mace\van,i 1885). Composition. The lack of an investigation along modern lines is pi-obably dtie only t(3 the tact, tiiat this interesting oil can not be obtained in the market. From older investigations of Martins- (18;]8), Pelouze'^ (1840) and Gerhardt* (18-I:;i) it can be seen that borneol ■' is the characteristic constituent of the oil. More recent investigators, however, like Lalle- mand" (18(30) and Macewan i (188.')j denj- the presence of this alcohol in the oil. According to I'elouze^ the liquid part of the oil has the same composition as the supposed terpene "borneeu," which is obtained b.y the action of jihosphoric acid anhydride on borneol. As Wallaeh "? has shown (1885), there result by this treatment several hydrocarbons; "borneen"' is therefore a mixture of severtil substances. Although nothing positive can be drawn from this statement of Pelouze, it is, nevertlieless. probable also from other considerations that camphene is contained in tlie liquid parts of the oil of Borneo camphor. The oil investigated by Lallenmnd had been brought bj' JiTnghuhn from Sumatra, and had been obtained by distilling various comminuted parts of the tree. It turned the plane of polarization to the right (a for red light = +7°) and on distilling began to boil at 180°. The fyaction going over at this temperature was relatively small (sp. gr. ().8G, aD-\-Vi°) and yielded after passing hydrochloric acid through it and treating the resulting product with fuming nitric acid, a solid hydrochloride (dipen- tene?). The principa.l part of the oil went over from 2G0 — 270°, had the sp. gr. 0.90 — 0.92 and yielded a compiound Oi.-,Hl>4-2HC1 melting at 125°. Overlooking the somewhat high melting point the body might be looked upon as cadinene hydrochloride. As already mentioned this Borneo camphor oil contained no borneol. 227. Oil of Gurjvm Balsam. OhigIiN and History. Gurjun balsam, called wood oil in India, has been known there for a long time and used as an excellent varnish. 1) Phariii. .Touni., III. I'i. pp. 79."; anil 104.-. 2| Liebig'w Annali^ii. '2~ , p. HB. 3) Compt. rend., 11, ]). 36.=;; Eiebig's .Vinialen, 40, p. 320. *) Lieblg'H Annalen. 4.5, p. 88. 5) The borneol fi-oni the Borneo camphor tree i.s dextrni^yrate. Fluckiger, Pharni. .Journ., III. 4, p. 8211. 6, Liebig'8 Annalen, 114. p. 193. V) Liebis's Annalen. 230, p. 237. 504 Special Part. The balsam is obtained in East India, in a manner similar to turpentine, from several s])ecies of Dipteroccirpu.s (Family IJiptei-ocHijiH- cenp), especially from 1). turhinntiis Gaei-tn. fil., D. hicanus Roxli. and I). ;datU8 Eoxb. The Dij)ti^roc:ir]iun trees l)elonf;- to the most magnificent trees of the Indian mountain forests, and are so productive, that full grown trees yield up to 180 liters of balsam during- a, summer. The eollection is as follows: At the end of the dry season a transverse slit 2 inches in lengtli and (5 inclies in width is made with an axe through the bark into tlie wood, just above the ground. At the base of this a dee]) cavitv is made, which is capable of holding at least 1 liter of balsa.m. This is heated by means of a coal fire which has been started in it, until the walls are charred. The cavity is then emptied and cleaned. The balsam soon begins to flow at such a rapid rate from the slit, that the cavity serving as a reser- voir has to Vie emptied several times a day. When the flow diminishes or is retarded by drying on tlie walls, the crusts are scraped off or the walls are again heated. When exhausted, the same operation is repeated on the opposite side of the trunk. i The principal places of export of the gurjun balsam are Saigon, Singapore, iloulmein in Tenasserim and Akyab, Gurjun balsam, according to its son7-ee arid manner of collection, differs 'in consistency, color, and behavior to solvents. The better varieties are of a greenish gi'ay color ; with reflected light somewhat turbid and slightly fluorescent, with transmitted light it appears entirely clear and reddish brown. Odor and taste remind of copaiba balsam. Its sp. gr. is 0.96—0.97. By .steam distillation up to 70 p. c. of oil are obtained. In Eurojie attention was called to gurjun balsam in 1811 by Franklin 2 and in 18l;i by Ainslie,3 but its .source and manner of collection was first described accurately by Roxburgh about 1S27.J^ The sinnlarity of tlie action of gurjun balsam to that of copaiba balsam was made known in India about the year 1812 by the physician (;)'Sha,ughnessy." The lialsa,m also gained in India a considerable reputation as a cure against lepro.sy and was used later in England in dermatology." 11 Pharin. .loiirn.. III. .">, p. 729: III, Is, p. 1(U; 11. Hniibiuy, Science Papers, p. lis. 2) TractH on the dominions of Ava. London, 1811, p. 2tj. 3) Materia niedica of Hindoostan. Madras, 1813, p, 186. ■^) Plants of the coa.st of Coromandel. 1828, voi. :^. ji. 10. s) Bengal Dispensatory, Calcutta, 18-42, p. 22. fi) Pharniac. .Tonrn.. TTJ, .5. yi. 729. Oils of the Cistaceae. 505 Properties, (iurjun balsam oil is a yt^llow, soniewliat viscous liquid, of the sp. gr. 0.915—0.930. It lias at times a very high rotatory power, namely '/.u = — 35° to —180°. Most of the balsams give laevogyrate oils, but strongly dextrogyrate oils have also been observed.- The oil is not eorapletely soluble in 90 p. e. alcohol, and even in 95 p. e. alcohol the solubility is limited. It contains no sa.poni- flable constituents, but probably small amounts of alcoholic bodies, for after acetylization the saponification number 9.6 was obtained. Gurjun balsam oil boils for the greater part at 255 — 256° and appears to consist almost wholly of .sesquiterpene, ^ Ci5H24- With hydrochloric acid this does not give a solid hj^drochloride. but only a fine dark blue coloration. Whether this hydrocarbon is identical with one of the known sesquiteryjenes has not yet been determined. Oil of gurjun balsam is on account of its weak odor a very dangerou.s adulterant for other volatile oils. On account of its high boiling point, its strong rotatory power, and its difficult solubility in alcohol, its detection, however, usually offers no great difficulties. 228. Oil of Ladanum. Origin and History. The ladanum-'' resin, u.sed since antiquity as incense and embalming agent, is an exudation of the bush-like plants Ci.stus cjvtieus L., C. Indauiferus L. and others (Family Cistaceae) indigenous to Asia .Minor, Crete, Cyprus and a few other islands off the coast of Asia Minor. Up to the beginning of this century it was an officinal drug, valued for its pleasant odor, and is often mentioned along with the ancient aromatics storax, myrrh and frankincense in literature and has often, especially in the translations of the Bible, been confounded with galbanum. Latel}' it has gone almost altogethei' out of use. Ladanum oil, distilled at first with wine or spirits of wine {aqua vitae) was already known to Ryff, (j-esnei-, Rubeus, and to Porta. It was taken up in medical books, first in the Dispensatorium Noricum of the year 1589 and in tlie Pharmacopoea Augustana of the year 1613. Properties. The oil distilled from the leaves of f'intuv ladaniferus L. has an unpleasant, narcotic odor. It has the sp. gr. 0.925 and boils from 165— 280° with decomposition and splitting off of acetic acid.* i| Pharmaef)j2;raphia Inflica, vol. 1, ]». 10.3. -) I'harmaeoffnosie, 2nd ed., p. 102. Comp. also Wt'rner. Zeitschr. f. Chem. nnrl Pharni., 5, p. 5H» : .JahreHb. f. Chem., 1862, p. 4t;i. 3) Also Rpelled labdaniun. 4) Bericht von S. & Co., Oct. 1889, p. ."j3. 506 Special Part. Upon distillation of ladaiiuiii resin Schinimel & CoA obtained a o-olden yellow oil, of a fine strong amber odor. After standing for about lialf ;i year, niagnifieent crystals separated out, wliicli mnde n]! about the fourth part of the oil.- 229. Oil of Canella. Omia.N- AXTi HisT(jKY. The evergreen busli CnrK-lL-i nUni Murray (P'jiinily Canellnri^.-ie). indigenous to the "West Inilies, has a. pleasant aromatic bark, which, when it was lirought with other drugs from the new world to Europe, was c-onsidered as a variety of cinnamon l:ia.rk, and latei- was i'onfi:)unded with otlier medicinal l)arks, especially Avith Winter's bark, fi-om Drimyn wiutfri Forst. The volatile oil of canella bark was ]irobably first distilled 'in 1707 by Sloane in Enghmd. and lati-r. in 1,S2(), liy Henry, but appears to have found no a.pplication. It was investigivted in 1S48 liy Meyer and von Reiche and later by Bruun and Williams. Properties. Upon distillation of canella bark, ().7-"'> to \.'2'> \i. c. of volatile oil are obtained, the . Optically it is slightly dextrogyrate up = + 1° i~l'- CoxsTiTUENTs. By shaking out with alk.-ili, a phenol, engemil"'- (benzoyl eugenol, Brunn^) (-ould be separated. By the distillation of the remaining portion the lowest fraction went over from K;.")— 17(1.° (Sp. gr. (».,S,S,S; ,/i) = — :',,:{H°). The presence of l-]iineue (Williams "i) was demonstrated by preparing the pinene nitroso- chloride and the pinene lutrolbenzylamine base, melting at V2'2 — 12H°. The next highest fraction consists of cineoU' (cineolic acid, ni. p. 107°). ^ The highest boiling parts of the oil contain ca.r3'ophyllene.-> the presence of which was sliown by preparing the crystalline car.yophjdlene hydrate, melting at !)2— O.".". 230. Oil of Damlana Leaves. Sevei-al s]>e(-ies of Turner;! (Family I'lirufrncenf). especiallv Tnriwr;i aplirodisiar;! Ward and Tuniern diffusn ^^'ard have been named as the botanical soni-ces of damiana leaves, used medicinally since lS7."i in America.. The leaves of other ]ilants, li()we\-er, are also sent into the market as daminiia leaves, for instance those of Bigvlnvi.-i veiiot;) Gray 11 Berlcht vnii S. &ro.,.\pr. I.SVI.?, |i.G3. •*) Prof. Wise. Phai-m. A.ssor . 1 S'.c-!, ji. .'tij. -'1 Ibidem. Oct. 1S!I3, ii. 24. ■■!) Pliarm. itmiil«cliini, 12, p. IsH. 3| Eicblg's ,\nnuien, 47, |i. 22+, o) P.eriolit vi.>n S. & Cu., Oi-t. ls;)o. p. ."3. Oi/.s of the Myrtaceae. 807 {Aplopappus (]Jscoi(I(:-ut< D. C). The dift'erence.s in the material employed no doubt, explain also the ilifferences noticed in the oils obtained bv distillation at different times. Pantzepi obtained in ISST (1. 5 p. c. of a yellow oil of an aromatic odor and a warm, camphor-like, bitter taste. Schimmel & Co.^ obtained O.f) p. c. of a oiled between 250 and 310°. The hif;he.st boiling- fractions were blue. FroTii anotlier consignment of leaves the same fli-m obtained 3 in 18!)() 1 ji. c. of oil of the following properties: sp. gr. 0.943; '/-D = — 23° 2.")'; saponification number -tl.S. On standing in the cold, the separation of crystals on the upper surface could be noticed, similar to those which are observeij = + 23.5°. The priiK-ipal jia.rt of the oil, about 75 p. c, l)oils from 155 — 157° (sp. gr. 0.8():!5; «, = -,-31.28°). has the com])osition CkiHtc, and yielils with liydrochloric acid a monohydrochloride melting at 120°. On heating this fraction to 2(;o— 270° dipentene resulted (tetrabromide, ni. p. 125—126°). From this it follows that the hydrocarbon boiling fi'om 155 — 157° is d-pinene. The fraction boiling about 17(1° (15 p. c.) consists of cineol, as was shown by the formation of the ilneol bibromide ('loHisOBrj, which separates in red crystals from tlie petroleum ether solution on the addition of bromine. About 10 p. c. of the oil pass over, on distillation, from 220—280°. The composition of this fraction has not yet been deterinined. 1) Derielit von S. & Co., .\|ir. Issvi, p. ^s. 2) Gazz. chim. ital., 21, p. 270; Bericlite, 24, Referate, p. ."i72 3) Pharmaceutische Zeitun;^, 8.5. p. 224. 4) Airhiv (1. Phanii., 22C,, p. (jfjS. Oi/,-. of tlip Mrrtacfiw. SKQ 234. Oil of Pimenta. Oleum Aiiiomi sen Piiiienlae. — Piineiitol. — Essence de Pimeiit, Origix akd Preparation. The evergreen shrub Pimentti officinalis Liudl. (Family ilyrtnvenf). indigenous to the West Indies, grows on calcareous soil near the coast, in Cuba, Hayti. San Domingo, Trinidad, Antigua, and espeoiallv in Jamaica, further in Central America, Mexico, Costa Rica and Venezuela. For obtaining pimenta valued as an aromatii' or allspice, i the unripe berries are gathered and dried in the sun. The ripe fruit contains a sweet jelly, but is almost odorless and has therefore no commercial value. Pimenta yields on distillation, whi(;h is at first accompanied by a strong evolution of ammonia, 8 — J:..5 p. c. of volatile oil. Properties. Oil ol pimenta is of a. yellow to brownish color and has a pleasant aromatic odor, similar to clove oil, although sharply differentiated from it, and a piercing, sharp taste. Sp. gr. 1.024^ to 1.050. Slightly laevogyrate. It is soluble in all proportions in 90 p. c. alcohol, and soluble to a clear solution in 2 parts of 70 p. c. alcohol. Composition. The experiments of Bonastres,^ (1825) who prepared the alkali salts of the acid constituents of pimenta oil, already indicated that the similarity of this (.)il to clove oil was due to the eugenol which was common to both. The proof of the identity of these two phenols was furnished by Oeser^ in 18(14, who separated the eugenol from the oil by means of an alkali solution, and analysed it. That part of the oil which did not combine with the alkali, boiled at 255° and was slightly laevogyrate. The analysis gave results agreeing with CsHs. This is therefore a sesquiterpene. The odoi' of oil of ]>imenta indicates that eugenol and sesquiterpene are not the only constituents. An investigation of the oil according to modern methods might be a profitable and a not too difficult problem. Oil of pimenta leaves. An oil distilled in Trinidad from the leaves of an undetermined species of Piuipiita. is a yellow liquid, smelling strongly of lemon, of the sp. gr. 0.882 at 25°; «d=— 0°37'. The lemon-like odor is due to citral, the presence of whi(;h was demonstrated by forming the citrvl ^5-naphtho cinchoninic acid." 1) Odorograpliia, vol. 2. p. .51 . 2) Bericht von S. & Co., Apr. is'.jo, p. M<.). 3) .Journ. de Phartn., 18. \>. -Hit;. Coiup. also ibid., 11, ji. 1S7; Troninisdorff' s Nenes .Journ. d. Pharrn., 11, I, p. 127. 4) Liebi/Jr'.s Annalen, 181, p. 277. 5) Bericht von 8. & Co., Oi-t. IS'.Kl, p. 77. olO Special Part. 235. Oil of Bay. Olenni Myrciae. — Bayijl. — Essence de Myrcia. Okkiix and Pbepabatiox. As the numerous s])ecies of tlie genera Myrcin and I'imeiitii are verj variable and very [similar to earli otlier, it is liio'lily ]trobable tliat tiiese small botanical differences are not ()l)serveil in colleetinf;-, and therefore the bav leaves of commerce are not always derived from one and the same plant, i^ but are ra-ther mixtures oF tlie leaves of several species. Accordin;^' to Holmes 2 the botanical source of the genuine bay leaves is Pimentu, ii.rris Wight { Eugenia ni-ris \^'iglit et Arnott) ;ind not Myrci.-i ncrin D. (\ as is given in the U. S. P. The bay tree is indigenous to the Wi'st Indies and flourishes especially on Jamaica, 8t. Thomas. Antigua, Guadeloupe. Dominica and Barbadoes. The oil is obtained only in part from tlie fresh material o)i the islands themselves; the larger part is probaljly prepared in Xew York from the dried lea,ves. On distilling, part of the oil separates in the receiver on top of the water and another part sinks to the bottom. They must' be mixed if a nornml oil is to be obtained. This appears not always to be done, as ba.y oils of a, specific gravitj' greater than water often apj>ear in tlie market. The yield from dried leaves is 2 — 2..") p. c. Pbopbkties. Bay oil is a yellow liquid, soon becoming brown on exposure to tlie air, of a pleasant odor reminding of clove and a sharp spicj' taste. The sp. gr. of the normal oil varies from 0.96.') to 0.!(85 and is as a rule above (».1)70; optically it is slightly laevogyrate, «d = up to —2°. The fi-eshly distilled oil is soluble to a, clear solution in an e(]ual volume of 90 p. c. alcohol; on standing, however, it soon loses its solubility and then gives only turbid mixtures, a behavior which is due to the polymerization of an olefluic terpene, myrcene. contained in the oil. The content in phenols (eugenol and chavicol) amounts to .''>9— 60 ]). c. according to volumetric determinations with dilute potassa solution. Composition. The identity of the main constituent of greater specific gravity of the oil with eugenol appears to have been first recognized by Markoe^ in 1877. The first complete investigation of the oil was made by Mittmaun-i in 1889. He found besides eugenol a small amount of methyl eugenol, which statement was later corroborated. By fractional distillation he obtained a small fraction, boilim- from t) Odnrographia, vdI. 2, jp. Gij. 3) Proc. Am. Ph. Akk(k\, 2.j, ji. 4.38. 2) Phiirm, .roiini., Ill, 2], ji. s.0. 51 2 Special Part. The constitneiits of oil of bay arraiis'eil acconliiiR' to the a mounts pi'esent are as follows : 1. Eugeiiol. C]()Hi20l'. 2. Myrceue, r.ioHiii, :■!. Chavicol, 0„Hi„O, 4. Metliyl eiig'enol, CiiH]4*-*2. ."i. :\[rtliyl chavicol, ('10H12O. ('). I'hellandreiie, ('kjHkj. 7. Citral, C-toHieO. Examination. As oil of bay contains no pinene, any turpentine oil which may have been added, can be detected without diffli-ulty. Fi-oiii 10 cc. of bay oil 1 ec. is slowly distilled off from a fractionating flask, and tlie distillate mixed with 1 ec. of am.vl nitrite and 2 ee. of glacial acetic acid. To this is added drop by drop with agitation, while the -whole is kept well cooled in a freezing mixture, a mixture of equal parts of glacial acetic acid and hydrochloric acid as long as a blue coloration results. If pinene is present a white precipitate of pinene nitrosochloride i.s foinied. In this manner 10 p. c. of turpentine oil in bay oil can be detected. 236. Oil of Cloves. Oleniii Caryophyllonim. — XelkeniU. — Essence de Girofle. HiSTOHY. Oil of cloves ajipears to have been distilled fiir the first time in the fifteenth centurj-, but ])i-obabIy, like other aromatics, with wine or the addition of spirits of wine. Thi.s method of distillation was described by Eyff, Gesner, Ijonicer and others, (-fesner also mentic.ms the distillation of the oil, per cleseensuni. The pure oil was, however, shortly afterwards distilled Ijy Cordus, by Winther of Andernach and by Porta. In the Dispensiitorium Noric-um, oil of cloves was not admitted until the edition of ir,H'.). [n drug ordinances it was first mentioned in that of the city of Berlin of l.")74. The yield of volatile oil from cloves was determined by Boei'hnave, Hoffmann, Neumann and Tromnisdorff. Boerhaave remarked tlmt the quite different yield olrtained on distillation was sometimes due to the adulteration with cloves which Imd been exhausted of their oil bv distillation and then ilried again. Bonastrei in 1S27 recognized the a.(/id nature of clove oil and investigated the saltdike compounds of eugenol that were fi^rmed with alkalies. Ettling and Liebig^ in l,s:i4 first showed that liesides Xelkeii- sHiiiv, eugenic acid, there is also]pre.senT in the oil an indifferent body. 1) .Joiini. de I'harin., II. 1 a, [ip. 4c,4, rn :i: Pogsendorffs Annaleii, le. i)ii. c.d'.i. (HI . -) Liebiji''s Aniiali'ii, i), p. i;s. Oils of the MfrtaeeHfi. 513 Of the older investigation^!!, wliieh were restricted mostly to eugenol, those of Dumasi (1883), BockmannS (18:-58), StenhouseS (1843), Calvi* (1856), Bruning"' (1857), Williams* (1858), Hlasiwetz and Grabowski '^ (1866) and Erlenmeyer* (1866) may be mentioned. Origin' and Preparation. The ever-green clove tree, Eugenia carro- phylhitti Thunb. {CaryophyUus aroinuticun L,.) (Family Myrtaceae), was originally indigenous to the Philippines and is now cultivated on Amboina, Eeunion. Mauritius, Madagascar and Malacca (Penang). The plantations on the largest scale are, however, found on the east African islands Zanzibar and Peniba, which taken together produce about Vo of the total clove production of the world. Cloves are the undeveloped blossoms, dried in the air, of the clove tree, which is aromatic in all its parts. Its inflorescence is a perfect cyme containing as many as 35 individual blossoms. Each blossom has a pulpy receptacle nearly 1 cm. in length, which at first is of a light col(jr, later green, and just before blossoming becomes dark red. When this color appears, the blossoms are gathered, because they are then richest in oil, and dried in the air. Tlie flower buds of the culti- vated trees contain more oil than those of the trees growing wild. The berry-like fruit collected just before ripening, formerly came into commerce under the name of AnthophyUi, mother-cloves. Only the Zanzibar cloves (under whii-li designation are included the cloves coming from Pemba) are used for distillation. The cloves from Amboina and Eeunion are indeed richer in oil, but on account of their better appearance command a much higher price than the difference in the oil content justifies. The most expensive is the Madaga.scar clove, from St. Marie on the southern point of the island. It yields 18 p. e. of oil, which is considered as finer by the Parisian perfumers, but from othei- considerations no especial advantages can be assigned to it.i The cloves are distilled either whole or in a comminuted (iondition ; according to the method of distillation (water or dry steam) there is obtained an oil of higher specific gravity and richer in eugenol, or a lighter oil, in which the non-phenol constituents are relativel,y larger. The oil collecting in the receivers partly sinks in the water and partly floats upon it. By mixing both parts normal oil of cloves is obtained. The jdeld from Zanzibar cloves amounts to 15—18 p. c. 1) .inn. rle Chim. ct de Phye., II, 5«, p. =) Ibidem, 104, p. 202. 1«.5; Liebig's Annalen, 1). p. 6S. '^) Ibidem, 107, p. 2.3S. 2) Liebig'B Annalen, 27, p. 'i'jo. '') Ibidem, 1.S9, p. '.)Tt. :i) Ibidem, 9.5, p. lO.S. **; ZeitKclir. f. Chemie, 9, p. 9.5. 1) Ibidem, 99, p. 242. 33 514: Special Part. Properties. Oil of cloves is, when freshly distilled, an almost colorless to yellowish, strong'Iy refracting liquid, which becomes darker with Mge. The odor is strongly aromatic, the taste persistently bnrning. The specific gravity varies according to the method of distillation from 1.045 to 1.070. The optical rotation is slightly to the left, «d = np to — 1°10'. The oil dissolves to a clear solution in 2 parts of 70 p. c. alcohol. The chemical reactions are partly those of eugenol, several color reactions are. however, produced by the traces of furfurol present. Upon distillation oil of cloves goes over between 250 and 2(j0°. Composition. Of the constituents of oil of cloves, eugenol, which is present t(.) the extent of 70 — 85 p. c, was the first to attract the attention of chemists (comp. History, p. 512). Eugenol, a phenol of the formula CioHi202, boils under ordinary pressure with slight decomposition at 258 — 254° i (thermometer com- pletely in the vapor). It is the most characteristic and valuable constituent of clove oil; its quajititative determination is described on page 516, its properties and compounds on page 180. Pure eugenol is obtained bj' treating oil of cloves with weak (2 — 5 p. c.) soda solution and after shaking out the alkaline solution several times with ethei', decomposing it with dilute sulphuric acid. Besides free eugenol, there is contained, according to Erdmanii,^ in oil of cloves also 2 — 3 p. c. of acet-eugenol, which is found in the oil not attacked by the alkaline solution. In this the acet-eugenol can be detected and removed by saponification with alcoholic potassa or by heating with a concentrated aqueous solution of potassa. The oil remaining after removing the acet-eugenol consists principally, as was already recognized by Church s in 1875, of a sesquiterpene, which was more closely investigated by Wallach-^ in 1892 and called ca.ryophyllene. Caryophylleue, C1.5II24, is a colorless liquid boiUng from 258—260°, of a weak odor which does not resemble cloves and the sp. gr. 0.9085. By taking up a molecule of water it is converted into the nicely crystalline alcohol, caryopliyllene hydrate, C15II20O, melting at 96°. For further information see page 125. Si'heuchs in 1863 pointed out the presence of small amounts of salicylic acid. The correctness of this statement was, however, rendered 1) Bericht von ,S. & Co., Apr. 18112, p. 28. i) Liebig's Annalen, 271. p. 287. 2) .Journ. t. prakt. Chem., II, .56, p. 143. o) LiebiR's Annalen, 125, p. 14. 3) .Tourn. Chem. Soc., 28, p. 11.3. Oilf: of the Myrtaceae. 813 doubtful by Wassermanni in 1875. Erdmann^ definitely showed the presence of salicylic acid in oil of cloves and found that it did not exist free but probably as acet-salicylic acid ester of eugenol. Of other minor constituents of oil of cloves, methyl alcohol must be mentioned, which is best obtained by collecting the first portions in working up the cohobation waters and fractionating this repeatedly. Finally a liquid boiling at 6.")..") — 66° is obtained which can be identified as methyl alcohol s by means of its oxalic acid ester, melting at -"54°. By continuing the distillation a liquid boiling at 162° is obtained, which consists of furfurol-' and was identified by its intense color reaction with aniline and p-toluidine, by converting it into its phenyl hydrazone melting at 96°, as well as by splitting it into pyromucic acid and furfurol alcohol. Furfurol is probably partly the cause of the darkening of oil of cloves. In the fraction boiling at 1.50 — 15.5°, which cannot be completely separated from furfurol by distillation, is contained methyl amyl ketone,* CH.3. CO .C.oHii. If from the fraction mentioned, the furfurol be removed by shaking with permanganate solution, the pure ketone, boiling at 151 — 152° remains. The elementary analysis corresponded to C7H14O. By heating with chromic acid mixture it was gradually oxidized to valerianic acid (together with some capronic acid) and acetic acid. Although the methyl amyl ketone is present in oil of cloves only in a fraction of one percent it, nevertheless, has a considerable effect on the odor of the oil, as it gives rise to the peculiar fruity odor which accompanies the heavy eugenol odor. A further substance, which has been found in the oil, vanillin, ^ may have been formed by the oxidizing influence of the air on the eugenol. It is worthy of notice that vanillin is already present in the cloves. Examination. As nearly all adulterants which can be considered, are specifically lighter than clove oil, the determination of the specific gravity is not to be omitted. When it is found less than 1.045 it is to be tested by means of fractional distillation for turpentine and similar low boiling oils. Its solubility in 2 parts of 70 p. c. alcohol is also to be observed. Oils of cedar wood, copaiba and gurjun balsam would show themselves by their difiicult solubility and simultaneous increase of the rotatory power. The German Pharmacopoeia gives a test for the highly improbable presence of carbolic acid, in that it directs 1 cc. 1) Liebig's Annalen, 179, p. 369. ■!.) Bericht von S. & Co., Apr. 1897, p. 50. 2) .Journ, f. prakt. Chemie, II, 50, p. 143. s) Chem. Centralbl., 1890, II, p. 828. 3) Bericht Yon S. & Co., Oct. 1896, p. 57. r,16 Special Part. of oil to be shaken witli 20 ca-. of hot water, and that the filtrate obtained after allowing the mixture to cool, be treated with ferric chloride. A blue coloration would indicate the presence of carbolic acid. Much more common than the adulteration of clove oil, is the sub- stitution of the cheaper and less pleasantly odorous oil of clove stems, the sure detection of which is only possible to a well trained nose. Investigations on a physical or cliemical basis are entirely inadequate. Perhaps the recently found fact that oidy oil of cloves, but not oil of clove stems, contains acet-eugenol, might be used as a means of dis- tinguishing between these oils. It n\&A' often be desirable to know how much eugenol is contained in a clove oil (or clove stem oil). For this purpose H. Thorns i has worked out a method of determination which depends on converting the eugenol into its benzoyl derivative, separatiuii and weighing as such. The method is as follows: 111 a tared beaker of about 150 cc. .j g. of clove oil are treated with 20 k- of sodium h.vdrate solution (15 p. c. ) and tlieii (i g. of beuzo.vl cliloride added. Tlie mixture is well sliakcii, wlieii a considerable amount of heat will lie liberated, until it i,s uniformly mixed up. .Vfter cooling-, 50 ci-. of water are added, and then heated until the crystalline ester has again become oily and again allowed to cool. 'I^lie clear supernatant liquid is filtered off and the crystalline mass remaining in the beaker is a.gain treated with 50 cc. of Av.iter, heated on a water bath until the ester is melted and filtei-ed after cooling. This operation is repeated with 50 cc. more of watei'. The excess of soda a.s well as of sodium salt 1ms then been removed. .Vfter having returned any crystals which may have been w.ashed on to thfr filter to the beaker, the still moist benzoyl eugenol is at once ti-eated with 25 cc. of alcohol of 90 p. c. by weight, and heated with agitation on a water bath until solution is effected; the beaker is now removed from the wi>ler bath and the agitation continued until the benzo.vl eugenol hns se|iarated in fine- crystals. This takes plaee in a few minutes. The mass is then cooled to 17°, the preciijitate tran.sferred to a filter of 9 cm. diametci- and the filtrate collected in a graduated cylinder. About 20 cc. of hltrate are usually obtained; the alcoholic solution which is hchl in the crystallint' mass is forced out by adding so much of 90 p. c. alcohol by weight until the total filtr-ate measures 25 cc. The still moist tilter with its precijiitate is transferred to a weighing tube (the latter with the tilter having jireviously been dried at 101° and weighed) and dried at 101° until the weight is constant. 25 cc. of 90 p. c. alcohol dissolve at 17° 0.55 g. of pure benzoyl eugenol, which amount must be added to the result obtained. If a is the amount of benzoic acid ester, h the amount of clove oil used (about 5 g. ), and if 25 cc. of the alcoholic solution of the ester are filtered off I) Ber. Helbins's rhnrmarolosical Kecorrt, VIII, 18112. Oils of thu Myrtacen.p. 529 ill. The Phosphoiuc Acid Method. This depends on tlie property of phos- phoric acid to combine with cincol to form a compound analogous to the addition jiroducts of h.vdrobromic and hydrochloric acids. According to Helbing and Passmorei the method is as follows: Concentrated phosi)lioric acid (sp. gr. 1.75) is added droj) by drop with constant stirring to Ht g. of eucalyptus oil in a beaker. During this operation the beaker must be kept cold with water, and care must be taken that the contents do not warm up. By the careful addition of the phosphoric acid scarcel.v a yellow or reddish color is developed. The reaction is complete as soon as a drop of the acid produces a dark red coloration of the mass. The crystalline mass formed is sharply pressed between hiter paper, for which purpose an ordinary copying press raa.y be used. The pressing is repeated with fresh filter paper until no grease spots ai-e visible on the latter. The crystals are then weighed in a beaker and by multipl.ving by 6.11 the percent of the cineol is obtained. The factor 6.11 is gotten from the following equation, based on the as- sumption as yet unproven, that the double compound is an addition product of 1 mol. each of phosphoric acid and of cineol. CoHisO + H3PO4 = CuiHisOHiiPOi. The results obtained by the phosphoric acid method are about % higher than those obtained by the freezing- method, but are still con- siderably {rom the true valtie. Kebler- obtained with pure cineol only 02.14 p. c. instead of 100. He, therefore, recommends the following modification of the method. -t cc. of phosphoric acid (1.75) are added to 8 g. of oil contained in a beaker cooled with ice water. It is then slowly but thoroughly stirred and the cineol phosphate expressed, decomposed with hot water and the acid titrated with normal alkali. In this manner Kebler found for pure cineol, instead of 100, 103.75 p. c. Experiments witli mixtures of known cineol content were not made, and there is, therefore, no basis for judging the applicabilitj^ of the method to eucalyptus oils. Wlien it is considered how difficult it is to reniove quantitatively the excess of the viscid phosphoric acid, no I'on- ftdence can be extended even to this modification of the pliosphoric acid method. Allen 3 has recently tested the method by malting mixtures of pure euc-alyptol with tlie eucalyptol-free constituents of a globulus oil. In oil containing more than 50 p. c. the experimental result differed from the theoretical by at most V/2 p. c. With a content of from 20 to 50 p. c. the highest difference was only 2% p. c. With (ills containing less than 20 p. c. the method was found to be inapplicable. 1) Helbing's fhariiiacological Itecord, 2) Am. .rourn. Pharm., 70, p. -492. XXIV, 1898. 3) f'hemist & Dnissisl. 54, p. 641. .34 530 Sperinl Part. 230. Oil of Bucalyptus Odorata. Eucalyptu.s odornta Behr. is n tree indigenous to Soutli Australia, Victoria ;iiid New South Wales. The yield of oil from fresh leaves amounts to 1.4 p. c. The light yellow oil has an aromatic camphoi'-like taste and smells after cineol and Roman caraway oil. 8p. gr. 0.899 to 0.925; slightly laevogyrate. It boils from 157—199° (Maiden') and is often so rich in cineol (identified by the hydrobromic acid compound) that it solidifies in a freezing mixture witliont being fractionated. From the rectificHtion residue a consideralde amount of cuminic alde- hyde was sepa-rated Ijy means of its liisulphite conijiound. It was idcntitied l)y oxida-tion to cununic acid.- 351. Oil of Eucalyptus Cneorifolia. The oil cif this buslidike eucalyptus species, growing on Kangaroo island in Soutli Austi"dia has only lately appeared in the market. Its ac(;oni])anying odor reminds of dill and caraway. !Sp. gi-. 0.S99— 0.928; [«]d = — 4 to —14° (Wilkinsons). A firm in Adelaide, which had introduced the oil into the market, at first designated it .-is coming from Eucalyptus oleosa. This is due to the fact that E. ciworU'oha is now considered as a separate species, whereas it was formerly considered as a variety of E. oleosa.^ 352. Oil of Eucalyptus Oleosa. Eucalyptus olt^osa F. v. Miill. likewise belongs to the bush-like eucalj^itus species. The yield of oil is 1.25 ]). c ; ' sp. gr. 0.90()— 0.92(1 : [«]d=+4 to 5°.'^ It contains cineol and cundnie aldehyde. 353. Oil of Eucalyptus Dutaosa. Eucalyptus (Iumosa° is found in northern Victoria, in southern New South Wales and in Soutli Australia. Yield about 1 p. c. ; sp. gr. 0,884 to I ».915 ; '/D =4-0° (•)' to + <)° 30'. It contains large amounts of cineol." 354. Oil of Eucalyptus Amygdalina. OuiaiN. The tree, known in south-eastern Australia as white and brown peppermint tree. Eucalyptus ainygilaliua Labill., is one of the 1) The iinerul native pUints of .\iistrnUa, p. 272. 2) Berlclit von S. & Co., Apr, 1,S,S0, ]i ly. 3) Pi-Dc. Royal Soc. of Victoria, 1893, p. 19.^. *) nerlcht von S. & Oo., Apr. 1S92, p. 44. 5) The useful native plants o! Australia, p. 2r,7. 6| Berieht von S. & Co.. Oct. 1,S89, p. 2(1. Oils of the MyrtacPHf^. i S31 tallest of the eucalyi]tu.s species. Aeeordino- to F. von Miiller it reaches a height of over -tlH) feet. Its leaves contain more oil than anv other species, yielding on distillation over ;i p. c. of oil. Formerly it came in great quantities into the market, bnt it has I'ecently been replaced more and more by the oils richer in cineol. According to Baker & S^mith^ the commercial oil of Encniytus Hinygdnlirm Labill. is not obtained from this species Imt from E. aniyg-- didinn var. hitifuJhi Maiden et Deane. The true oil of E. amygdalina Labill. contivins according to Baker and Smith, when the leaves are di.stilled at the proper time, about 4.") p. c. of cineol. Pbopehties. TliH oil is light yellow or colorless. Its cineol odoi' is almost masked by the terpene odor; sp. gr. (l.!S.")() — ()..S8(); «d = — ^"i to — 70°. The higher the specific gravity and the lower the rotation, the more cineol and less phellandrene does the oil crmtain. The phellaudrene reaction mentioned Ijelow is characteristic for the oil. It is much less soluble in alcohol than oil of EuCcilyptiis fflolailus. As a rule more than (5 parts of f)0 p. c. ali'ohol are necessary for solution, whic-h in most cases is not even perfect. Composition. According to Wallach and (lildemei.ster- the oil of Eucalyptus nniygdnliiin consists principally of pliellandrene. If the oil diluted with twice its volume of ]ietruleuin ctlier be treated with a concentrated aqueous solution oi sodium nitrite, and then acetic acid be added in small portions, the quantities of phellandrene nitrite formed are so large, that often the entire liquid solidifies to a jiasty mass. It may 1)6 interesting to note that the phellandrene is laevogyrate and that this optical modification was found for the first time during the investigation of this oil. Cineol is pre.sent only in small quantities in tlie amygdalina oil. Its presence cannot be shown by the hydrochloric acid reaction ; on the other hand, its hydrobromie acid addition product can be readily oljtained from the petroleum ether solution of the oil.- 355. Oil of Eucalyptus Rostrata. Eucalyptus rostrata Schlechtd., indigenous to Australia and there distributed from South Australia to northern Queen.sland, is much cultivated in southern France as well as in Algiers, where the tree is said to be better able to withstand the heat than E. globulus. The 1) Chemist and UiMiggist, ri4, p. S64. 2) I,iel]ig'.s Annnlen, 246, p. 27fi- 532 Special Part. yield of oil from fresh leaves amounts to onl.y 0.1 p. e.i The oil is yellowish in color and reminds in odoi- of the oil of E. odorata.. Sp. OT. 0,912—0.025; aD =— l°S'to + 18".2 It is soluble in 2 parts of 70 p. e. alcohol, boils according to Witt- stein and Miiller from 137°(?)— 181° and contains valeric aldehyde and large quantities of cineol,-^ but no phellandrene." 356. Oil of Eucalyptus Populifera. Encnlyptns populifeia Hook, is distributed over Xew South Wales, QueeTisland and Xorth Austi-alia. The bright red oil smells of eaieput.i Ifc contains besides cumiuic aldehyile a fair amount of cineol.* 357. Oil of Eucalyptus Corytnbosa. Eucnlyptus coi;vinl)osti Sm. is found in the coast districts of Xew South \\'ales and in northern Queensland. According to Wittstein and Miiller the oil smells slightly of lemon anil rose (?) and lias a bitter, somewhat ca.niphordike taste.-' Sp. gr. 0.881. According to Schimmel &_ Co. it contains mucli cineol.* 358. Oil of Eucalyptus Resinifera. hJiical,vptut< resiuifem Sm. grows in Xew South Wales nnd (Queens- land. According to Gladstone" the oil consists principally of a hydro- carbon smelling of turpentine oil; Schimmel & Co.. however, found in it much cineol. An oil, coining from Portugal, and pr<3bably obtained from E. ivNinifei:i, had the sp. gr. 0.89;], and the rotatory- power «D = — 1~°8'. It was not soluble in 70 and 80 p. c. ^d(•ohol and con- tained besides cineol (iodol reaction) also ]ihellanili-ene.'^ 359. Oil of Eucalyptus Baileyana. Eurnly/itiis Iiailfy;in;i F. w Miill. oc(;urs in the neighborhood of Brisbane in Queensland. The fresh lenves yield on distillation 0.9 p. c.» of oil of the sp. gi-. O.O-tO. It boils from KiO— 18.")° and contains about ;!0 p. c. of cineol." 1) Maiden, The iiwefnl TiMti\e plants of .\nstralia. p. 1278. -') WilkuLSDn, I'roc Itoy. Soe. ril' Victoria, IS'i::!, pp. 107, 10s. :m Berielit von S. & Co., Oct. ISOl, p, 40. -1) Bei-lclit von S. & Co., Ai>r. ISOa, p. 28. ^) Maiden, loc. ci(.. p. lIOCi. «) .Joiirn. Chern. Soc, 17, p. 1; Jahresb. f. Cliemie, ISIvi, p. .", + 1. 'I Bericlil von S. & Co., Oct. 189S, ]). 2(>. ■"j Berir-lit von S. & Co., A|)r. ISSS, p. 10. Oils nl the Myrtncfne. 63^ 260. Oil of Eucalyptus Microcorys. Eucalyptus microcoiys F. v. Miill. is distributed in the iiortliern coast districts of New South Wales to Cleveland Bay (Queensland). Yield from the fresh leaves 1 — 2 p. c, sp. gr. 0.80(3 — 0.935. The oil boils from IGO — 200° and contains besides terpenes about HO p. c. of ciueol.^ 261. Oil of Eucalyptus Risdonia. - Under this name a. pleasant and mild smelling' eucalyptus oil was hitrodui-ed in 1874 in London. 8p.gr. O.Ol.^j— O.OlO : y.D =^ — 4°4:0'. It contained cineol and phellandrene.^ 362. Oil of Eucalyptus Leucoxylon. Eucalyptus leucoxylon F. v. Miill. (E. shleroxylon A. Cunn.) grows in South Australia, Victoria., New South Wales and in southern Queens- land. Bosisto-"- reports about 1 p. c. of oil, but remarks that the leaves used for its preparation had lost a part of their oil through heating. Odor and taste are said to be similar to those of the oil from E. oleosa. Sp. gr. 0.915—0.027; [a]i_,= + 0.5° to + 2.7°.''' 263. Oil of Eucalyptus Hemiphloia. Eucalyptus heuiijihloia F. v. Miill. is common in eastern South Au.stralia, Victoria., New South Wales, and in southern Queensland. The reddish-brown oil contains cinedl a.iid large amounts of cuminic aldehyde. •"' 264. Oil of Eucalyptus Crebra. Eucalyptus crehvn F. v. Miill. (Iron Bark) is indigenous to the coast districts of Queenslaml and New South Wales. The oil is light yellow, very similar in its odor to the oil of E. gloliulns, and like this is rich in cineol." 265. Oil of Eucalyptus Macrorrhyncha. The oil of the leaves of Eucalyptus macvorvhyncha Y. v. Miill. a tree known in New South Wales as red stringybark^ has been investi- gated bv Baker and Smith." i| Bericht von S. & Co.. Apr. 188S. p. T.i. 2) .IccordinK to Maiden Eufalyptiis risdmii lliinli. i.s identical with E. mnygchiUna Labiil. or at least elo.sel.v related. 3| Bericht von S. & Co , jVpr. 18'.)4, p. 211. 1) .Maiden, The useful native plants etc., p. 270. 5) Wilkin.son, Proc. Ko.v. Soc. of Victoria, 1893, p. 19s. «) Bericht von S. & Co., Apr. 1892, ]]. 2s. 7) Bericht von S. & Co., Apr. 1893, p. 28. S) In Australia the followins species of Encalyptns are designated as stringybark : E. ohilqa Herit., li. haileyana F. v. Miill., E. macrorrhyncha F. v. Miill,. E. capitellnta Sm., E. ejigenioitles Sieb , and E. fOjStiffiita Deane et Maiden. 9) .Tourn. and Proc. of the Tlo.yal Soc. of N K. Wales, .'!2, p. 10-t. •'i^U Spfcifl! Part. They obtained l),y distillation a yield of 0.28—0.31 p. c. of oil. The oil is reddi.sh-brown, has the sp. i;r. 0. 1)24— 0.927 at 22°, and begins to biiil at 172°. It contains a trace of phellandrene, ciueol, and the crystallized eudesinol • described nnder oil of E. pipn-itn on p. 'uiS. 366. Oil of Eucalyptus Capitellata. Baker and Smith- suggest the name of brown stringybark ff)r Eurnlyptus cnpitellnts Smith. The leaves yield on distillation only 0.1 p. r-. of a ilark red oil of the sp. .7 .'ind -|-."i.2°. The oil contains cineol. l)ut no phellandrene. 368. Oil of Eucalyptus Obliqua. Eucalyptus ohlicpia Herit. is found in tlie southern coast districts of Xew South Wales, princijiall.y, however, in Tasmania, Victoria, and South Australia. Yield O.o p. c. A reddish-yellow oil of mild udor and liitter taste; sp. gr. 0.S99. It boils from 171— 19.">°.« An (.)il obtained in Poi'tugal had the sp. gi-. (1.914 and the rotat(U-v pcjwer «D = — 7°28'. It was soluble in an equal piirt of SO p. c. alcohol and contained cineol (iodol reai-tion) and phellandrene -t (nitrite). 369. Oil of Eucalyptus Punctata. The tree from which the oil was obtained, Euca.ly]>tus punctata D. G. (E. tereticornis Sm. var. hrachycoris), is called grey gum in Australia, nud 3-ields besides kino a useful hard wood. It is found in the coast ilistricts of New South Wales, of Queensland as far as the border of Vii'toria. For the preparation of the oil, the leaves iind twigs wei-e used. Altogether nine distillation.s were made of material collected in different districts. The yield varied between O.G:! and 1.19 p. c. The sp. gr. was between 0.9122 anil (1.920."') at 17°. Two oils were laevogyrate 1 I .rom-Ti. anil Proc. iif the Uo.v. S(.e. of .\. S. Wales, :i;i, p. si;; Borli-ht Ton ,s. & Co .\pr. 19110, p. 2+. -) .Jouvn. and Proo. ot the Ro.val Sof. of N. S. Wales, Hi', p. 104. ■') JIaiilen, The useful native plants ete.. p. 27L'. i] Bericht von S. & Co., Oct. 1S9S, p. 27. OUn of tlie MyHsceae. 585 ( [«]d — < '.9:2° and — 2.52° ), the other seven were dextvo-ivrate ( [«] d + 0.54° to 4.44°). A sample mixture of all the distillates had tlie following properties: sp. gr. 0.915 at 1G°. [«]d= + 0-027°. Aeeording to the phosphoric acid method the eineol C(intent of the oil wa-s from 4(5.4— <)4. 5 p. e. No phellandrene is present in the oil of E. jniuctcitu.^ 270. Oil of Eucalyptus Loxophleba. Euenlyptu.s loxophleba Benth.- is called liy the i)eople York guni, on account of its frequent occurrence in the vicinity of the city of York. The oil has a highly unpleasant odor, and produces fits of coughing when inhaled. Sp. gr. 0.8828 at 15.5°; angle of rotation about + 5°. Upon distillation the following fractions were obtained : 168 — 171° 68 p. c; 171—176° 14 p. c. ; 176—182° 2 p. c. ; 1.S2— 187° 8 p. c. ; residue 8 p. c The oil contains phellandrene and eineol. The amount of the latter is estimated ;it 15 — 20 p. c. On shaking with biKul])hite the oil diminished in volume 20 p. c. which allows of concluding that a considerable amount of aldehydes and ketones is present. Aniyl alcohol, of which small quantities were found in the oil of E. gloltulas, and to which, no doubt, are jiartl.y due the irritating action of this oil, is not present. 371. Oil of Eucalyptus Dextropinea. The oil of Eucalyptus dcxtropinea Baker ^ has been prepared by Baker ajid Smith, ^ as has also the oil of E. laevopiiiea. Baker, from the fresh leaves of these trees. Both ai'e indigenous to New South Wales. The yield was in one case 0.825, in another 0.850 p. c. The deep red colored and strongly dextrogyrate oil has the sp. gr. 0.8743 — 0.87()3 at 17°. By distillation the following fractions were obtained: 15(5 — 162° ()2 p. c; 162—172° 25 p. c. The oil consists almost entirely of d-piuene.^ The main fractioii. Anally boiling at 156—157° ha ];i."). 536 Special Part. For the identification of the pinene tlie foUowinf:^- derivatives were prepared: pinene nitrosoehloride (in. p. 108°) and from this nitroso- pinene (m. p. 128—129°), fnrther terpin hydrate, as well as pinene monohydroehloride fni. p. 121 — 124°). Besides pinene the oil contain.s small amounts of cineol, which was i-ecof^-nized Ijy the behavior of the higher boiling fractions toward iodol and bromine. 272. Oil of Eucalyptus Laevopinea. From tlie fresh leaves of Eucalyptus laevopinea Baker, i silver top stringybark, Baker and Smiths obtained O.fJIi p. c. of a reddish oil having the .sp. gr. 0.8782. The following fractions were collected: 157— 1()4° 60 p. c: 1(54— 172° 28 p. c. Just as the foregoing oil con- sisted almost entireljr of d-pinene, this oil consists almost entirely of 1-pinene. The frai-tion boiling at l.")7 — 158", which can probably be considered as fairly pure pinene, had the sp. gr. 0.8(i26 at ^^ and [«]li = — 48.(33°. The same derivatives of the pinene were prepared as with the foregoing oil. This oil likewise contains only small amounts of cineol. 273. Oil of Eucalyptus Smithii. The leaves of Eucalyptus smithii yield on an avei'age 1.85H p. r. of oil whii/li contains over 70 p. c. of cineol.^ The oil contains d-pinene. but no phellandrene. The eudesmol, described under tlie oil of Euca- lyptus pijjerita on p. 588 has also been found in tliis oil."' Second (irouj): Citroiiellal-coiitainins;- Oils. 274. Oil of Eucalyptus Maculata. The sjJottiMl gum-ti-ee. Eucalyptus maculata. closely related to E. citrioclora Hook., grows in New South Wales and <,)ueensland, liut has also been transplanted to (Jeylon and Algiers. The oil, of citronellal- like odor,« has tlie sp. gr. 0.900, boils from 210—220° and cannot be distinguished from tlii' following oil. 1) See footnote 'A on ji. .'i/Jo. 2) See footnote 4 on ]). 5;^.^). 3) Aecording to Smith lUniost all of the oils olitainecl from speeles elosel.y related to /7. ^Inbnliis contain iiinene, sneh as the oils from E. hritli^-esi.'Min. E. ii-(iiijni;-ilvx. etc J) Proc. of the Linnean Soe of X. s. \\'ales, IS'.i'.l, II, p. •2'.->2 : P.eriehl von S. &('o., Apr. 1900, p. 24. ■I) .lonni. and Proe. of the Itoy. Soe. of .\. S. U'.-iles. :\3. p. .sO: nrriclil von S & Co.. Apr. I'tOO. p. 24. 0) Berieht von S. & Co., Apr. ISSS, p. 10. Oils of the Mrrtficefie. 587 275. Oil of Eucalyptus Citriodora. Eucalyjttu.s ritrioclora Hook, is probably only ii variety of E. inaru- lata Hook, and is for this reason sometimes designated as E. macula ta Hook. ra/'. eitviodora. The tree grows best in .stony ground. It is indigenons to Queensland and has also been planted with success in India, in Zanzibar and on the Magdalene River. i The leaves are distilled in Gladstone (Queensland) and give in the fresh state 1—1.5 p. c, in the dried state 8 — 4 p. c. of oil. The oil. distinguished through its pleasant citrouellal-like odor, is much u.sed as a perfume for soap. Sp. gr. 0.870 — 0.905. It is inactive or slightly dextrogyrate («DUpto +2°) and is soluble in 4 to 5 parts' of 70 p. c. alcohol. It consists to the extent of H(l — 90 p. c of r-itronellal, (JioHisd. The remainder of the oil. judging from the odor, cousi.sts of geraniol and citronellol. Cineol is not contained in it.- 276. Oil of Eucalyptus Dealtaata. EucaJvptUK (leuVia.ta A. Cunn. {E. viwiuali.s LtibiH.S) grows in Tiis- inania, South Australia, Victoria and New South Wales. The oil has an exceedingly fine, nielissa-like odor, due to citronellal. Besides this there is present another body of ]ileasant odor, reminding of geranium (geraniol?). The oil boils from 20(5 — 21 (i° and has the sp. gr. I). 871 — 0.885.^ An oil of E. wiminali'i (no author) described l)y Wittstein and Miiller is so different from that just given, that it is impossible that it should have come from the same plant. The odor was unpleasant: it had the sp. gr. 0.921 and boiled between 159 and 182°, that is, at a tem- perature at which the oil of E. dfalbata. had not begun to boil.^ 277. Oil of Eucalyptus Planchoniana. The fresh lejives of the tree, Eucalyptus iilanclionJaria F. v. Miill., occurring in northern New South Wales and in southern Queensland, yield according to Staiger" only 0.06 p. c. of volatile oil. It has a peculia.r, citronelh.i-like odor and the sp. gr. 0.915. 11 V. Miiller, Si-leet I-:xtra-Tropical Plants, '.ith ed.. ]>. 1S7. 21 Bericht voii S. & fu., Apr. 188K, p. 2(1: Oct. ISllO, p|i. ir, and 211: .\pr. ISin. p. 19; Apr. ISDK. p. 27: Oft. 1893, p. 17. 31 Maiden, The useful native plants ete., p. ."27. ■t) Bericht von S. & Co., Apr. 18x8, i>. 19. 5) ^[aiden, loc. fit., p. 274. 6) Maiden, loc. cit., p. 273. r,3S SpccJal l^RTt. Third Group: Citral-contiiiiilng Oils. 278. Oil of Eucalyptus Staigeriana. Eucalyptus ataigeiinmi, F. v. Miill. grows in northern Queensland. Its leaves yield upon distilla,tion 2.75— 3.8(5 p. e. of an oil, smelling- pleasantly like lemon and verliena.. It lias the sp. gr. ().H8o. = 1 Bei-ioht von S. * Co., A\tv. 1SX8, p. 21); Oct. ISSS. p. 17. ■<> Thi.s tree i.s alBO (le.siguated .Sydney peppermint in order to distinKiiisli it from ilie white and l»ro\vn peppermint tree, tlie E. tiiny^-(lalin:t. 4) .ionrn. and F'roc. of tlie Lloyal 8oc. of .\. S. Wale.s, 81, p. l;i.~i. OjAs of the Myrtnceae. 539 fractions pliellandreiie and cineol were fonucl. From the fractions boiling at 266 — 272° there separated a compotmd in well formed crj'stals, which was called eudesmol. Eudesuiol boils at 270 — 272° and melts at 74 — 75°. Endesmol has lately been subjected to a more thorouiih study by Smith. 1 It i-rystallizes in white milky needles melting at 79—80°. Its analysis corresponds witli the formula CioHmO, but contains neither an hydroxyl nor a ketone group. It yields a dinitro compound melting at 90° and a dibromide melting at 55 — 56°. Wilkinson 2 found for an oil distilled from E. ynpmtii the sp. gr. 0.918 and ['/]d= + 1.(;°. Fifth Group: Oils L^ss Known tiiid of Iinleflnite Odor. 282. Oil of Eucalyptus Diversicolor. Euciilyptus r]ivri:->icol(>7- F. v. .Miill. grows in south-western Australia. Ceylon and Algiers. The oil has the sp. gr. 0,924: [«]d= +■ 9.7°.^ 283. Oil of Eucalyptus Fissilis. The oil from the leaves of EunilyjifnN few/'/w '^ has the sp. gr. 0.928 and is optic-ally inactive.- 284'. Oil of Eucalyptus Goniocalyx. Eucalyptus g-oniornlyx F. v. Miill. is indigenous to Victoria and New South Wales. Yield from the leaves 0.9 p. c. The light yellow oil has a penetrating, quite unpleasant odor and obnoxious taste. Sp, gr. 0.918—0.920; [«]d = — 4.H°;2 boiling tempprature 152—175°.+ .\ccording to Smith i the (jil ccuitains eudesmol. 285. Oil of Eucalyptus Gracilis. The oil of Eucalyptus gracilis F. v. Miill., growing in Queensland, Victoria and south-western Australia, has the sp.gr. 0.909; [«]d = + 9.3°.5 286. Oil oi Eucalyptus Lehmanni. Eucalyptus Lehmanni Preiss. occurs in south-western Australia. The oil obtained from it has the ,sp. gr. 0.92;i; ['/.]r, = + 5.9°.2 i| .Jouni. and Vyitv. of the Roy. Soc. of X. S. Wales, 3a, j). S6 : Bericht von S. & Co., X\)r. 1900, p. '-ii- 2) Proc. of the Koyal Soc. of Vk-toria, 1H93, p. I'.IS. 3 I .According- to Mairlen. Eucalyptus fisnilis V. v. jMiill. is synonynions with E. nniyg- ilaliiia LabilL, the oil of which is Ktrong;ly laevosryrate. Its specific gravity also does not agree with that obtained by Wilkinson from E. flssiliK. 4) Maiden, The nsefnl native plants etc., j). 268. 5) Wilkinson, loc. cit., p. 1117. ■ " 540 Special Purt. 287. Oil of Eucalyptus Longifolia. EwnlyptuN longifolia Lk. is disti-ibuted in Vir-toria and in New Sduth Wales as far as Port Jackson, Tlie oil is viscid, has an aromatic cooling taste and caTnyjlior-likc odor. 8p. rt. ().!»4(»; boilinj:' temperature l!»4-21.-.°.i 288. Oil of Eucalyptus Occidentalis. Tlie lea\'es of Exii-nlypfiiH orr/Je;; to /;.w En dl. ^rowiri.u' in south-western Anstraha (; ; ['/]d = + -'."°-- 289. Oil of Eucalyptus Pauciflora. Eiiralyjifus ptincitiora Sieb. is founil in Tasmania. A'ictoi-ia and New Sonth Wales. The oil of the leaves has the s]). ^-r. (».S!»4— (1.020 : ['/.JD^ + to +17°.- 290. Oil of Eucalyptus Stuartiana. Evcnlyiitus stuniiiana F. v. Miilh, distributed from Tasmania to Qneenslanrl, contains a golden yellow oil. smelling sti-ongly of cvniene. but not of cineol.-' Sp. gr. 0.01 7—0. 0:!i' ; [,/]i, = — 7° to —10°.- 291. Oil of Eucalyptus Tereticornis. Euc-ilyptiK fpi-eticornin Hm. or red guai is found in \'ictoria ami Queensland, ami contains a red oil, of a dittlcultly definable , \i. 2S. i) Proc. of the [.innean Soc. of N. S. Wales. IS'.I'.), II, p. -JU-J ■ Bericht von S. & f'o.. .\iir. 101"), |i. L.U. Oils of the Umhelliferae. 541 294. Oil of Eucalyptus Camphora. The leaves of Eucalvptas cawpbora, known as sallow or swamp g-um, give an average yield of (.1.398 p. e. of oil. Sp. gr. 0.916. It contains pinene, cineol and mnch eudesmol.i 295. Oil of Chervil. By the distillation of the fresh fruit of garden chervil, Anthiiscus cerefolium Hoffm. {Chaerophyllum sativum Lam., Family' UmbelUferae) Charobot and Pillet^ in 1899 obtained 0.0118 p. c. of a light yellow oil of an ani.se-like odor, reminding of estragon. It consists principjally of methyl chavicol. On treating the oil with alcoholic potassa, anethol (m. p. 20 — 21°) was formed, which was converted into anisic aldehyde by oxidation. Gutzeit^ in 187-3 had distilled the unripe chervil fruit and obtained from 10 k. 27 g. of oil. He showed the presence of ethyl and methyl alcohol in the distillation water. 296. Oil of Coriander. Oleum Coriandri. — Corianderol. — Essence de Cnriandre. Origin and Histoky. The coriander plant, Corianrlruin sativum L. (Familj' UmbelUferae), cultivated in many countries and in nearly all climates, was used as a kitchen spice even before the Christian Era. As such, coriander fruit is mentioned several times in Sanscrit writings, in the Bible and in later Roman writings. Coriander fruit has also been found in old Eg^^ptian monuments of the tenth century B. C. among other still recognizable offerings. Coriander is also mentioned among the useful plants recommended for cultivation by Charlemagne, but it appears to have received, as with the Arabians, so also with the Grermaus in the middle ages, (jnly slight consideration. The fruit is again mentioned in the medical and distilling books of the sixteenth century, although it had been employed now and again as a, kitchen spice. The di.stilled oil of coriander appears to have been first obtained bj" Porta in the sixteenth century. In the price ordinances of spi(-es, the oil is first included in that of Berlin of 1574 and Frankturt-on-the- Main of 1.387 and in the 1-589 edition of the Dispensatorium Noricum. 1) See footnote i on p. .340. '■>) Liebig's Annalen, 177, p. 882. 2) Bull. Soc. chim., Ill, 21, p. ,368. 542 Sjipcial Part. Coriiinder oil was investig-nted in 1785 by Hasse, in IN;!.") by Tromnisdorff.' in 18r,2 liy A. Kawalier-' and in 1«81 by B. Grossei-.s A true insifiht into its composition, however, was broug'lit jibout by the investig-ati(jns of Senunler (18!)1 ) and of Barbier (18!t8). Preparatiox. Coriander oil is distilled from the fruit *^ which has V)een i-rushed between rollers. For the preparation on a large scale, only the (-(ji-iauder from JMoi'avia., Thuringia and Russia is used, the Yield being 0,8 — 1.0 p. c." Only in cases of necessity is the fruit of other districts, which are all much poorer in oil. used. . o4-4 Special Part. :\\ Oil from rijip coriander fruit distilled immediately after the harvest. Yield 0.88 p. c t^p. <^v. 0.87(i; an^ + 1S foimd that eununol combined with sodium bisulphite and thus recognized its aldehyde nature. This gave at the same time a rational way for the preparation of the body in a pure form. According to Kraut '^ (ISo-t) the lower boiling portions are distilled off and the residue shaken with sodium bisul]ihite. After standing 2-t hours the thick mass is expressed and decomposed by distillation with soda solution or dilute sulphuric acid. Cumic aldehyde, CmHioO, has the sp. gr. 0.972 at 13° (Kopp,* is.").",), boils at 109. .j° under l;!.-") mm. pressure, at 282° under 760 mm." and is optica.lly inactive. The presence of a. terpene in cumin oil lioiling at 15, p. 73. 85 546 Special P;trt. represented in the fruit, somewhat sparingly, but still in quantities sutfifient for preparation, in the green herb, while the roots give an aromatic water upon distillation, but no oil. B,y distillation with water vapor about 2..")— H p. c. of a very mobile and colorless oil are obtained from the seed. It smells and tastes strongly of celery, has a sp. gr. of 0.870— 0.80.') and «d = +67 to +79°. Composition. Celery oil consists of about !)0 p. (•. of hydrocarbons. In ail investigation in the laboratory <5f Schimmel & Co. a fraction boiling constant a-t 17(5 — 177° was obtained, tlie rotation of whii?h was aD = + l(.)7°. By the action oi bromine a solid bromide was formed which melted at 1().'>°. Aci-ording to this, il-linionene i is a constituent of celery oil. Other terpenes, it appears, are not present, in any case, pinene is excluded, as notliing came over before 170° when distilled. This is of interest, as adulteration with turpentine oil can now be readilj' recognized. The amount of tlie oxj^gena.ted constituents to which are due the celery odor is very small compared with the terpenes. 8oiiietimes a separation is effected during distillation, in that the heavier portions settle at the bottom of the receiver. Usuall,y, however, no heavy oil is obtained. This is only dithcultly volatile with water vapor and there- fore often partially remains as residue in the still when the oil is rectified. Such a residue, as well as the so-called lieavy o\\ was nseil l)y Ciamician and Silber^ in 1897 for their investigiitions. They found the following compounds : 1) Palmitic acid; 2) a phenol possessing the properties of guaiacol; ;!) a second phenol, white needles, melting at Gd— 67°. of the com- position CinHodUg; 4) a liquid Ijoiliug from 2(12 to 269°, probably a ■sesquiterpene; •'>) sedanolid, a lactone CioHisOo. It boils at 18.5° under a pressure of 17 mm. The corresptrnding oxy aind, sedanolic ai-id C12H20O3, melts at MS— 89° and, is ea-sily changed to sedanolid. From the oxida,tion results it follows that sedanolic a,i-id is o-oxyamyl- J-'^-tetra- hydrobenzoic acid, (i) Sedanonic acid anhydride. Ci2Hi(i02. Sedanonic acid, (J12H18O3. is an unsaturated ketone acid (in. ]i. 11:{°), o-valervl- Ji-tetrahydrohnnzoic acid. Sedanolid and the anhydride of sedanonii- acid are to be consiilered as the constituents giving the diaracteristic odor to celery oil. Their constitution is shown l)y the followinu- structural formulas : 1) Bericht von S. & I'l... Api-. 18',)2, p. :!.-,. 2) Berichte, »l>. |i]i. 4<.I2, .jOl, 141 '.I, 1424. 1427. Oils of the Uiiihi'Ilifi'rae. 54:7 CH . ('4H9 C : ('iHs CO CO Sedanolid Sprlanoiiic acid aiili.vdiirlp. 299. Oil of Celery Leaves. Oleum Apii (Jraveolentis Folioniiii.—Sellerieblatterol. — Essence de Feiiilles de Celeii. The oil prepared fi'om tlie fresh herb' (yield about 0.1 p. i-. ) has a strong odor of the fresh celery leaves. It is very fluid and of a greenisli- yellow color, has the sp. gr. 0. 848— U. 850 at 15°, the rotatory power '/u=+-48 to +52° and is soluble to a clear solution in 10 parts of 90 p. c. alcohol. 300. Oil of Parsle^. Oleum Petroseliiii. — Petersilieiisamenol. — Essence de Persil. Oriuix an'd History. Parsley, I'f'fi-unfliiiiun .sHtivuin iio¥im. {Apiiiin ]>etroselmuia L., Curnm ]iPtr(>seUmun Benth, et Hook. ) (Family f^nihflli- feme), was originally indigenous to the Mediterranean countries and to Asia Minor, but is cultivated as a spice in nearlj' all moderate climates. Distilled parsley water was during the time of the distilled waters a much used remedy and is oftwi described in the distilling books of the fifteenth and sixteenth centuries. Distilled oil of ]:)arsley does not appear to have come into use uutd about the middle of the sixteenth century. It is first mentioned in the drug ordinances of Frankfurt-on-t lie-Main of 1587 and later in the 1589 edition of the Dispensatoriuui Xoricum. The apiol contained in the oil, and crystallizing out at a low temperature, was observed as early as 1715 by Link, apothecary in Leipzig.2 and in 1715 by Walther.-' The oil from the fresh herb and the fruit was preparetl by Pabitzk,\-'t in 1754. Further, the oil and the C'rystals separated from it were mentioned bv Dehne-' in 1778, by Bolle'' in 1829 and by Bley'^ in 1827. 1) P.ericht %'on S. & Co., Oft. isn.". |). .5. 3) De oleis vea^etabilium eHSentia.libus. DUsertatio. I^eijr/.iii-. 174.", p. 17. ^) Braunschweiffer .\nzei,2:er. 1 7.'j4, j). \20r>. 5) Crell's cheml.sehe.'i .Tournal, 1778, I, p. 4iol, that it i.s half soliil at ordinary temperature. French seeds, however, give an oil much poorer in apiol. t'OMPOsiTioN. Apiol can be ccmsidered as the ]>riiicipal constituent of parsley oil. It has lieen studied by v. Gerichten -^ in lS7° and boils at •'i04'^. P)y the oxidation of isi)a])iol is formed: 1) Apiolaldehyde. ('kiHkiO.-,. small iieeilles melting at 102°. 2) Apiolic acid, CuiHidOd, m. p. 17.'>°. '■'>) .Vpiijiketonic acid. ('iiHuiOy. (a-ystallizing in long, yellow neeilles, which melt at KiO— 172°. The terpeiie frai-tion of parsley (jil Ijoiling at KiO — MW' ' has, ;n-i-oi-d- ing to V. (lerichten the sp. gr. ().«(;.') at 12" and the angle of rotation in a. loo mm, tube — .''.O.S". Hy conducting into it hydrochloric acid no solid hydrochloride w.'is obtained immediately; by diluting with alcohol anil pouring on a largv surface one was ol)tained in small (|uantity melting at ll.'>— IKi". .Vccording to this it is iiroliable th.-it 1-pineni' is a constituent of parsley oil. '1 Liebig's Aniiiilen, i;, p. 3(11. 5| Bi'i-ichte, 21. i>ij. '.IIM, IGL'l: -22. p -I LiebiK'.s Aimalen. 82, p. 2s;i. 24si; 28, p. 2288. :') Ilerichtp, V), pp. 2.''iS, 1+77. «) These are nieiitiuned under dill oil. i| I'.ei-ieliie. 21 , |i[). n;i2. 2.">14: ibid.. 7| ( Jriiiilins i Dis.sertaticii, Strassburs, ''■ !'■ ■'-•■■ is7!ii f(]iiiid the lioiling point of the terpene at 1.-.SO. Oils of the Uiitbellifenip. 549 301. Oil of Parsley Root. Th(:' root of parsley contains only very little oil. According to Schimmel & Co.' the yield on distillation from the dry root was 0.08 p. i\. from the fresh ().().") p. c The oil had the sp. ixr. 1.040 and sei)arated crystals even at the ordinary temperature (probably apiol). 302. Oil of Parsley Leaves. The yield of oil obtained liy distillation from fresh parsley herb amounts to only ().0(;— U.OS p. c.- Propebties. Oil of parsley leaves is very fluid and of a greenish yellow color. It has the full odor of fresh parsley which is cnly shglit in the oil from the seed. 8p. gr. O.OOO— (1.02.". : ,/d=+0°1() tM+:',°l()'. The oil distilled at OH — 17(1° under a pressure of 12 mm.; the principal part boiled fi-om T.S — 0(1°. By means of Zeisel's methoxyl determination made on the fractions which corresponded to the boiling point of apiol, it was ascertained, that only small quantities of this body were contained in the oil. 303. Oil of Water Hemlock. The fruit as well as the rout of the poisonous water hemlock, Ciaitn viirjsa L., contain volatile oil. Oil of the fruit. Trapp'^ obtained from the fruit collected in the autunm and dried, by distillation 1.2 p. e. of an almrjst colorless, quite fluid oil, lighter than wjiter and having the odor and taste of Roman caraway oil. By shaking with sc.idium bisul])hite solution a solid conqjound was obtained whicli hii.d the com])Ositi<.)n of cuminal hydroxy sulphonate (jf sodium. The oil not acted upon by the bisulphite solution consists of cymene: by treatment with fuming suljihuric acid cymene sulphonic acid was ol)tained. The oil of the fruit of water hemlo:-k contains therefore the same constituents as the Rcjinan caraway oil from Cuinhium cyminnm L., cumic aldehyde ainl cymene. Oil of the root. The roots yield on distillation 0.12-^—0.30" p. c. of an oil smelling of water fennel and celery and having the sp. gr. 0.870 1) Berlcht von S. & Co., Apr. 1894, p. ~>r,. 2) Berlcht von S & Co., Oct. 189,^, ii. 59. 3) .Journ. t. prakt. Chemle, 74, p. 428: .^i-chiv il. Phanii., 2H1, p. 212. ■t) Liebiff',s Annalen. 81, ]). 25.8. 5) .Journ. r. prakt. Cliernie, 105, p. 151. ' ■ • 5o<) Special Part. at 18°. It is entirely different from tlmt of the frnit, as it contains neither cyniene nor cunii(.' aldehyde. Upon fractional distillation a dextrogyrate terpene boiling at 166° "eicutene" was i.solated. By eon- dncting hydrochloric acid into eicutene a hydrochloride was formed, which solidified when cooled. Cii-utene is probably not an individual hydroi-arbon, but rather a Tnixture of several terpenes (pinene and pliellandreue?). The oil from the root of the water hemlock was formerly considered as poisonous. That this is not the case was shown by Simon. i who exjierimented on animals. SO-t. Oil of American Water Hemlock. The frnit of the poisonous ]ilant, ('icuta inaeul;it;i L., widely dis- tributed in North America, gives on distillation (Glenk-) 3.S — 4.8 p. c. of an oil smelling like Chenopodium nntliplininticum and having the sp. gr. 0.840 — o.8."5.5. The larger part boils between 176 and 188° and consists, as is .seen from the elementary analysis r)f the two fractions 176— 178.,-.° and 178—188°, of terpenes. 305. Oil of Caraway. Oleniii Carvi. — Kuiniiielol. — Essence de Carvi, (.)Ri(4iN ANii HisTOEV. The caraway plant, Cnniin carvi L. (Family rinhellifprcie), is cultivated largely in Europe and Asia,. Distilled oil of caraway is first mentioned in the price ordinances of Berlin for 1.574 and that of Frankfurt for 1589, as well as in the 158!» edition of the Dispensatorium Noricum. Prepahatiox. If all the oil contained in the caraway is to be extracted, it, like all other seeds, must be crushed between rollers before distillation. The crushed fruit must be distilled at once, as a great loss of oil is experienced by exposure to the air. At the beginning of the distillation considerable quantities of sulphuretted hydrogen are liberated. The cause of this has not yet been satisfactorily explained. This phenomenon, which also takes place with a few other umbelliferous seeds has been noticed as early as 1828 l)y Planche,-' Schimmel & Co.* have found methyl alcohol, furfurol and diacetyl in the distillation water, Acetaldehyde is also liberated in large quantities during the distillation. 1) Lk-Ule'H Amialen, 81, p. 1!.j8 ; vomv. also Phariii. Riiiulsihau. 18, p. 108. 2) .\mer. .rourn Pharm.. 63. p. 330: Stroup, ibid., (i8. p. 236. 3) Trommedorff'B .\eiiea .Tonriial. 7, \. p. 3,^8. *) Bericht von S. & Co., Oct. IS'.i'.i. p. 32. Oils of the UmbelHferae. 551 The modern distilling apparatus (fig 48 on p. 79) will hold about 2.500 k. of caraway, which yields its oil completely in 6 — 8 hours. Formerly it was customary — and is even done now and then at the present time — to distil earawaj^ in the uucomminuted state. The exhausted seeds are dried, and used in cheese manufacture or for pur- poses of adulteration. Of rourse, the seeds are not entirely deprived of their oil by this treatment, and the yield of oil is therefore less, which is. however, more than counterbalanced by the sale of the dried seeds. Caraway which has been exhausted by distillation, is distinguished from the fresh seed by its darker color, by the very faint oilor and taste, and the shrivelled appearance of the seed. Under the microscope, the broken, empty oil cells, and tlie torn upper layers of t'ells can be seen in a cross-section. The exhausted, comminuted caraway is also dried in special apparatus i and then used as a cattle food, which is highly prized for its nourishing qualities. According to a series of analyses made at the Royal Saxon Agricultural station at Mockern.- dried caraway fodder contains 20 — 2H..5 p. c. of crude protein (of which 75 — 85 p. o. is digestablel and 14 to 16 p. c. of fat. The yield of oil varies according to the source of the seeds. Schim- mel & C'o.'^ found as an average the following yields for the different commercial varieties: riavariaii, wild 6. .5 — 7 ji. c. (Teniian, cultivaterl ;i..5 — .5 FiiiiiiKli, wild 5 — (5 " • ialician 4..") Heesiaii, wild 6 — 7 Dutclj, cultivated 4 — (>.') '■ .Moravian 4 Norwegian, wild 5 — G..j " East Frisian ."i.Ti — (i East. Pru.ssian, cultivated r, — .j..") " Russian, wild 8.2 — HJi Swedish, wild 4 — (;..t " Styrian 6 " Tyi'olese, wild 6.5 " Wiirttemberg, wild 5.5—0 " The Dutc-h, Norwegian and East Prussian are the commercial varieties principally used for distillation. The caraway cultivated in 1) Miispratt-Stohmann. Techni.sche Cheniie, 4th ed., vol 1, p. HO. 2) UhlitzBCh, Die land wirthsehaftlichen VersiicheHtatloneii, 42, [>. 48. 3) Bericht von S. & Co., Apr. 1S97, Suppl. p. 26. 552 Special Piirt. Other places of northern Germany, is, in spite of its fine H])pearanee, not suitable for oil distillation, on account of the low yield. How extremely large the consumption of caraway is in Germany is seen from the following tigui-es.i Imported through Hamburg : 1896. From the Netherlands 1,(301,900 kilos " Norway il.OOO " " France 14,500 " Further imyjort from the sea l;),400 By rail and from the upper Elbe 105,700 Total 1,S30,500 kilos Add to this : Import to Germany by rail via (Troninnen... 31(;,600 kilos 2.153,100 kilos Of this came fi-om Holland : Conveyed by spa 1 ,()() 1 ,000 kilos liy laud, 310,000 •• Total l,0T.s,500 kilos a cjuantit}' equiyalent to ;.i9,.57() bales or fully <)(> p. c of the yield of a normal Dutch harvest. Several thousand bales, which were trans- ported to Au.stria, are indeed included in thesp ftguT-es. These are. however, more than corapensarted for by the caraway gi'own in Gei-many itself. The consumption of the Leipzig factories is probably not over- estimated iit lU, 0(1(1 to 12, ()()() bales per year. As to profit, the yield is not the only factor that comes into con- sideration, l)ut the quality of the oil as well. This depend.s largely on its carvoue content, which is indicated by the sjiec-ific gravity of the oil. It might happen, that the distillation of a consignment of caraway with a lesser yield of oil of high specific gravity would be more profitable than that (if another of higher yield liut lighter oil. For the preparation of carvone (carvol, Olftuu Cni-vi of the German Pharmacopoeia), the caraway oil is either fractionnteil in a vacuum or with water vapor. The fractions fi-om the sp. gr. O.'.XiO on are collected separately as carv(jne. The limonene (i-arvene) obtained as a by-product has the sj). gr. ().S.5() and is used as a c-heap soa]i perfume. Propekties. Normal cai'away oil is a c7. p. :n . Oils of tlw Umlipllilprae. 553 lies between 0.fl(>7 and — 2 parts of 70 p. c alcohol, and 1(3 — 20 parts of ."JO p. c. alcohol are sufficient for complete solution. The soluVjility in 50 p. c. alcohol is a good criterion of the purity of the carvone, as carvone containing 2 p). c. of linmnene will not dissolve clearly in 20 parts of 50 p. c. alcohol. Caraway oil, and especially carvone, is colored yellow by exposure to the air. The oil becomes thereby more viscous and of a higher s])ecific gravity. If 1 cc. of such a carvone be di.ssolved in an equal volume of alcohol and a few drojjs of a very dilute solution of ferric cliloride be added, a reddish-violet coloration will fje produced wliicVi, howevpr, vanishes on the further addition of ferric chloride. Fresldy distilled oil does not give this reaction. This reaction may perhaps be due to the formation of a ])henol by the decomposition of the carvone.' The proof, however, that a pjhenol is indeed formed, is still wanting. Composition. Volckel* in 1810 recognized that caraway oil was a mixture of two bodies, an oxygenated body and one free from oxygen. The i-arrier of the caraway odor, and therefore the most im]:)ortant constituent, is oxygenated. It has the composition CiiiHi40 and was formerly called carvol ; ^ Wallach.-t however, in 1893 changed the name to c-arvone in order to express the ketone nature of the <-orapouud. Pure carvone, liberated from its hydrogen sulphide a,ddition product, has the sp. gr. 0.9(34 and the specific rotatory pjower'"^ ['/]d = +(32.07° 1) Arcliiv fl. I'harm., 222, p. .3(j2. .Journ., Ill, 2, p. 74(5: .ratiresb. f. ('hem 2) IJebiR'K Annalen, 8.T, p. 308. 1872, p. 813. 3) Liebijr'M Annalen, 8."», p. 246. (jiad- +1 Liebiff's Annalen, 277, p 107. stone, .lourn, f'heni. Stic., 2.", p. 1 ; Fharm. =) Archiv d. Pharni., 221, p. 28:!. 554- Special Part. and boils at 229—280° (therniometer completely in the vapor). Good carawaj' oil rontain^i 50—60 p. c. of earvone. For the chemical behavior and derivatives of earvone see p.i.ji'e KiO. The liydrocarbtni of caraway oil boiling at 17.5° and called carvene by Sc-hweizer.' is, according- to Wallach's- investigation, d-limonene (tetrabromide, m. p. 104—105°). The odor of the carvene obtained by fractionation is quite different from that of pure linionene. It can be chanued to the (/liaracteristio It'nion-like cidor of hmonene by removing tlie last traces of earvone by means of the acetate of phenyl hydrazine and then shaking the preparation repeatedly with a dilute solution of potassium per- manganate. Examination. Caraway oils are often met with in commerce from which part of the valuable earvone has been removed. On the other hand under the designation "earvone" are fomid oils ivoni whieh a part, but not all limonene has been removed. Such products are readily recognized by their abnormal speeific lii-avity. In judging I'arvone its solubility in 50 p. i-. alcohol is also to be considered. The earvone content, and thus the value of a caraway oil, can be i-alculated from its density, by taking the specific gravities 0.9(;4- for earvone and 0.850 for limonene as a liasis. If ;) is the .'^peeitie ni-avity of tlie oil investigated, I) the spccitic giavity of one of the components (linionene), and c the difference of the spccitic jiva.vity of earvone (l).964| and linionene (0.850). the amount of tlie other component (enrvonel .v in ]iercents is given by the following formula: _ a — b . 1(H) e This method of deternnnation. which is sutticient fur practical purposes, re.sts on the assumption, that earvone and limonene are the only constituents of caraway oil. An adulteration often found is tli.at with alcohol, whidi. moreover, gives the impression that the consumer ha.s under consideration a readily soluble oil, especially suited for the liquor manufactui'e. For this reason the specific gravity determination atid the test fen- alcohol should never be neglected. For the direct determination of ("irvone in volatile oils. Kremers and 8chreinei-8 have recommended a method in which the earvone is 1) Journ. f. praU-t. Cheni.. 124. p. 2.-)7. -U I'imnii. Review, 14, p. 70. '-' ) Liebiff's .\linaleii. 2L'7, p. 2'.H. Oils of the UnilipUi ferae. 555 converted into its oxiiue, and sepai-ated fri:>ni the terpene by steam distillation. Th'> method is as follows: To a solution of 10 g. of tlie oil to be tested iu 25 cc. of alcohol is added 5 g. of hj'droxylamine hydrochloride (in case more tlian 50 p. c. of carvone is supposed to be present, the amount of hydroxy lamiiie is correspondingly increased) and 0.5 g. of sodium bicarbonate and the mixture boiled on a water bath in a flask connected with a reflux condenser for Yj hour. 25 cc of water are then added and the alcohol, which carries over a large quantity of limonene, is distilled off from a water bath. Steam is tlien passed slowly through the liquid until traces of carvoxime come over. In order tliat thesn are not lost for the determination, the last portions of distillate are collected separately in test- tubes, and when trace.s of crystals of carvoxime appear on the surface the distillation is interrupted. The tube of the condenser is theu washed with a littV hot water and this, as well as the last collected distillate, containing some carvoxime. returned to the flask. When thoroughly cold the solidified carvo.xime is collected on a force filter, washed, and dried by suction. The air- dried carvoxime is then transferred to a tared glass evaporating dish . and heated for one hour on a water-bath, and when cool weigln^d. To the weight thus obtained 0.1 g. is added as this is about the quantity lo.st during the heating. The Aveight of oxinie found gives by multiplying by the factor 0.9088 the amount of carvone present. It i.s to be regretted that this method, which can, perhaps, be improved, gives only approximate result.s. In order to determine the extent of the error. Schimmel & L'o.i prepared mixtures of pure carvone, prepared from its hydrogen sulphide addition product, with carefully prejiared limonene, and found differences of nearly 7 j). c. between the found and the real carvone content : \ 50 p. c. mixture gave 48.18 p. c. carvone. " 25 " " " 19. .36 " " " 12.5 " " " 8.51 " The source (jf error lies in tliat the exact point at which the distil- laticin is to be interrupted, is diflicult to determine. Moreover, a mix- ture of oxime and limonene, which remains liquid for some time, goes rjver and i.s lost for the determination, before crystals are noticed on the distillate. The details of thi.s method have been more carefully studied and the above results refuted by Kramers. 2 Walter'* has also based a method on the action of hydroxylamine on carvone. He treats the oil with hydroxjda.mine and determines the excess by titration with iodine. The applicability ami accuracy of the Tuethod can not be iudged from the available abstrai-t. 11 Berifht von S. «: Co., Oct. 189(j, p. 49. 3j Cheni. Zeitiins. Hepert., 2M, p. 264. 2) F'barni. ArchiveK. 2, p. 81. fjot) Sjifcia! I'uvt. In order to see in what succestsion the forniation of tlie individual constituents of carawaj' oil takes place in the plant, Schinirael & Co.i distilled caraway plants at different stag-es of growth and examined the oils obtained. Oil No. 1. From long' i-ut, fresh plants, parlly in bloom and partly in seed, Sp. gr. ()..SS2; nu at 17° l,4,s:i(»(); ».d = + O-'i' 12'. Oil No. 2. From fresh plants of the same cutting, but after removing the infiore.sceuce and fruits. 8p. gr. about O.NN (not accurately determined as the amount was small) ; ud at 17° l.-'iOs:', ; '/£, = + 2()°30'. Oil No. ;i. From fresh plants in an ad\-aiiced state of development, but in which the seeds were not yet fully ri])e. >Sp. o-i-. ().i)l,~i4-; no at 17° 1.4.s,S2.".; «D= + gave (/arvoxime in good yield. The result of the fractional distillation indicates that the carvone content of the oil is the lower, tlie more undeveloped the caraway plant is when distilled : it is highest in the oil distilled from riyje material. The reverse is true for the terpene content. Ac-cording to this it seems probable, that the terpene is fli-st formed in the plant and from tliis the oxygenated constituent. In both oils, the fraction boiling- from 240 to 270° (-ontains a body (jf quite high specific gravity, which is absent in normal (.-araway oil. This compfiund, which does not possess the properties of a phenol, and gives with ferric chloride no color reaction, has not been prepared in a pure state, and its relations to the other constituents of the oil are unknown. 306. Oil of Ajo-svan. OriCtIN a.\d History, ('iiruiii ajowiin P.entli. et Hook. [Ptyehotis njownn D. ( '. ) is an annual t)elong-ing- to the UmJielUfeine. and is culti- vated in India fi-om Panjab to Bengal and the S(_)uth Decan. It also grows in Egypt. Persia, and Afghanistan. The grayish-brown fruits are similar to tliose of parsley but are distinguished from these by their rough surface and different odor. The ajowan seeds found in Eurojie are almost exclusively of Indian source ;nid enter commerce from Bombay. Marwar in Rajputana is reported as the ]>riucipal Indian market. The plant is c-alled in India. Ajwnn, Ajwaui or Oiiiiun. The thymol crystals separating from the oil are known in the bazaars as Ajwiiu K;i-jjhul. that is, flower of ajowan. The thymol as well as the distillation water (Ouiinn water ) are u.sed medicinally in India, es]iecially in cholera. Ajowan oil mixed with fatty oil is used medicii]all,v like ajowan water in India. ]'kep-Vk.vtio.\. The i-omminuted fruit yields 8 — 4 ]>. c. of oil by distilliition. The exceedingly large amount of fat in the distilled and dried seeds, makes them very good fodder U)r cattle. They contain l."i — 17 p. c. of ]irotein and 2') — H'2 p. c. of fat (Uhlitzsch i ). Properties. Ajowa,n oil is an almost colorless or brownish lii|uid of a, decided thyme oilor and a sharp, burning taste. S]). gr. O.OOO — 0.1):!(); it is slightlv dextrogyrate. 1) Die InndAvirthsch-artlicln'ii N'er.siich.swtationen, 42, p. 55^ Special I'nrt. Composition. In ICuropp, ajowaii oil is distilled exclusively for tliH preparation of its principal coiistituent. thymol, of which it contiiins 4") — o'l p. c. Thymol, CioHnO, was found in the oil l\v Haines i and Stenhouse- almost simultaneously in 1855 — 5(5. It crystallizes in part from the oil and can he. completely separated by shaking with sodium hydrate solution. The remaining- part of tlie oil, about one half, consists of hydi-o- carbons. wliich are sold in commerce under the name of thymene as a soii.p perfume. Thymene is a mixture of eymene.i and a terpene boiling nt 172°, but not further investigated. 2 Thj'mene is the cheapest sourc-e for the preparation of cyinene. 307. Oil of Anise. Oleiiiii Aiiisi.—Aiiisiil. — Essence d'Anis. r)Ri(iiN AND History. The anise plant, Pimpiiiflhi. aiii.sum L. (Family Umht^Uifenie) comes originally from the orient, but is now cultivated in nearly all ])arts of the world. The European market is principally supplied l)y Russia, Germany, Scandinavia,, Bohemia, Moravia, France, the Netherlands and Spain. The greater jiart of this anise seed is used for distillation for the preparation of anise oil and anethol. Distilled oil of anise has, on aceouTit of its property to solidifv. no doubt been noticed as long as anise has been used for the preparation of anise water. Tlie distillation of the oil has. howevei-, been first described in the woi'ks of Brunsehwig, Lonicer, Hyff, Gesner, Rubens and Porta,, Valerius Cordns in 15-l-() called attention to the ready solidifi- cation of the oil. Nearly a, century later Robert Boyle again descrii)ed the "butter-like" soliditicatioTi of ani.se oil. Anise oil is mentioned in medical books and ordinanc-es first in the Pharnuii'op(ea Augustaiiii of 15,S(). the Dispensatoriuin Xoricum of 15,S1», and the Berlin ordinance of Mattliaeous Flacco of 1574. The first accurate investigations of a,nise oil were undertaken by Saussure-^ in 1H2I), by Dumas* in ls;?:i, by Blanchet and Sell-" in l,s:{y. 1) .loiirii. Ciieni. Sou., S, p. 2811: .Jahi-t-.sli. il. Clic.i].. IS.IC, |>. '(iL>2. 2) Ijiebiff'w Aunaleii, i*H. ]►. 26'.); OS. p. yo'.i, 3) Ann. de fhim. et Ph.vs., II, l:!, p. 2S(I ; Sclnveiffsvrs .loi.niiU f. Che[ii un.l Phv- 2'J. p. Kj.T. ■*) Ijieliiff's Annnleii. c., p. 24.". 5) Iliidcni, 0, p. 2S7. OiV.s- of the UinlMlUli'ini'. 559 Cahoursi in 1S41, by A. Laurent- and Gerhardt-^ in 1842. Gerhardt called the stearoptene of anise oil anethol and Cahours again pointed out the identity of the .iiteai-optenes of ani.se and fennel oils, previously recognized by Blanchet.* Production. The anise used for distillation comes at pre.sent principally from Russia. The cultivation is particularly carried on in the gouvernenients Woronesh. (districts Waleysk, Birjutschensk and Ostroy). Kursk, Charkow. Chersson, Podolia and Taurida. A part of the anise is used for the preparation of the oil at the place of production, the rest is for home consumption and export. The average export for the last 10 years amounted to 150,();i2 puds valued at 458.721 rubels per annum. The suburbs Krassnaja and Alexejewskaja (gouvernement Woronesh) are the commercial i.-enters for anise. The cultivation is principally done by the peasants. Anise oil was produced in Russia in 1898 to the value of 10.", ."■)((() rubels.-'' The yearly average of anise exported from Russia during the years 1882—1891 amounted to 1:!T,000 puds« at a value of 28."), 000 rubels. The iiicrease during this iiitei'val of time is interesting:" Kx-pm-t 1S82, (ill, 01)0 piid.s, value 1(S9,000 niliels ISOl, ITU, 000 " '■ ."i04,000 One de.sjatine* usually yields -lio puds and under favorable conditions of weather as much as 100 puds of anise. If, however, the weather is cloudy and rainy at the time of blossoming, the yield sinks to 20 — 2.") puds. The harvest in Russia was estimated in 1896 at 4.880.000 kilos. The exports of the diffprent ani.se i-ultivating countries in 189() was as follows : . ( Export over Libau 722,600 kilos "''*'^ \ '■ " Riga 396,000 " Levant " from Chios 400,000 " . f '• " Cadiz 24,200 " ^'"^'" \ " •• Malaga 102,000 " Bulgaria 402,463 '■ 1) Liebis'.s ,\iinalen, 41, p. ."tj ; ".(>, p. 177. 2) Ibidem, 44, p. ai3. 3) Ihlflem. 44, p. .31.9; 48, p. 234; .lourn. f. pnikt. Oliem., 3G, p. 267. i) Liebig'M Annalen, 41, p. 74. 5) W. .J. Kowalski. Die Pr(>(]ukti\ kriifte Rus^lands. Oerman eriitinii b,v E Daviilson. Leipzig, 1898, p. 322. 6) 1 Pud = l().37.o k. T) From "Oddi-iferous plants and volatile oil.s," a book in the Itu.ssian language b,^■ A. Bazaroff and X. Monteverte. 8) 1 DeHJatine = 109.2.5 Ar = 2.68 acres 500 Speeinl Part. Pkepakation. Tlie odor and taste of anise seed is due to its volatile oil. They yield their oil only completely when they are distilled in :i (■(ininiinuted condition. The yield obtained from the different comnieri;ial vtirieties is seen from the tollowinf;' table: Chilian aiiiise Yield 1 .9— 2.() ]i. c. Italian ( lioloKual " " 'i'l ('■pngiicKcr") " " 2.7— ;!.0 " JIaccdiiiiiaii " " 2.2 Moravian " " 2.4 — ;!.2 Me.Kican '■ " l,i)— 2.1 " East Pi-ussian " " 2.4 Kus.sian " " 2.4 — 8 2 Siianisli " ■' -'i.!) Syrian " " l.r,— (jO " Tlinriiif^ian " " 2.4 The rather marked (lifferen(;es in yield ai-e not always due to the diffi'i-eiices in the seeds themselves, but more often to the accidental or intentional admixtni-e with stems, other seeds, earth and small stones, sometimes amountinji' to -iO p. c. In Russia, and Moravia, earthy particles, very similar to anise in size and cr)loi- are said to lie especially ma-nufactnred. They are readily reco;;nize(l and separated wlien a samjile of the seeds is treated with chlorofoi'm or a i-oncentrated solution of salt in a test-tube. The seeds will rise to the surface, whereas the earth particles settle at the bottom. The amount of hii >i';:a,nic adniixtui'e can lie determined by means of an ash ileter- mination. Pure a.nise gives 7 — U) p. c. of ;rsli. Tlie distilled anise is dried in s]:iecial apparatus^ and sold as fodiler for rattle, foi- which pur])ose it is highly valued on aci'onnt of its high ];)rotein and fat content. According to analyses made in tlie Koyal Saxiai Ex]i(^i-iment Station at Miickia-n, the anise residues eout.-iin 17—1!) p. I-. of protein and 16—22 p. c. of fat (Uhlilzsch^), 11 might be nn^ioned that during the distillation, snl]ihuretted hydrogen is given off. I'BOPERTrES. Anise oil is, at medium temperatm-e (above 20^), a colorless, highly i-efrai-toi-y lii|uid of charai-teri.stic oclor, ami jiure, intensely sweet taste. In the cold it solidifies to a sm)w-\vliite. crystnlline mass, which bi'gins to melt al l.'i° .■ind bi'comes completely liipiid at l".l— 20^ The oil can umler certain eoniliticins be cooled far below its solidification point, without becoming sdlid and can be kept 1) .Mn!,^.si)rHtt-Stohni;iTiii, Technische Chemie, 4tli t'lV. vol. t. \>. i;9. -'I Die laiulwirtlischfiftlichen VersucliK.statioiieii, 42, ji. li'.i. Oils of the Uinlielliferae. 561 for a long' while in this over-cooled condition. The falling in of a particle of dust, touching with a crystal of anethol, a sharp agitation, or scratching of the walls of the flask with a glass rod, produces a sudden solidification of the entire mass, with considerable rise in temperature, the thermometei- rising up to the true solidification point of the oil. This is, as it is dependent on the anethol-content of the oil, a good indicator of the quality of the oil. In normal oils it lies between 15 and 19°. The method for determining the sohdiflcation point is described in detail on p. IHT. The sp. gr. of the liquid oil is 0.98(1—0.990 at 1."°. The plane of polarized light is shghtly turned to the left, ^d = — 1° ."lO'. (Different from fennel oil and fennel stearoptene wlii(.'h turn the light toward the right. ) For complete solution 1% — 5 vol. of 90 p. c. alcohol are requii-ed. Anise oil can be distinguished from star anise oil only by the odor and ta.ste. The reaction with alcoholic hydrochloric acid, recommended for this, which was discussed under star ani.se oil on p. ;!.')9. does not give reliable results. If ani.se oil be exposed for same time to the light, in contai-t with air (especially in the liquid state), its crystallizing tendency is diminished and finally disappears altogether. i The jihenomenon is due to the formation of oxidation products (anisic aldehyde and anisic acid) as well as polymers- (metanethol and photo anethol?). At the same time the sp. gr. is increased, which maj' go so far as to make the oil heavier than water. The oil becomes also more readily soluble iu 90 p. c. alcohol. When anise oil, star anise oil, or anethol (about 2 g. ) are evaporated in a small dish on a water bath, a conqiaratively large amount, 9 — 10 p. <:.. of a non-volatile residue remains. This is viscous, odorless, no longer tastes sweet, and propably consists mainly of photo anethol, a polymer, which, according to the in^'estigations of de Varda^ is foi'med l:)y the action of light on anethol. Composition. Ani.se oil consist principally of two isomeric com- pounds (J10H12O, namel.y, of the anethol, solid at ordinary temperature, and of the liquid methyl chavicol.* 1) ThLs was known at the besinninff of this century and is mentioned by H.aaen, Lehrbueh der .Vpothekerliunst, Ijth ed. (1806), V(d. 2, p. 411. 2) According- to Orimau-V anetliol loses its tendency to crystatiize by jn'olonjjcd heatlns (Bull. Soc. chim., Ill, l.", p. 778i. ■it Gazz. chim. ital., 21, I, p. ISH; Berichte, 24, Uef., p. ,164. 1) Bericht von S. & Co., Oct. lS9."i, p. 6. Bouchai-dat & Tardy later substantiate the occurrence of nieth.yl chavicol (estragol) in Russian anise oil (Conipt. rend., 122, p. 624). 36 562 Special Part. The cliariieteristii; properties of the oil ermaceti and fatty oil. All l| Ooiiipt. iTllil., 122, p. I'.lS; Bull. Soc. clliill., Ill, 1."., p. (512 = ) liericlit von S. & fit.. \\n-. IsitG, ]>. 7. Oils of the Unibelliferae. - 563 tliese adulterants are deterted by the determiuatiou uf the physieal properties, as specific gravity, optical rotation, solubility, and solidi- fication point (see p. 187). The admixture with fennel oil or fennel stearoptene is frequently practii;-ed. Even small amounts can, however, be recognized by the dextrogyi-ation in the polariscope. Dextrogyrate anise oils are, there- fore, in all cases to be rejected. In taking the sample for investigation, care must be taken that all the oil is melted and mixed to a homo- geneous liquid. Attention is here again called to the changes described on p. ."i(;i under the heading "Properties," which a normal oil" may suffer when carelessly kept and which must be considered in certain cases when the genuineness of an oil is to be determined. The best criterion for the quality of anise f)il is its solidifli'ation point, which lies normally between l.") and 19°, usually, however, at + 17°. 308. Oil of Pimpinella Root. The oil of the wliite pimpinella i-oot of Phnpinelln .snxifnign L. (Family rnibellifenw) is a golden yellow liquid (if a penetrating and unplea.sant odor, reminding .somewhat of parsley oil, of a disagreeable bitter, scratching taste. i Sp. gr. 0.9.'i9 at I.t." It begins to boil at 210°. then rises to about 3i)()°, a part even passing over above :MH)°, with considerable decomposition. 2 The oil of the black pinqjinella root, PinqiiueUa nigra Willd. (yield 0.38 p. c.) is light blue, floats on water and smells less penetrating than the preceding. It is changed in the sunlight even in closed vessels to a green color.-' 309. Oil of Fennel. Oleuui Foeiiiciili. — Fenclieliil. — Essence de Fenouil. History. The oil of fennel 1ms no doubt been known since the time of the preparation of the distilled waters. In the sixteenth century it appears to have been introduced along with fennel water as a remedy and its preparation described by Brunschwig and by Porta. In the municipal ordinances of drugs and spices it is first mentioned in that of Berlin of 1.571 and of Frankfurt-on-the-Main of 1.582; also in the Pharmacopcea Augustana of 1580 and the Dispensatorium Noricum of 1589. ij Trominadorff' e Neues .Jourii. d. Pharm., 12, II, p, 68. ^,) Bericht von S. & Co.. Apr. 181K>. p. 37. 3) TrommHdorff'.s Xenes Journ. d. Pharm., 1 ;-J, II, p. 48. 564 Special Part. Earlj' investigations of fennel oil were made in 1770 by Heyer of Braunschweig-, 1 in 1792 by Gertinger of Eperies in Hungary,^ and in 170a by Gottling of Jena and Giese of Dorpat. P\irther observations, which like the above deal mainly with fennel camphor (anethol), were juade by BnchnerS and by Goebel. Blanchet and Sell-^ recognized in 1H83 the identity of the stearoptenes from fennel and anise oils. This was corroborated in l.SJ:2 by Cahonrs." AVallach " investigated fenchone, a body characteristic for fennel oil, which possesses considerable theore- tical interest on account of its similarity to camphor. Origin. Fennel, Foenk-ulum rnlgare Gaertn. {F. {■apillnceum Gilib., Anethum foeniculuni Jj.) is a. fine umbelliferous plant, which is cultivated in Germany (vicinity of Liitzen), iloravia, Galicin, Roumania and Mace- donia, in France and Italy, also in India and Japan, partly on account of its edible root, but principally on account of its much used fruit. The fruits of the fennel cultivated in the various countries differ not only externa^3^■^ in form, size and i/olor, but the oils distilled from them show greater differences than is the case with the diffei-ent varieties of anjr other plant. The oils of the fennel from Liitzen, Roumania, (jalicia, Moravia and Japan, are distinguished by tlie l)itter tasting fenchone, which, together with anethol, produces tlie characteristic fennel odor. Fenchone is not found in the sweet Roman (French) and Macedonian fennel, anethol. cm the other hand, is either entirely absent, or present only in traces in the wild Ijitter fennel. Ill the individual fennel oils the greatest variety of terpeues is found. The oil of the fennel from Liitzen cc^ntains pinene and dipentene, wild bitter fennel jilielhindrene and ilacedonian fennel limonene. From this it follows tliat under the name of fenin'l oil ;ire understood oils of entirely different ])roperties. In the following the term "fennel oil" applies to the ordinary fennel oil of coniiiierce, the Oleum Foeniculi of tlie Pharmai-opueia, as it is obtained by distillation from the feimel from Liitzen, Roumania, iloravia and (-ialieia. 1) Crell'B Cht'ii). .JiMunul, :!, ]>. 102. 2) Oottlinft'-s .A.linana{--h fiii- .Scheiilekiinstk^r iiuil Apotheker. 14, i>. 140. 3) Biichiier'H Repert. t. die Phai-ni., 1.", p. KJS. ■^1 LiebiR'"s Annalen, 0. ]). 2S7, 5) Liebiff's Annalen. 41, \t. 74; .Innrn. I'iir itrakt. Chriii.. l.*4, ]>. S't'j. 6) Liebift's .\iinalen. 2.~)0. ji. 824; 2(>;j. p. 12'.t, 7) In an artlrle on the commercial Yai-ietie.-< of fennel and tlieii- essential oils (Pharm. .Ii>nrn., ."s, p. 22.". I I'inney in 1S97 deseribed and illusti-.-iteil the different varieties of commerce. Oils of the riiibeJIiferae. 565 Upon distillation of cru.shed seeds, the principal varieties give the following j'ield : Saxon fennel (Lutzen) Yield 4.4 — 5.5 p. c. Galician " " 4.5 — 6 Moravian " " 4 '' Roumanian " " 4.6 " The distillation residues, which form a valuable cattle food (comp. under caraway oil. p. 5ol) contain after drying 14 — 22 p. e. of protein and 12—18..". p. c. of fat.i Phoperties. At a medium temperature oil of fennel is a colorless or slightly yellow liquid of the peculiar fennel odor, and a taste, which is at first bitter and camphor-like, but having a sweet after taste. Sp. gr. 0.965— (). 975: '/.d=+12 to +24°. The solidification point of the normal fennel oil, determined as descril:)ed on p. 187, lies between + 8 and +6°. As with ani.se oil, so also here, tlie oil of the highest solidification point is the best. Fennel oil is soluble in an ecjual volume of 90 p. c. alcohol, while 5 — 8 vol. of 80 p. e. alcohol are required to dissolve 1 vol. of fennel oil. Composition. The constitnent of fennel oil longest known is anethol, crystallizing out in the cold. (See p. 179.) Good oils contain about 50 — 60 p. c. of this body. A second compound is also characteristic of the oil.- It is found in the fraction 190 — 192°. and has an intensely bitter, camphor-like taste. According to the investigations of Wallach and Hartmann ^ it is a ketone, which was tirst called fenehol, later fenchone. Fenchone, OioHioO, is isomeric and closely related to camphor, and gives a series of analogous derivatives. It boils at 192 — 198°. has the sp.gr. 0.9465 at 19°, is strongly dextrogyrate. [a]u = + 71.97°, solidifies at a low temperture and melts again at + 5 to + (i°. By reduction with sodium it is converted into fencliyl alcohol. GioHisO.'* For further information see p. 166. Of terpenes, d-pinene and dipentene are contained in common fen- nel oil. Pinene was detected in the fraction boiling at 157—160° (y-o = + 41°58') by converting it int(_i pinene nitrosochloride and pinene benzvlamine, melting at 122°. The fraction boiling at 180° after ten 1) Die lanrlwii-thschaftlichen Versiichsstationen, 4i.', p. :in. 2) Bericht von S. & Co.. Apr. 1890, p. 20. 3) Liebig-'H Annalen. 25!.l, p. 324; 26.=!, p. 129. i) Laboring under the supposition that this reaction in a (luantitative one, Uniney has elaborated an assay methort by convertina' fenchone into tenchyl alcohol and this into the acetate. Inasmuch, however, as it requires repeated treatment with sodium to completely reduce the fenchone to fenchyl alcohol, Cmney's results must be nnich too low (Phanii. .Journ., ."jS, p. 22.".). 500 SjieciaJ Part. fractionations g'ave, on shalving mth liydro1:)vonnc acii] in j^laeial acetic acid solution, dipentene diliydrobromide, ineltin;oj at 94° ; by bi-omina- tion, dipentene tetrabromide, melting at 123—124°, was obtained. The presence of pinene, fenchone and anethol is corroborated by a more recent investigation by Tardy i on an oil from French, c-nltivated bitter fennel. Newly found were methyl chavicol, as well as anise ketone. Anise ketone combines with bisulphite and boils between 2(J0 and 2(J5°. Upon oxidation with potassium perma-nganate, acetic and anisic; acids result. These meager results, together with an elementary analysis, the results of which do i^ot agree very well, lianlly justify the assumption / WITT _ of a new bodv of the formula <.'oH-t<,,,T 'V.r> cu ( 'tT2 . tU . t rig. The product obtained by Tard^' by condui;ting di-y hydrochloric acid gas into fraeticin 17(j — 177° could be separated by distillation in a vacuum into two portions, of wliicli the one consisted of eymeue, the other of dipentene dihydroi/hloride. Although the original fraction yielded no ]ihpllandrene nitrite. Tardy, nevwtheless, proclaims it as a mixture of phellandrene a,nd <:-yniene, assuming that the latter previ-'uts a positive phellandrene reaction. In order to make this explanation more plausible, it would first ha,ve to l>e proven that the eymi-'ne was originally in the oil. and that it did not result by the treatment with hj'drochloric acid. The oxidation products present in all anethol-i-ontaining oils, namely anisii- aldeliyde and anisic acid, were also founil in tliis ft^nnel oil. ExAiriNATioN. Th(j principal test is tliat for oils deprived of a jiart of their anethol by fi-a,ctionation or freezing. The solidification of such oils is then l)elow +8°, wliich can lie considered as t)ie lowest alhiwable limit. The addition of af<-oliol. which has sometimes been observed, is recognized by the ]o\vering of the specific gravity. The same is true for turpentine oil. The fennel oils described in the following paragraph liave more scientific than practica.l interest. Oil from the Sweet or l{oniaii Fennel. The variety of fennel cnltivateil in soutlierii Finance, and formerlv designated as Fni'iiiciiIuJii duh-t^ I). C, yields on distillation 2 — 3 ]>. c. of oil. It distinguishes itself by its higli anethol content and by the absence of fenchone. Sp.gr. (t.076— O.OtSO ; 2 -/^ = -f 7° ."()' to + l(i? 80' ;- solidification point +10 to +12°. i| Bull. Sue. cliim.. Ill, 17. |). (W.d. ;) T'miiey, Pliarni. ,Inu™., .TS. i,. L'l'r,. Oils of the LniilwUifenip. 567 Oil from Macedonian Fennel. The Macedonian fennel oil is very similar to the oil from the sweet fennel. It has a purely sweet taste and hig'li anethol content. Yield 3.4— 3. H ]). c. Sp. gr. (1.970—0.980; «d= + -"') to +12°; sohditication point +7 to +12°. Fenehone is entirely absent in Macedonian fennel oil. The terpenes boil from 170—180°. The fraction 170— 17.'>° («d = + •"')7°53') gave with glacial acetic acid and sodium nitrite a faint, but pronounced pliellandrene reaction. The fraction 175—180° ( ud = + . 40. Schimiiiel & Co. =) Phariu. .lourn., .j.S, p. 220. -I Lieljiji's AniialPii. 41, p. 74. cj Pharni. .Toiirn., .~i7, p. '.'1. 3) Zeitsclu-. t Chemie, .'., ]). ~j7'J. ~t Bericht von S. & Co., Oct. l.Sii.^., p. 40. ',r,H SjiecinJ Part. Oil from tlie Sicilian Ass Fennfl. The sharp tastinp,- fruit of the Foruirulum piperitum D. C. (Fmocchio rFusino) used in southern Italy as a spice, yields upon distillation 2.9 p. c. of oil. The sp. gr. of the oil is O.y.il. It can contain only traces of anethol, as on cooling to —5° no separation of anethol took place. Oil of Fennel from Asia Minor.^ Yield I). 75 p. c. ; sp. gr. o.DHT. Oil from the Syrian Fennel. ^ Yield l.G p. c. ; sp. gr. 0.072. Oil froTU tliH Persian Fennel. 2 Yield 1.7 p. c. ; S];i. gr. ().!)77 ; '/r,= + 14:°; m. p. 11.2°. Oil from Kussiaii Fennel. - Yield 4.8 p. c. ; sp. gr. (».0(;7; «d = + 2;!° ; m. p. 4.4'-. 310. Oil of Metitn Athamanticum. Biirwurzol. The dry roots of Meuiii nthnjii.-iiiticuui Jac(:j. ((lerra. BTirwurz). gave on distillation 0.(57 p. c. of a dnrk yellow oil, very similar iu odor to lovage oil. Its sp. gr. at 21° is 0.99i). It Ijegan to lioil at 170° and above ;iOO° greenish-lilue frartions. smelling like celery, came over. By distillation from a, glass tlask ahont half the oil I'esinifled.'^ 311. Oil of Silaus Pratensis. Siliniiil. The fruit J^ of Sihnis yirntfiisis 15essi'r (Family UniheUiferae). growing wild in (Termany, gives hy distillation 1.4 p. c. of oil, tlie odor of wliidi reminds strongly of estragon. A stearoptene separates in fine needles when exposed to the cold. Sp. gr. 0.9S2: «d=+<*°7'. Saponification number 20. S. 313. Oil of Water Fennel. Oleum Pliellaiulrii Aciuatiei. —Wasserfeiiclielol. — Essence de Feiioiiil d'Eaii. The fruit crt' the water femiid, (h'lmutlii' mpinticti Laui. (Oenanthe jilieUnndriuin Lani., I'lii'll^niilriuiii :i. 3) Bcrioht von S. & Co., Apr. ISN'.I, p. 4/!. i) Kelicht von H. & Co., Ort. Ls'.!.", p. ."'j. Oils of the UnibelMerae. 569 volatile oil. Oil of water fennel is at first a colorless to wine yellow liquid, becominii' darker with age. It has a strong penetrating odor and burning taste. The sp. gr. is 0.85—0.89; aD= + 12° 42' to + 15° 30'. It begins to boil at about 170° and about 50 — 60 p. c. go over up to 172°. On fui-ther heating the thermometer rises gradually to 300°. and flnallj' a black resin remains in the flask (Bauer i). According to an investigation by Pesci^ in 1886 the oil consists to the extent ot 80 p. c. of a terpene, characterized by a nitrite melting at l(->3°, which has been called phellandrene, after the name of the plant yielding the oil.s For the properties and derivatives of this hydrocarbon see p. 121. Haensel * has observed the separation of a, small amount of a heavy oil on tlie bottom of the Floi-entine flask during distillation. 313. Oil of Lovage. Oleniii Levistici. — Liebstockol. —Essence de Liveclie. Origin and Histoky. The original habitat of the umbelliferous plant Levisticum officinale Koch [Angeliai levisticum Baillon, Ligusti- cum levisticum L. ), now much cultivated as a kitchen spice, has not been determined, nor has the plant been definitel.y found growing wild. The distillates from lovage root are often mentioned in the later treatises on distillation. The oil distilled from the root appears to have come into use about the middle of the sixteenth century. It is mentioned as Oleum Levistici in the price ordinance rjf Frankfurt-ou-the-main ot 1587 and as Oleum Ligustici in the 1589 edition of the Dispensatorium Noricum. All parts of the lovage plant contain volatile oil. Formerly only that from the root was prepared, but lately the oil ivoxa the fruit and herb is also made. Phepabation. The aromatic, fresh roots of lovage yield upon distillation with water vapor 0.3 to 0.5 p. c, the dried roots 0.6 — 1 p. c. of oil, the odor of which resembles that of angelica, oil. According to whether the fresh or dried roots are u.sed in the distillation, a yellow or a brown oil is obtained. These oils show but a slight difference in specific gravity, but behave differently during the process of distillation. •' When dry lovage root is distilled there appears together with the oil, 1) Ueber daH iUheiiHche Oel von P/je/Mri- •>) Liebis's Annalfii. -I?/.), p. iO. ilrinm aquaticiim. InailS'. Dissertat. Frei- *1 Pharm. Zeitung, 4.3, ]) TtiO. bui-g, 1SS.O. °) Bevicht von S. & Co., Api-. 189.j, p. e distilled with water va])r)r and then fractionated theiv will be obtained. acc(ird- ing tc) Bfauii,' a fraction boiling at 17(j'^' under ordinary atmospheric pressure (sp. gr. 0.sri:-!4, «ii^ + ."i°) and having the composition of a terpen(^ Schimniel & T'o. isolated as jirim-ipal fraction a li(piid l)oiling between 107 a,nd 11.")° under l.'i mm. ])ressure. From this could be separated at ordinary ])ressure a fraction boiling at 217 — 2lN'-. which solidified to a crystalline mass and ha.d all the properties of solid d-ter])ineol ; •' «d (in over-cooled condition) ;= + ~!'° l^*' at 22". M. ji. of terpinyl phenyl urethane 112°, of terpineol nitrolpiperidinc l."il — l."i2°. The dihydriodide prepared from the terpineol melted at 77 — 7.S°. 314. Oil of Lovage Kruit. The fruit of lo\-agc yields ujioii distillation 1.1 p. c of a distillate very similar to that obtained from the root. iSp. gr. O.iCi.'i.^ 315. Oil of Lovage Herb. The fivsh herb and flower stems of Levi.stiruni otticimUe yield 0.0." — 0.1."i p. c. of oil. whiih is very similar in odor to that of the root. It has the sp. gr. 0.!)0d— 0.<)40, «u- + lb to -f 4(;°. It is solubli' in an equal jjart of bO p. c. alcohol. 316. Oil of Angelica. Oleum .Viigclicae. — Angelicinviirzeliil. — Ksseiico «l\Vii!;eli(iiu'. Origin and History. Angelica (tici-. luigvhvur/.). Ai-rli.-niai'licii offii-i- U!ili» Hoffni. (Angvlicii ;ii'fli:iiigvlic;i L. ) (Family riiihrllili'nif], gi-(.)ws 1) Archh (1. rimriii., 2:j."), |ip. 2 anil Is. ^) FliickiK-er ( rhariiiin-oani)BU-, r'.rd vi]., ]i. 4Ciiii foiincl an uil, the s.uiiTf nf wliii'li is not nu'ntifineii, tit be laevoffyrate. 3) Berie-lit viin S. i Co.. .V|ir. IS'.IT, p. 27; (.)i-t. IS'.IT, ji. '.), footnote :1. i) Ileriellt von S. & Co., Xyn: 1S9(), p. 4s. 0;/,s of the Umhellifer.ip. 671 here and there throiiuliout northern Europe as far as Siberia and is niueli cultivated as a drug and for the manufacture of hquors. The plant is the finest of the north European nnibellifers and contains in all parts a peculiar aromatic volatile oil, especially in the root and fruit. The fresh green parts of the plant serve as a much liked vegetable in the northern parts of Europe, Sweden and Finnland, and on Iceland and Clreenland. Angelica appears to have first come into use as a spice plant during the fifteenth centurj^, and was no doubt first used for the preparation of the distilled angelica, water, the preparation of wliich is described in Brunsi-hwig's and in later treatises on distillation. The distiUed oil of the roots was not prepared until the .second half of the sixteentli century and first mentioned in the price ori]inance iif Frankfurt in l.")S2 and in the Dispensatorium Noricum of 158!). Recently tlie oil from the fresh roots, the stems and leaves and that of the fruit, have also come into u.se. In composition the oils of the various parts, and of the fresh and dried plants, are on tlie whole identical. Marked differences exist, how- ever, in the quality of the aroma. The aroma, as witli so many plants, appears to l)e affected by the place of growth, the moisture of the atmosphere and the intensity of the hght during the time of develop- ment of the plant. Oil of angelica root was investigated by Buchner in l)S4:2,i Ijy Beilstein and Wiegand \n 1S82,- tjy Xaudin in l!S83,-'' and by Ciamician and Silber in ISfXi.i Preparation. Tlie oil of the roots as well as tliat of the fruit (oil of .angelica seed) finds practical application. The distillation material comes mostly from Thuringia and Saxony (Erz-(jebirge), although sometimes the fruit from France, from Moravia, and the Harz are used for the preparation of the oil. The yield from the dry root is ().>\^i — 1 p. c: fi-om the fresh root, which gives a finei- oil, 0.2 — 0.;!7 p. c. Properties. The oil from the root is. wlipn freshly dtstilled, an almost colorU'ss li(juiil of a pleasant balsa mi(/ odor. It becomes yellow to brownish when kei)t, due to the action of light and air. The odor is very aromatic, pepper-like with a slight admixture of musk. The taste is .spicy. Sp. gr. 0.8.'T— O.OlS ; uy,= + lC, to +32°. i| Hiichiier'.-i Kepert. f. d. Phfinn., 7r>. p. ]li7. 3) Hull. Soc. i.-liim., H'.i. p. 114-. 2) Berichte. !.">, p. 17-tl. *) Beiichte, 2'.l. p. 1811. 572 Special Part. Composition. The oil investigated by Beilstein and Wiegand- gave on distillation a principal fraction at 160—175° ; a small part boiled between 175 and 200°, and still less above 200°. Tlie lowest fraction had after repeated fractionation the constant boiling point 158° and the composition C]oHi«. The terpene absorbed 1 mol. of hydrochloric acid gas, but did not separate a solid hydrochloride. The fraction going over between 170 and 175° formed the principal product and likewise corresponded to the formula CidHia. From this fraction a hydrochloride melting at 127° crystallized out, after passing hydro- chloric acid gas into the oil. After repeated treatment with sodium the fraction boiling originally at 175—200° boiled constant at 176°. The analysis indicates a mixture of terpeues and eymene. From the diffi- cultly volatile portions a hydrocarbon boiling at 250°, probably a sesquiterpene, was obtained. Naudin^ obtained by fractionation a pepper-like smelling terpene of the boiling point 16(5°, which he called --terebangelene. Schimmel & Co.'' showed the presence of phellandrene in the oil by the preparation of the nitrite. As the solution c:)f the phellandrene nitrite in chloroform turns the ray of polarized light to the left, and as the rotation of the nitrite is in the opposite direction to that of tlie hydrocnrbon, it follows that d-phellandrene is contained in angelica root uil. From the investigations of Beilstein, Wiegand and Naudin it can be concluded that other terpenes (probably pinene) are also present. No doubt the /3-terebangelene of Naudin can be considered as a mixture oi phellandrene with a lower boiling terpeiie. The high boiling fractions, in which the carrier of the musk-like odor is present, were investigated by Ciamician and Silber.-t Fi-om the fraction obtained last iluring a. steam distillation, tine crystalline leaflets of the melting point 71 — 77° separated. The amount was too small for a detailed investigation ; it was probably the an- hydride of an oxy acid. The oil distilled in a. v.icuum was saponiiied with alcoholic potassa. The non-saponiflable part had the characteristic odor of the sesquiterpenes and boiled between 240 and 270°. iSulphuric a,i'id separated two acids from the alkaline solution; 1) a. valerianic acid, methyl ethyl acetic acid, the calcium salt of which crystallizes with Ave mol. of water; 2) oxy penta decylic acid, CisHjj.Oa, which when crystallized from ether, forms sta,r grouped needle.s df the m. p. 81°. i| P.eviehte, ITi, jj. 1741. 3) Bericht von S. & ('i>., .Vpr. ISiU, p. M. -') Bull. Soc. chim., II., 39, \). 407. *) Berlfhte, 3;i, p. ]sn. Oils of the Umhelliferne. 573 Of the deri^'atives of thi>< acid were prepared tlie barium salt, the acet- penta decj-lic acid of tlie m. p. 59°, the brom-penta decylic acid, m. p. 6.5°, and finally the iod-penta deeylic acid. m. p. 78—79° and crystal- lizing in pearly scales. ' It may be mentioned that the next lower homologue of oxy penta decylic acid, oxy myristinic acid, is contained in the oil from angelica seed. 317. Oil of Angelica Seed. Aiigelikasaiueuol. Angelica seed yields upon distillation 1 — 1.2 p. c. of oil. Phoperties. The oil is very similar to that obtained from the root. Bp. gr. 0.850—0.890; aD = +ll to +12°. CoMPOSiTiox. iXeither of the investigations for the terpenes of the oil from the seed made by Midler^ in 1881 and by Xaudin- in 1882 yielded positive results. The rjnly hydrocarbon definitely determined is phellandrene.^ It is j)robable that, as in the case of the oil of the root, phellaiidrene is not the only terpene. Of oxj'genated constituents Midler found • after saponifying the oil with alcoholic potassa two acids. 1) A valerianic acid, namel.y method ethyl acetic acid, as was shown by the ]jroperties of its barium salt. 2) Oxy myristinic acid, jiearly leaflets of the m. p. 51°. It is found in the highest boiling and in the non-volatile portions. A number of salts were prepared and analysed. Benzoyl oxy myristinic acid, crystallizing in small white leaflets ami melting at 08°, was also prepared. 318. Oil of Angelica Herb. Angelikakrniitiil. Fresh angelica lierlj yields about It.l p. c. oi oil* on distillation. In odor it differs litit slightly or not at all from the root oil. 8p. gr. 0.870-0.890; «d = + ''^ to +21°. 319. Japanese Oil of Angelica. Japanisclies Angelikaiil. Two species of angelica are cultivated in .Japan for tlieir roots. Tliey are Angelien reirnctn Fr. 8c-hmidt (-Japanese Senkiyu) and Angelica, anomala Lall. = Angflifa japonieu A. Gray (Japanese Biyakushi) (EeinS). 1) Berichte, 1+. p. 247(1. 3| Bcricht ron S. & Co., Apr. Lsill. ]). ;:i. 2) Bull. .Soc. chilli., II, H7. p. HIT: *) Bericht von S. & Co., .Apr. IS'.io, j). 10. ■Compt. rend., r):^, p. 1140. S) ,Iapan. I.eipziff, ISSii. vol. II, p. l.";V). 574 Special Part. The Japanese angelica rooti is somewhat poor in oil, containing only 0.07— 0.1 p. c. Sp. gr. 0.910 at 20°. At +10° the oil separates i.-rystals and at 0° it solidifies. The crystal mass obtained by freezing: and suction filtering has the property of a fatty ai:-id, the melting point of which, after several recrystnllizations, was (W— (>5°. (Impure oxy penta decylic acid?) The boiling point of the oil lies between 170— ;ilO°. The fractions coming over last are of a fine bluish-green color. The residue solidifies upon cooling and i-onsists mainly of the non-volatile ficid. The odor of the Japanese oil is exceptionall,y intensive and persistent, also sharper than that of the German oil. It also has the characteristic admixture of nmsk odor. From the fruit of the Japanese angelica Plural obtained 0.67 p. c. of oil.i 320. Oil of Asafetida. Oleum Asae Foetidae. — Asaiitol, Oel von Asa foetida. — Essence d'Ase Fetide, Ohi(4ix and History. Asafetida (Ger. A.'^nnt, Stinkasant or Teufels- dreck ) is the dried-up milk sap) of several species of Feivln: and Peuee- dujijiui, especiall.v of Femla asn tbetkla L. gro'ving in Persia, Afghanistan and the table lands of northwestern Asia. In the mediaeval distilling books, asafetida is not used by itself, but as an addition in the distillation of alcoholic balsams. The volatile oil of asafetida is apijiarently first mentioned in the price ordinance of Strassl)nrg for 1(585. Asafetida yields upon distillation 3 — (17 p. c. of volatile oil. which possesses to a high degree the un]ileasant odor of tlie drug, reminding of onions and garlic. Its color is yellow to brown. Sp. ^r. (l.n7.">—0. !)'.»() ; optical rotation- ajj-= — '.)° l."i' (single observation). (Composition. According to an investigation l)y Hlasiwetz ■' in 1819 the oil is free from oxygen and nitrogen a,nd i-ontains (('nHn )2l8. hexenyl sulphide, and (CeHii)2S2, hexenyl disulphide. Semmler,-!- however, in 1891 reached entirely different condusions. He found a snndl amount of oxygenated compounds and an entirely 1) Bericlit von S. & Co., .\pr. ISS'.l. p. 4. = ) Fliickiger (Phai-macognosie, 3rsition for the .sulphides. He .separated from tlie lowest Vioiling fractions, by repeated distillation from metallic potassium, two tei'penes : A hydrocarbon apparently identical with pinene. Sp. g'r. O.S()02 at 10° ; ,/.v =-- -\- '■Vl° 30', It formed a liquid dibrom addition product GioHittBra, A second terpene in smaller amount, which o-ave a solid tetvabromide CioHioBr4. From the highei' boiling portions the following compounds were isolated : A disulphide C-H11S2, b. p. 83— .S4° at 9 mm, ; sp, gr. 0.9721 at 1.";°; '/.i)= — 12° 30'; it is present to the extent of !•") j). c. in the crude oil. A disulphide ('11H20S2, which makes up 20 p. c. of the oil. Sp, gr, 1,0121 at 11°; b, p. 126—127° at 9 mm,; «d = — 18° 30', The repulsive odor of asafetida oil is due principally to this compound, A body (CioHioO)n. Sp. gr. 0.9(i39 at 22°; b. p, 138—115° at 9 mm.; aD = — Ti°. It is contained to the extent of 20 p. c. in the crude oil. By treatment with sodium, cadinene C15H24, results, A compound CsHiriSj. B, p, 92 — 96° under 9 mm, pressure, A disulphide G10H1SS2, B, p, 112—116°, 321. Oil of Galbanum. (Talbanuiiiol. Oeiui.n and History, Galbanum, a gum resin, is the dried milky juice exuding from the trunks and larger branches of the umbelliferous plant Ferula vnbricaulis Boissier, F. galhaniflua Boissier et Buhse (Peucediinum rubriaiule H, Baillon, P. gulbanifluum H. Baillon and probably also of Ferula (Peucedanum) Schair growing in Persia. Distilled oil of galbanum was prepared by Ryff, by (Je.sner, and by Rubeus. It was included in the l.')89 edition of the Dispensatorium Xoricum and in the Pharmacopoea Augustana of l.jHO, and mentioned in apothecary and spice ordinances about 1.560, Early cursory in- vestigations of the oil were made by Neumann about 1728, by Walther in Leipzig about 1711, by Fiddichow in 1815 1 and by Meis.sner in 1810,2 Preparation and Properties, The aromatic, not unpleasant odor of galbanum is due to its large content of volatile oil. The yield on distillation is different according to the age of the drug and varies between 11 and 22 p, c. 1) Berl. .Jahrbuch der Pharmack', ISIU, p. 230. -) TrniiiiiiKdorff's N. .Joiirn. d. Pharm.. 1, I, p. .'J. 57(i Speci,-il I'iirt. Oil of galbarmm is j^ellowish, has the sp. gr. 0.910—0.940 and turns the ray ot polarized light either to the right or to the left, aD = + 20° to —10°. According to Hirschsohni Persian galbanum yields a dextro- gyrate, levant galbanum, however, a laevogyrate oil. Composition. An oil investigated by Mrissmer.^ which boiled almost completely between 160 and 16.")° cannot be considered as normal, as the distillation with water from a glass retort will yield only the lower boihng portions and not the difficultly volatile, higher hydrocarbons. The dextrogyrate hydrocarbon GioHio, boiling at 160—161°, gave with hydrochloric acid a crystalline compound, which agreed completely in its properties with the corresponding body from turpentine oil. Mossmer did not succeed in obtaining terpin hydrate with nitric acid, but FliickigerS was successful in preparing it in this manner. The terpene of galbanum oil, is therefore, d-pinene. Fraction 270—280° contains, according to Wallach,^^ cadinene. CiuHoj, the presence of which was shown hx the preparation of its dihydrochloride, melthig at 117 — ll.S°. 332. Oil of Sumbul. Oleiiiii Suiiibiili. — Moscliiiswurzel- oder Sumliulwurzeliil.- Essence de Sumbul. In East India the roots of several aromatic plants are design:-ited as sumbul. The root of Nardostuchyn jcittirnnnsi D. C. is known as Sumbul Khifli, the ro(jt of Yalerhinii celtica L. as Sumbul EkJeti, Sumbul Ekelti, Suinliu! Kurni and SumJiul it;ilicus." The root of Doivnin amiiioniacuni Don. often used for a.dulteratiug the genuine sumbul ro(_>t, is known as Bombay sumbul (u- Boi.'' The genuine suniliul rorjt comes from Fpvula suinlnil Hooker fil. Euryangium sumbul Kauffmann) and was first broui^Iit into Europe in is;-!."). On distillation it jdelds 0.2 — 0.1 p. c of a viscous, dark colored oil of musk-like odor, and a sp. gr. of O.O.'il — 0.901. The sa]:)onitication numlier of the oil is 92 (single determination). It is not soluble in 10 vol. of 80 p. c. alcohol but m a.n erpial volume of 90 p. c. alcohol. Nothing is known as to the composition of the oil. 323. Oil of Gum Ajntnoniac. Aniiuojiiakg'uiiiuiiJVl. Okigin and History. The flow ot a gum resin from the umbelliferous plant DovMua ammoniacum Don. (Pmceclauum aimnornacum H. Baillon), 1) .lahi-e.ib. f. rl. Pli;u-iii., ^H^^,. p. ll;i. t) Liebig's .-Vmialen, 2as, p. ST. 2) Llehlg's Aiinalen, llil, p. 2.57. 5) Pliarm. .lourn., I. 7, p. Ti+li. 3) Pharinacogiiosie, 8nl e(L, ]>. \ I, .Vi'iol 11, Which of these two formuhis belongs to the api(.)l fr(jm parsle,y oil and which to that from dill oil is still to be determined. 328. Oil of Peucedanum Sativum. Pastinakiil. Tlie dried fruit of Pfiuveilanum mitivnm {P;istin;iea sntivn L.) yields by distillation with water vapor 1.5 to 2.5 p. c. of oil.- The oil is j^ellowisli and has a penetrating, ])ersistent odor. Sp. gr. 0.87 — 0.89; "i) = — 0°15' to — 0°80'; saponitication number about 170. (.'OMPOSITION. The chemical <'omposition of the oil appears to cli.ano-e with the ripening (jf the fruit. Van RenesseS in 1878 found that the greater part of an oil, distilled from the ripe fruit, boiled Ijetween 244 and 245° and consisted of the 1) Berichtc, 211. ]>. 1799. '■:) Witt.Mti-in In 1839 (BufhmT's Kepert. f. d. I'harm., (i8, p. l,') obtained a yield, of l»nt 0,7 ]-i. e. ^M Liel>iy".s ,\nnalen, HUj, p. S4. Oils of the Unihellifenip. 581 •octyl ester of normal butyric acid. Tlie acid contained in the portion distilling- over below 244° gave on the analj'sis of its silver salts figures which point to a mixture of butyric acid with an acid of less carbon <-ontent. Whether this is propionic acid, as van Renesse suspects, or some other acid, cannot at present be decided. An oil distilled by Gutzeiti from ripe and half ripe fruit was less simple in composition: It consisted for the greater part of the following three fractions : 195— 21U° uw.6 ]i. ('. 233—240° 20.3 " 240—270° 12.1 " The presence of ethyl alcohol was shown by Grutzeit in the distil- lation Writer. 329. Oil from the Fruit of Peucedanum Grande. The oil from the fruit of Feuvednnurn grnnde C. B. Clarke lias an exceedingly strong, spicy odor,^ reminding of the carrot oil. Sp. gr. O.OOdS at iry-,°: ao = + ;!(;°. It lioils from 18."— 228°, leaving a quite large residue. '^ 330. Oil of Peucedanum Root. The dry root of Pfiii-ednnnin officinale L. gives 0.2 p. c. of a yellowish-brown oiH of an intensive, persistent odor, hardly pleasant and reminding most of senega root. Sp. gT. ().f»02; '/.D^ + 29°4'; saponification number (52. Upon standing in the cold the oil separated a solid body, which when twice recrystallized from alcohol formed somewhat yellowish himinae melting at 100°. 331. Oil of Heracleum. Biirenklaiuil. The oils obtained from the fruits of different species of Heracleum are of nfi practical importance, but are very interesting from a scientific point of view. On the one hand because the esters of the fatty acids of alcohols of the paraffin series, otherwise difficult to obtain, are con- tained in them, and on the other hand, because the predominant con- stitu(jnts in different stages of the development of the fruit allow of drawing certain conclusions in plant physiolcjgy. It has namely been 1) Liel)ig'.s Annaleii. 177. p. .^72. 2) Berifht von 8. & Co., Apr. isni, |). ."(i. 3) Pharmncosrraphia Indica, vol. 2, p. 12i'>. 1) Berieht von S. & Co., Ajir. ISil.". p. I'A. 582 Special Part, determined that not only the oil ('outent, but also the chemical com- position of the oil is dependent on the stage of ripeness of the seed. In the oils distilled from half ripe fruit, compounds of low carbon con- tent are found which are absent from the oil of the ripe fruit, and which seem to disappear in the (bourse of the ripening. From this it appears that the bodies of low carbon content are first formed in the fruit, and are then used for the building up of the compounds of higher carbon content. The yield of oil varies ^ with the fruit of Heraelmin sphondvliuin L. from 0.3 ^—8 p. c.-' The oil is a j-ellowish, acid reacting liquid, of a penetrating and persistent odor and a sliar]> taste. Sp. gr. 0.80 to 0.8H. The rotatory power observed on two oils was -|-0°1.")' and -f ()°16'; saponification number 2(50 — 2i)0. Composition. An oil investigated by Zincke^ in 1860 boiled from 100 — 270° and consisted principally of acetic and capronic acid esters of nornml octyl alcohol. The free octyl alcohol also shown to be present is probably not a normal constituent of the oil, but a, decompo.sition produc-t of the ester, formed during the steam distillation of the ijil. Two oils distilled by Moslinger* in 187(5 were somewhat more comjilex in composition. They boiled from 110 — 291° and cojitained the following constituents: 1) Ethyl butyrate ; 2) an hexyl compound, probably liexyl acetate; 3) esters of octyl alccjhol, principally the acetate, caprinate and laurinate and possibly also esters of the acids between capronic and laurinic acids ; 1) methyl and ethyl nlcohol, as well as ammonia, were found in the distillation water. 332. Oil from the Fruit of Heracleum Giganteutn. The oil investigated by Franchimont and Zincke-" in 1S72 hail been distilled from a foreign heracleum species, most proba lily from iJ. gig/i/i- tcuiii L. its principal constituents were hexyl butyrate and octyl acetate. By tlie distillation of tlie not fully ripe fruit of H. icifx;)7itejirii L., Gntzeit'J in 187."') obtained ().."i(; p. e., from the ripe and partly dried fruit, however, 2 p. c of oil. U]ion fT-action;)! distillati(in it lioiled from 1 .-SO— 2.')0°. Fraction i;iO— 170° contained etiivl butvrate. 1) The )tve:U: variation in the yiekl iititained liy ilifferent in vestiRn tors is not fio innch line to differences in the oil i-onti'nt o( tiie fr\ut Jis t o differenees in the penen tase of w.ater. i. e., differences in the static of dryini:;. 21 Liebiff'K .lunalen, l.^>2, p. 1. SI Rericht von S. & Co., Oct. 18S(1, p. 33. *) llericlite, 9, ]). i»i)8; LieliiK's .\nnaleii. Is.", ji, o(',. ■'"'I Liebig's Annalen, 163, p. Iil3. 0) Liebig-'s Annalen, 177, p. 344 Oils of the Umlielliferae. 583 Methyl and ethyl alcohol were found in the distillation water. The methyl alcohol was more prominent in the distillation of the ripe fruit, whereas with the unripe fruit the ethj'l alcohol was present in larger quantity. 333. Oil of Daucus Carota. Mohrenol. Tlie oU distilled from the fruit of the wild carrot, Dnucus airota L. is colorles.s to yellow and has a pleasant, carrot-like odor. Yield 0,8— 1.6 p. c; sp. gr. 0.870—0.928; au = — V^ to —37°. According to Landsbergi (1890) the principal (Constituent of the oil is a terjiene, CioHio, boiling at 159—161°, sp. gr. 0.8.52."j at 2(1°, '/D^+ (?) 32.3°. By direct bromination it yields a liquid dibromide, after heating to 280°, dipentene tetrabromide, melting at 123—12.5° results. It is therefore to be con.sidered as pinene. IJpoTi fractionation of the parts boiling above 200°, the splitting off of water and acetic acid was noticed. The chemical nature of the compounds giving rise to this phenomenon has not been determined. Carrot root gives only 0.0114 p. c. of a r-olorless oil by distillation. Sp. gr. 0.8863 at 11.2° ( Wackenroder.s 1831). 334. Oil of Osmorrhiza Longistylis. The root of the umbelliferous plant Osworrhiza longistylis Eaflnesque, known in North America as sweet cicelj^, sweet root or sweet anise, smells distinctly of anise and fennel (Green, ^ 1882). Induced by this, Eberlitirdt* in 1887 subjected the root to distillation and obtained 0.68 p. c. of oil having a sp. gr. of 1.0114- at 10°. It solidified at 10 — 12° and again bec;ime liquid at 1(5°. On distillation the oil began to boil at 189°; the thermometer then rose rapiilly to 225°, the main portioii going over from 22.5 — 280°, while oidy a small part went over from 230 — 280°. The fraction 226—227° consi.sted, as its properties show, of anethol. By oxidation anisic acid melting at 184° was obtained. Tlie fraction boiling about 250° gave with bromine a bromide cry.stallizing in rliombic plates, melting at 139°. The nature of the compound forming the basis of this bromide whs not determined. 11 .\rtliiv (1. I'harin., 21.'8. p. HZi. sj Am. .loiirn. Phariii., .54, p. S9.5. -) .\Iafjaz. d. Phurm., 3-^, p. 14-.5. *; Phanii. Rundschau. .5, p. 149. 584 Special Fart. 335. Oil of Monotropa Hypopitys. The volatile oil of Monotropa hypopitys L. (Family Pivolaceae), often found parasitic on roots in forests, was first prepared in 1857 by Winekler.i From the plant almost in full bloom, Winekler distilled an oil which was identical with wintei-g-reen oil from Gaultherhi procuwhens. More recently (1894j Bourquelot^ again showed the identity of this oil with that of wintergreen. From his investigation it follows, that the oil does not exist in the plant as such, but is present as a glucoside, which is probably identical with the gaultlierin isolated by Schneegans and Gerocks from the bark of Betula lent a. This glucoside splits up under the influence of a ferment contained in the plant, or by dilute sulphuric ,'icid. into methyl salicylate and glucose. Neither the emulsin of almonds, nor the iliastase of malt, nor the ferment of saliva are capable of splitting up the gaultherin. 336. Oil of Labrador Tea. Oleum Ledi Palustris. — Porseliol. — Essence ile LeJoii. All parts of Lpclum palustre L. (Family Ericaceae] yield on distil- lation ().;-! — 2 p. c. of volatile oil, which is usually so rich in stearoptene that it solidities at ordinary temperature. Sometimes, however, no crystalline separation can be effected, even by placing separate fractions into a freezing mixture.* The reason for this fluctuation in yield, as well as in comjiosition, of the oil, lies according to Trapp in the different stages of development of the plant parts subjected to distillation. If a large yield and an oil rich in stearoptene is desired, the twigs must be distilled before, during, or immediately after blossoming. Hjelt on tlie other hand could notice no decided influence of the season or growtli on the amount of volatile oil. Properties. r)il of Labrador tea is a greenish or reddish viscid liquid of n penetrating narcotic odor arid sharp, unpleasant, persistent taste. S]). gr. O.OH— 0.96. The portions of the oil not consisting of leduaa camphor boil between 180 — 2.'iO^. Composition. The oil first prepared by Rauchfuss^ in 179G has 1) .Xenes .laliii). d. Pharm.. 7, p. 107; Murteljalirssrliritt I', prnkt. I'hanii., G, ]i, .""171; Jalire.Mb. f. Cheinie, isr)7, p. niiO. -) .lonrii. lie Pharm. ct Chiiii., V. ao, p. +ar> ; and \\. ?,, p. 577: Cnnipt. rend.', 119, p. 802: and ll.>2, p 1IHI2. 3) .\i-chiv d. Pharm.. 232, p. +:17. -I) Bericht von S. & f'o., Opt. 1HS7, |i, ">,■">. •^) ^rroniniKdort'f s .lonrn. d. Ptuirm., 3, p. 189. Oils of the Ericacene. 585 since been inveHtigated by numerous rheniists.' The chemical nature of ledum camphoi-, however, has only lately been cleared u]5 by Rizza^ and H.ielt.8 Ledum camphor crystallizes from alcohol in fine long- needles melting at lOJ— 105°. It boils at 282—283° and is slightly dextrogyrate in alcoholic solution, [a]j = + 7.98°. Ledum camphor is a sesquiterpene hydrate CisHaeO, the liydroxy group of which is so labile, that its alcoholic nature cannot be directly proven. By treatment with lienzoyl chloride or sulphuric acid ledene, G15H24, i-esults with splitting off of water. Ledene is a sesquiterpene lioiling at '2">°. Oxidation with nitric acid produces oxalic acid. Potassium permanganate does not act upon it. which indicates tliat ledum camphor is a tertiary alcoliol. According to experiments by Sundvik. ledum camphor is a poison, acting strongly on the central nervous system. 337. Oil of Wintergreen. Oleum Gmiltlieriae. — Wiiitergriiniil. — Es-seiice de (raiiltheria, Origix .4ND History. Wintergreen. Gnultherin pvocuwlwns L. (P^'amily Eric ice/ie) grows from the New England States to Minnesota and south as far as Georgia and Alabama. On account of the peculiar pleasant odor and taste which develops when the plant is chewed, it was early used by the natives. The distillation of tlie oil was probably begun in the first decades of this century along with that of sassafras bark (p. 39.5) and birch bark (p. 331) in the states of Pennsylvania, New Jersey and New York. At first these aromatics were used for chewing, later for the preparation of refi'eshing beverages and home remedies, and especially for the much used, supposed l)lood purifiers- A\'hen the preparation of the volatile oils was successful, these were C)ften used instead of the aqueous extraction of the drug. This use is of con- siderable importance to the historj' of the introduction of wintergreen and sassafras oils, as both of the.se were u.sed as popular remedies in the United States since the beginning of this century under the title of patent medicines. -The preparation and use of these remedies soon 1) MeisHner (1812), Berl. .Jahrb. d. I'liai-ni.. 18, II, p. 170. — Grassmann (ISai), Rep. f. d. Pharin., .88, p. 58. — Biichner (ISoti). ibid., p. .'7, and Neiies Rep. f. d. Pharm., ",, |i. 1. — Williel; (18.52). Wiener .Academ. Berichte. !i, p. 302. — Friihde (1861). .loiirn. f. prakt Chem., 82, p. 181. — Trapp (lSi;'.l), Zeitsihr. f. Chem., 5, p. 350; Bei-ichte, S (1875), p. 542; Pharm. Zeitsehr. f. Ru.ssl, 84 (18'.>5), pp. 561 and 661. — Ivanoy (1876). Pharm. Zeitsehr. f. Rus,sl.. 5, p. 577. — Hjeit & f'ollan (1S82), Bei-iehte, 15, p. 25eo. — Rizza (1883), Berichte, 16. p. 2311. 2) Zeitsehr. der rusa. phys-chem. Ges., 19, I. p. 310. Chem. Centralbl., 1887, p. 1257. 3) Beriehte. 28. p. 3087. 58(i Special Part. bei'ame general and with it came a greater demand for the oils. Winter- green oil was especially in demand for the preparation of one of the oldest popular remedies in tlie United States, namely Swaim's Panacea, introduced in 1815, which at that time had an enormous sale and in the etHcien(;y of which great confidence was placed. Wintergreen oil appears not to have been used at that time for other purposes. The first mention of it in literatui-e is found in a botanical work' by Bigelow, a pliysician of Boston, published in 1818. In it, gaultheriii, oil is mentioned as a stable article of the drug stores, and also that this oil occurs, besides in Gaultheria, also in Spiraea iilnittria. the r(3ot of Spirnea lobata, and especially in tlie bark of Betuhi leiita.- In ijharmaeopceias. the oil w;is first taken up in that of the United States of 1820. The medicinal use of the oil did not become general until after 1827, when the New York Medical Society made known its use in the preparation of the popular specific menticmed above. " Although the similarity of the volatile oil from Ganltheria procum- heim L. with that from the bark of Betula lenta. L. was known before 1818,1 the identity of their principal I'onstituent was shown scientifieally about the same time by Wm. Procter jr.* of Philadelphia in 184:2 and Cahours-'' in 1844:. From that time on the oil was no longer distilled exclusivel,y from wintergreen, but often frrjm this together with biri/h bark, or only from the latter. The oil came more and more into use as an aromatic for pharmaceutic and cosmetic preparations, for beverages and medicinal remedies," and thus became an important article of commerce. In rei-ent times, however, it was often adultei-ated with kero.sene and alcohol.'' Besides the investigations luentioTied nliove, the oil hns been more recently examined by Pettigrew'S in 1888, l)y Power and AVerl)ke" in 1) American Medical Botany, vcl. L\ p. 2S. 2) According: to the invertti^atiniis uf Bi.inr'inelut (Ci)ni]it. rend., ll'.t. ji. S02. and 122. p, 10O2), Schneeffans and Oeroclc (Archiv d. I'lmrni., 2:12, ji. 4-;c,t), methyl salicy- l;ite iH produced by the decomposition c)f the y:luc(iside gaultherin by the ferment betnla.'^e. 'I'his trlucoside seema to occur not only in wintergreen and sweet birch, but also in a number of other plants, e. r-., in the roots of various polyRala species, in those of Spiraea iiliii:iri;i, S. tilijiendiil:!, ,s'. s:ilicifol!:i. S. Inhntn, and tlie flowers of Azalea, in Mdnutropa h,v/jcipit,v!<. aTid many other jilants. .\s to CiiiUheria pracunibens, a part ot the oil seems to occur as such in the leaves, for by crushins them a slroni;- iehi!''.s .Vnnalen, Is, )i. CD; ,52, p. n27. 0) .\ew York Medical Recoi-d, 22, p. .".O." ; S(|uibb's Kphemeris, M, ]i, ',l.-,0. 7) Pharm. Ilnndschau, 7, p. 2.^11. «) ,\ni. .Journ. Pharm,, .'."i, p. .'is."; ;ind ."(>. p. 2(JC». '■M Pharm. Hnndsdian, 'i, p. ijo.s; 7, p. 2s:-i: s. p. ;-!S ; 10, p. 7. Oils of the Ericaceae. 587 5H8 Special Part. 18.S8— 18!.)2 and finally by Power and Klebei-i in 1805, who determined the nature ot the constituents other than methyl salicylate. Methyl salicylate is prepared on a large scale and brought into the market as artificial oil of wintergreen since 1886 by the firm of Sr-him- mel & Co. It is official in the V. S. Pharmacopoeia. Preparation. The preparation of oil of wintergreen has always been carried on in a primitive manner, the distillation being conducted by smaller farmers at the place of growth. This was first done in the New England states ^ and later in the mountain and forest districts of the states of New York, New Jersey, Pennsylvania, Mrginia, and Mary- land. Usually old copper whiskj^ stills of various sizes, mostly from 200 to 400 gals, capacity, serve as stills. ^ Hometimes the distilhition is done in boxes of oak wood about 8 ft. long, 4 ft. high, and 1—5 ft. broad, mostly, bow-ever, in larger alcohol barrels, helil together by strong ii'on hoops, the jjerforated bottom of which is placed as tightly as I'jos.sible into a suitable cast iron kettle, which is filled with water for distillation. On the upper part of the bari-el is placed a copper helm, which is connected with a condensing worm in a large wooden tub. In the distillation, wdiich is carried on for only a few months in the year, the still, barrel or box, is filled witli finely cliopped, well wetted plants. The charge is allowed to stand over night and firing Ijegun in the morning. The distillation is usually complete in eight hours. About 00 p. c. of the oil pass (.)ver during the first 2 — 8 hours, the renin ining 10 p. c. in the course of the next 8 — 1 hours. The crude oil is coloi-ed dark by the iron of the condenser. The small producers sell the crude oil obtained to wholesale druggists, who purify it liy rectification.^ Properties. Gaultheria oil is a colorless, yellow or reddisli liquid of a characteristic, strongly aromatic odor, which is distinctly different from that of the oil from Betnl;i lentn. The sp. gr. is 1.180—1.187, the l)oiling temperature lies lietween 218 and 221°. Gaultheria oil differs from the inactive betula oil in being slightly optically a.ctive, m.d = — 0° 25' to — 1° . It yields a perfectly clear solution witli 6 ]). of 70 ]). c. alcoliol at 20°. This pro]>erty, togethei- with tlie sp. gr. and the optical rotation, allows of the ready detection of most of the adulterants, especially the frequent one with petroleum. Mixtures with the otlierwise equal oil of Betula Ifiitn. or with artificial methyl salicylate, can only lie detected by the depression of the rotatory power below — 0°25', I) Pharni. RinulHCliau, l:i, p. 22,s, 3) Am. .Idiirn. rii.-iriii., ."1, p. 4:;,<.). -•) Proc. Amer. riiarm. A.ssoc. 2s, p.2ii!l; *) Am, .lourn. I'linrm., .->(',. p. 2114. :W. p. 184. Oils of the Erieacene. 58S> The details tor further te.sts have been desc-ribed under oil of birch bark, page 8;34:. Composition. The principal constituent of wintergreen oil, the- meth.vl salicylate, was recognized by Cahours and Proctor ' at the beginning of the forties. Quite contradictory views exi.sted as to the- nature of the other constituents. Power and Kleber^ in 189.5 cleared up the nature of the constituents other than methyl salicj'tate in wintergreen and also in birch bark (jil. In order to prevent any possible decomposition, these chemists did not employ the saponification method, whic-h had been used so far in the investigation of this oil, f(jr the- separating of the unknown compounds. They took advantage of thfr ])r(5perty of the methjd salicylate to form a, solid salt with potassa, potassium metlijd salicylate. The total amount of salicylic ester was- removed from the oil by shaking repeatedly with 7..") p. c. potassa, solution. Only 1.05 p. c. of the oil did not combine with the potassa and remained as a semi-solid mass at ordinary temperature. This consisted of the following compounds: 1) A paraftin, CnH2n+2, which on account of its melting point, 6.'5..'j°, must be considered as tricontane, (JsoHol-. 2) An aldehyde or ketone, which when separated in a pure form from its bisulphite comp(.iund, has an odor like oenanthie aldehyde, and on oxidation with potas.sium permanganate yields an acid, the silver salt> of whii-h corresponds to the formula 0iiH902Ag. 8) An alcohol, OsHioO, boiling between 160 and l(j.5°, which corresponds to the ketcjne or aldehyde mentioned. 4) An ester, C14H24O2, boiling at 2:50— 2:!-")° (l;-5."i°' at 2.") mm.). This on saponification splits up into the alcohol, CsHicO,. and the acid, CoHioOo, resulting by oxidation from the ketone. The- alcohol and also the ester possess the very penetrating charac-teristic odor, by which wintergreen oil is lume, [G. frugrtiiitisahna Wal- lich. G. fivigTaiis D(.)n, Arhntun lauriiolia Hamilton, '^ give upon distil- latic)!! 1.1.") p. c. of a volatile oil, which seems to be identical with that of wintergreen. De Vrij -^ in IH.")!) prepared the oil from plant* which lie found in the exhausted volcano Patoea on Java, and in 1871 ascertained that it consisted almost exclusively of methyl salic-ylate. 1) See p. .">8H. fo. f'oTiip. alsii Krenierw and .Jaiiie.^, IMiarin.. 2) Phfirnt. IIund8chaii, l;-i, p. '22H. l;evie\\-, Ifl, [). ll.).~. 3) Sa-\\-er. io. Tpon oxidation with chromic acid, carbon dioxide and salicylic acid resulted ; Ijy boiling with potassa there resulted, besides salicylic acid, a very small ann)unt of a second acid, which gave a beautiful dark blue coloration with ferric chlorirle. 341. Oil of Jasmine. The general method of obtaining the volatile oils by water or steam distillation is not applicable to a, large numlier of lilossoms, as at best only traces of the volatile oil are obtained l)y it. To these Ijelongs the jasmine blossom of Ja.smimim granditlorum L. (Family Oleaceae). In 1) Berichte, 12. p. '2i(\. i) Lieliig'e .\nnaleii, 1 s.",, ,,. 222. — Comp. = ) Phariii. .loarn.. Ill, 2, [i. 281. alao lUinefekl (183(5). .l.iiirn. f. prakt. Cliem.^ ;tl I'harrii. .loiirri., Til, 2. p. r>ty.',, 7, p. 57, ami li;, \k 111. Oils of the Oleaceae. 591 order to isolate the odorous principles of the jasmine blossoms, Verleyi shook the jasmine ])omade obtained by Eniieuni ge ;} froid with vaseline oil and exhaust*^d the oil from this by treatment with acetone. On evaporation of the acetone a reddish colored oil smelling intensively of jasmine remained behind. Its principal portion came over at 100 — 101° under 12 mm. pressure and had the composition C0H10O2. Upon oxidation the compound yielded benzaldehyde, benzoic acid and form- aldehyde. By boiling with oxalic acid solution, stj'rolene alcohol, C6H5.(.'2H3(0H)2, was formed. This led to the conclusion that the body was the methylene acetal of phenjd glycol C0H5 . CsHs". >CH2. Verlej^ called the compound jasnial and considered it as the odorous principle of the jasmine blossoms.- •Jasmal can be prepared synthetically by heating phenyl glycol with formaldehyde and sulphuric acid. It boils at 101° under 12 mm., at 218° under atmospheric pressure. Sp. gr. 1.1H84 at 0°. Hesse and MiillerS reached entirely different conclusions in their investigation of the oil, which had been prepai-ed in a manner similar to Verley's and purified by steam distillation. They obtained from each kilo of jasmine pomade 4 — 5 g. of oil having tlie following properties: sp. gr. 1.007—1.018; «d=+2°30' to -^^"SO'. The ester-content was 69.1 to 78 p. c, calculated as benzyl acetiite, and 90.3 to 9.5.4 p. c, calculated as linalyl a,cetate. According to Hesse and Midler jasmine oil contains large amounts of benzyl acetate, as well as linalool and its acetate. According to a quantitative determination made by a method worked out by them for this purpose they found the following approximate composition for jasmine oil : 65.0 p. c. Benzyl acetate. 7.5 " Linalyl acetate (including possibly' other alcohol esters). 6.0 " Benzyl alcohol. 5.5 " otlier odorous principles. 16.0 " Linalool (eventually also other constituents). Benzyl acetate, CeHsCHi-OCHsCO, boils at, 215—216° and has the sp. gr. 1.069.3 1) Compt. rend., 128, IJ. 314; Bull. Soc. fhim., Ill, 21, p. 220. 2) According to A'erlej the homoioffueH of jasmal, the ethylidene, isobutylidene and amylidene acetals of pheri.\'l glycol have a jasmine-like odor. 3) Berifhte, 32, pri. 5(ir,, 765. 592 Special Part. Benzyl al(;ohol, CoHsCHoOH, boil.s at 88° under 9 irim. pressure. For identification the phenyl urethane meltiTig at 77—79° is well suited. i The jasmal of Verley was not present in the oil investigated by Hesse and Miiller. As the phenyl glycol methylene acetal is stable toward alcoholic potassa, it ought to be' possible to detect its presence after the saponification of the oil. This, however, was not the case, nor did so much as a trace of styrolene alcohol result by boiling the oil with oxalic acid solution. On the ground of these observations Hesse and Miiller came to the conclusion that the volatile oil of jasmine blossoms contained no phenyl glyc-cjl methylene acetal. Schimmel & C0.2 in their investigation of jasmine oil in 189.1 also found benzyl acetate, benzyl alcohol and linalyl ac-etate, but no com- pound of the properties of jasmal. More recently, Hesse ^ has found three further r;onstituents : 2..") p. c. Indol, CsHtN. 0.5 p. ('. Anthranilic acid methyl ester, CsHfiNOa. /!.<) p. c. Jasmone, (JnHmO. Jasmone. ('iiHieO has an intensive, pleasant jasmine odor when diluted. It boils at 2.57— 2.^18° at 7.j5 mm. and has a sp. gr. of 0.945 at 15°. It yields an oxinie, by means of which it was separated from the oil, melting at 45°, and a mixture of semicarbazones melting at 200 — 204°, from whicli by reerystallization a compound was obtained melting at 204— 20(i°. 312. Oil of Rhodium. Olemri Ligiii Rhodii. — UoseiiliolzoL — Essence de Bois de Rose,* on de Rhodes. Tlie so-(.'alled rosewo(jd. i. e. the wood of the roots of the shrubs Conroh'uliiN .scopnvhin L. and C. iioridus L. (Y-A-mWy Convolvulaeeae), indigenous to the ('anary Islands, is generali.y reported as the material used for the preparation of oil of rhodium. Tlie (jil of rhodium at present in the market is often nothing more tha,n a mixture of i-ose oil with sandalwood or cedar w(_iod oil. Oil of rhodium was investigated by (Tladstone^ in 18(54. The soui-(/e of this oil c-in naturally not be be determined at present. It was viscid, had the sp, gr. ().90(> at 15.5° and the rotatory power 1) P.erifht von S, & Co., .\|ir. ISfCJ. p. 27. 2) Bericht von 8. I'i Co., Apr. IS'.tO. p. 27. 3) Berichte, 82, p. 2C,11. i) The wood dewKBatea Bo/,s- Je ro.se femelle or male by the French is (Jnayana linuhje wood. Conii>- 1>. 493. ■•) .Journ. Chem. Soc, 17, p. 1; .Tahresb. t. Cheniie, 1SIJ8, p. 546. Oils of the Verhenaceae. 593. — 16° ill a i.jf) mm. tube. Four fifths of it eouf^isted of a hydrocarbon CioHia (more probably Ci.->H24) boiling at 249°, which had an odor of sandalwood and rose. The source of an oil distilled by Schimmel & Co.i in 1887 is also unknown. The oil had a fine golden-yellow color, with a pleasant rose- like odor. It solidified at 4- 12° to a mass of needle shaped crystals. A rose wood from Teiierife- recently used by the same firni for distillation, corresponded fairly well with the description of the root wood of Convolvulus scoparhis L. The odor of the oil did not fulfill the expectations. Sp. gr. 0.951 at 15°; y.D^+l°MO'; saponification number before acetylizatiou =0, after acetylization = 151.8. The oil dissolved with a slight turbiditj' in 10 p. of 95 p. c. alcohol. 343. Oil of Verbena. The true verliena oil from the leaves of Verhenu ti'iphylln L. (Aloy.sin citriodoi-n Ort., Lippi;i citriorlor;i Kth., Family YerlieiinceHe) cultivated as an ornamental plant in Spain, northern France and Central America is, as its high price stands in no relation to its true value, no I'egular article of commerce. It can in most cases be repla.ced by the much cheaper lemcjn-grass oil which is similar in odor, and has thei-efore been called East Indian verbena, oil. As genuine verbena oil is so difficult to obtain the statements concei'uing it have to l)e taken with some reserve. Verbena oil has a. fine, very pleasant, lemon-like odor, resembling that of lemrjn-grass oil. An oil distilled in Grasse, according to the statement of the manufacturers, from the leaves of Lippia citriodorn (yield 0.09 p. c. ), had the following properties: Sp. gr. 0.900; ai)^ — 12° 88'; soluble in 1 — 5 volumes of 90 p. c. alcohol, on the further addition of alcohol it became turbid. It contained 35 p. c. of aldehyde, which, as was shown by the preparation of /J-citryl naplitho cinchoninic acid (m. p. 195 — 197°), was citral (Schimmel & Co.) An oil described as ''Oil of true Vervain, '"s the sp. gr. of which is given as 0.902 and anas — 12.7°, agrees very well with the above. It was not soluble in It) p. of 80 p. c. alcohol, but in equal parts of 90 p. c. alcohol, and contained 28 p. c. of aldehyde. After acetylization a decided odor of linalyl acetate was noticed. By saponification of the acetylized oil an alcohol content (CioHigO) of 30 p. c. was determined." 1) Berieht von S. & Co., Apr. 1887, p. 28. 3) Chemist and Drusgist, .50, p. 218. 2) Bericlit von S. & Co., Apr. 1899, p. 41. 38 594 ^ Special Part. IJmnej'i reports on an oil distilled in Dunolly (Victoria, Australia) "probably" from Lippin citriodora. The sp. gr. alter removing the iilcohol which had been addeil, was O.SOi. ,/.d = — 16°- It contained 74 p. c. of citral. An oil early investigated by Gladstones (1864) and said to have come from Aloysia citriodora was much lighter, its sp. gr. at 15.5° being 0.8«1 ; its angle of rotation in a 250 mm. tube was — G°. 34.4.. Oil of Lantana Camara. The volatile oil of Lantana camara L. (Family Verhenaceae), widely distributed as a weed in Java, has been distilled in the botanical garden at Buitenzorg. Its odor is not especially pleasant, has a sp. gr. of 0,<)52 and turns the ray of polarized light (_)°24' to the left in a 100 mm. tube.'' 345. Oil of Yitex Trifolia. The leaves of Vitex trifolia. L. ( FaTnil,y Verbenaceae) are used in India for bathing purposes and as a remedy against various diseases. They contain a volatile oil, which Avas prepared in the botanical garden at Buitenzorg.* Its odor is pleasantly aromatic, somewhat camphor-like. The latter property is due to eiueol, whic'h was shown to be present by the iodol- cineol reaction. 346. Oil of Rosemary. Oleum Rorismarini. — Rosmariniil. — Essence de Romarin. Origin and History. The rosemar.y bush, Rosmarinus officinalis L. belonging to the Labiatae, grows in the Mediterranean countries and islands from Greece to Spain. The first mention of the distillation of rosemary is found in the writings of Arnoldus Villanovus of the thirteenth century. He distilled, probably for medicinal purposes, turpentine oil and rosemary oil. An alcoholic distillate of botti or only of rosemary was in use tor centuries as the first popular perfume under the name of Hungarian water. The distillation of the oil is described more fully by Raimund Lullus, a disciple of Villanovus. 1) Pharm. .louni., 57, ]). 257. 2| .Jmirn. Chem. Soc, 17, p. 1; .lahresb. f. ('hem., 186.3, pp. 540 and 549. 3) Bericht von S. & Co., Oct. 1896, p. 77. i) Bericht von S. & Co., Oct. 1S94, p. 74. Oils of the Labintae. tM Oil of rosemary was a much used oil in the middle ages and is often mentioned in the writings of that period. It is described in the index of the Compendium of Saladin at the end of the fifteenth century and in the works of Brunschwig, Eyff, Gesner, Porta, and others, and is mentioned in drug and spice ordinances of the fifteenth centurj^. In several of the treatises on distillation and in medical works of the fourteenth and fifteenth centuries, an empyreumatic oil of rosemary is also mentioned. One of the first investigations of rosemary oil was made by the Parisian apothecary Geoffroyi in 1730. A century later it was more fully investigated by Saussure- and in 1837 by Kane.^ Cartheuser in 1734 determined the yield of oil.* The so-called rosemary camphor was first noticed by Kunkel of Berlin in ISOS^ and a century later (178.")) by Arezula of Cadix." Proust prepared it in 1800. ''' Pheparatiox.* In commerce, two rosemary oils are principally distinguished, the Italian and the French. The Italian or more correctly the Dalmatian rosemary oil is obtained on the islands of Li.ssa, Lesina and Solta on the Dalmatian coast, where the rosemary grows wild and covers large tracts of land. It is surprising that rosemary grows neither on the mainland nor on the neighboring islands Brazzo, Curzola, Melada and Lagosta. The most pleasant smelling rosemary is that on Solta, where it is, however, more and more suppres.sed hj vineyards, so that distillers come but seldom to this island for the preparation of the oil. Most of the oil is produced in Lesina, which is also the commercial center for rosemary oil, Lissa is second in importance. Both islands are covered with bushes about a mrter in height. The "Rosemary forests" are the property of the community, which gives the license for distillation to the highest bidder at auction. The use of the forests is regulated by law, so that a full harvest is made only once in three years ; in the two following years very little oil is distilled. The dis- tillation takes place in Julj' and August, consequently after the flowering period, which lasts from February to April. After the cut twigs have been 1) Mem. de I'.icatl. de sc. de Paris, 1721, p. 16.S. 2j Ann. de Chem. et de Phys., II, 13, p. 278. 3) Trans, of the Roy. Irish Acad., 18, p. 135. — .Journ. t. prakt. Chem., 15, p. 156. 4) Elementa Chymiae, II, pp. 83 & 106. 5) Probierstein. p. 397. 6) P. 39; Resultado de las e.'cperiencias, p. 8. ') Trommsdorff's .lourn. d, Pharm., 8, II, p. 221. 8) Dingler'e Polytechn. .lournal, 22H, p. 46fi.— Bericht von S. & Co., Oct. 1896, p. 69. 596 Special Fart. dried for eight days in the sun, the leaves are stripped off and distilled with water vapor. The distilling- apparatus is very primitive, old cojjper whisky stills being mostly employed.^ From the port Cittaveehia the oil is shipped in tin cans to Triest. From here, often adulterated with turpentine oil, it enters into the world's commerce. No statistics of the production of the Da.lmatiajj rosemary oil exist. According to inquiries made at the place of production, 20,000 k. of oil are said tcj be obtained in those years when a full harvest is made. This estimate agrees with a statement made by Fliickiger^ in 1884. As far as the yield of oil is concerned, it has probably been but seldom determined in Dalmatia, as it may be assumed that the distillers do not weigh the material before putting it into the still. tSchinnuel & Co. 3 obtained from Dalmatian rosemary leaves 1.4 — 1.7 p e. of oil. The French rosemary oil is finer in odor and correspondingly higher in price. It is principally obtained in the Dcpartements du Gard, du Herault. de la Drome, des Alpes ilaritimes and des Basses Alpes. Here the erect shrub grows to a height of 2 m. and together with Thymus vulgaiis forms the brushwood of clearings. 2 The distillation is done in itinerant stills in tlie same manner as described under lavender oil (p. 602). vSchimmel & Co.* obtained by distillation from the dry French rosemary leaves 2 p. c, from the flowers 1.4 p. c. of oil. Whether the better quality of the French oil depends on the plant itself or on the more careful selection of the material is difficult to state. Inasmuch as rosemary is also found in 1-^pain, the oil is now and then distilled in that country.^* It appears, however, to lie almost always adulterated with turpentine oil. The properties of the pure Spanish oil are the same as those of the Dalmatian or French oil. as was shown by the recent examination of a Spanish oil in the laboratory of Schimmel & Co. The English rosenmry oil, which is obtained in Mitchani and Market Deeping in small amounts from cultivated plants, is no more important commercially than is the Spanish oil." Pboperties. Rosemary oil is a colorless or slightly greenish-yellow liquiil of a penetrating camphor-like odor and an aromatic, bitter, 1) See p. 07. 2) Archiv d. Ph.'iim., 222. p. 476. 3) Archiv d. Pharin., 235, p. 586; Berlcht von S. & Co.. Oct. 1897, p. 54,. 4) Bericlit von S. & Co., Oct. 1893, table in appendix, p. 34. ■•) Berlcht von S. & Co.. Oct. 1889, p. 53. 0) Conip. Holmes, Ph.irm. .lourn., IH, 12, p. 238; III, 20, p. .581.— Sawei, (.1doro- Sraphia, vol. 1, p. .370. Oi/s of the Labiatae. 597 cooling taste. The sp. gv. of the French as well as the Italian oil is always higher than 0.900 and sometimes rises to 0.920. The ray of polarized light is always rotated to the right, «d = +0^4.1' to +15°- The first 10 p. c. obtained by fractional distillation are likewise dextro- gyrate. One part of oil gives a clear solution with % and more parts of 90 p. (;. alcohol, and sometimes with 2, but often as many as 9—10 parts of 80 p. c. alcohol are required. Saponification number 12 — 20. The oils distilled by Schimmel & Co. from five different shipments of Dalmatian rosemary leaves had the following properties: Sp. gr. 0.904— 0.918; «D=+3°40'to +8°52'.i Two oils were distilled in Leipzig from French material.2 1) From flowers: sp. gr. 0.920: ()() m. 3) Bericlit vcjn S, & Co., Apr. ]K!)S, ji. 40. C;/.s of the L;ilii;it;ie. 601 .S a a 60a Special Part. The ai-eompaiiyiiig- illustration (fig. 78) shows such a Distillerip arnhulante^ in the neighborhood of the village Escragnolles, on the road from Grasse to Paris, thirty kilometers from Grasse. Tlie two copper stills are supported on a Are place made of stones laid in the form of a horse shoe. The condenser consists of an old petroleum barrel, from which the head has been removed, and into which the con- densing worm is fitted. The condensing water is furnished by the neighboring spring. In the foreground a laborer is busy turning the pile of lavender flowers with a hay fork, to prevent fermentation. The exhausted blossoms are spread out behind the still. After completion of the distillation the laliorer removes the still from the fire, empties it by turning it over, and replaces it by another which had meanwhile been filled. H. Laval- in 18S() made an interesting and exhaustive report on the distribution, collection and distillation of lavender in the Departement de Vaucluse. Although not of very i-ecent date, some of his figures may here be mentioned, in order to give an idea of the importance of this industry in southern France. On the southern slope of the Ventoux mountains lavender is found at a height of 700— l.l.'iO m., together with thyme and satureja. On the northern slope the lavender begins at 450 m., but rises here no higher than 900 m. The ground covered by the plants (lavandif're.s) on the Ventoux is approximately 11,000 hectares (27,000 acres); of these, 7,000 hectares (17,200 acres) are property of the communities, the remainder is of private ownership. At the time of flowering, in July and August, the men, women and children go up the mountains. The flower clusters are cut off above the leaves with a sickle and are carried on the head in bundles to the places of distillation. The collection of the lavender is commonly free on the properties of the commuTiities, some, however, make an annual charge of one franc for each family. The amount of fresh lavender flowers collected annually in the Ventoux is estimated at 1,700,000 k. Of tliese 1,200,000 k. are used for the dis- tillation of the oil (about (i.OOO k.) the lialance is dried. Laval describes from personal inspection three different methods of distillation. In a small factory at Sault the distinati(ni was effected by means of .sterini which was generated in a separate vessel and feil four cylindricaL cojiper stills. Kn.ch Imil n, capacity for l."i() k. of fresh ^ ) Sep ini. 2(> and (w . -"I .Tnurii. lie rii.'irni. ct ili- I'hini.. V, in, i)]i. .-,0:3 anil lii'.). Oils of the Lahmtae. 603 flowers. The warm water from the condenser was used for feeding the boiler. A distillation lasted 1% hours. Each still was filled 14 times in 24 hours and thus 8,400 k. of material were distilled daily. In a second factory in Villes the distillation was also with steam from two egg- shaped stills, each of which held a charge of 100 k. of fi-esh flowers. A third factory in Bedoin had cylindrical stills, :i m. high and 1% m. in diameter, which were heated by direct Are ; the flowers were supported on a false bottom, so that they wei'e not in contact with the water but only with the steam. 75 k. were placed on the lowest false bottom, then a second false bottom was put in which carried the same amount of flowers. Alternately a false bottom and flowers followed until the still contained 250 k. Five distillations w'ere made daily. In the third kind of distillation the flowers are put into the still with water and without sieve bottoms. This method is common to the itinerant stills, and is the one most generally used. The most rational method of preparation is probably the one with the false bottoms, as this is the most suitable for delicate oils. By the distillation with steam as well as with the water without false bottom no doubt more of the valuable ester is decomposed than in the method used at Bedoin. According to Laval in order to obtain 1 k. of oil, 200 k. of fresh flowers are necessarj', which corresponds to a yield of ().5 p. c. From dried French flowers Schimmel & Co. obtained 1.2 p. c, from German flowers as much as 2.8 p. c. of oil.i The English lavender oil industry is quite insignificant in com- parison with the French. Whereas in France only the wild plant is used for distillation in England the cultivated plant is u.sed exclusively. The lavender plantations ^ are found in Surrey county in Mitcham, Carshalton and Beddington, further in Canterbury (Kent), Hitchin (Hertfordshire) and in Market Deeping (Lincolnshire). The distillation, which usually begins in the first weeks of August, is done in the same stills used for the peppermint. The yield from the fresh flowers is given as 0.8 to 1.5 p. c. Both figures appear to be rather high. 1) Bericht vdii S. & Co., Oct. 1SH3. Table in the appenflix. p. 24. 2) More detailed aeconnts of the fultivatiou and distillation of English lavender can be found in the following journals and \V(»rks: Holmes, Pharin. .Journ.. Ill, S (1877), p. .301: Fliickiffer and Hanbury, Pharniacoj^raphia, p. 4-77: Sawer, Pharm. .Journ., Ill, 20 (1890), p. G.59. and Odorograjihia, vol. I, p. .356; Chemist and Druggist, .39 (1891), p. .398; Pharm. .Journ., 58 (1897), p. 52; Brit, and Colon. Druggist, 3-1 (1898), p. .338. G04 Special Fart. Properties. Fi-pnch oil of lavender is ;i yellowisti or yellowisli- g-reen i liquid of the pleasant, characteristic odor of the lavender flowers, and of a strong- aromatic, slightly bitter taste. Sp. gr. 0.88")— 0.895 ; «D = — -5 to — !)°. It is soluble to a clear solution in three and more parts of 70 p. c. alcohol. The linalyl acetate content is as a, rule 3()_40, seldom 45 p. i\ According to tlie ainount of e.ster the lavender oils can be divided into two clas.ses. First, those oils with 8(5 and more p. c. of ester. They come from the highest regions of the southern French Alps, possess the finest and mo.st intense aronm, ami ccm- sequently bring the highest prices. Hecond, those with 80 — 36 p. c. of ester. Oils with le.ss than 80 ]i. c. of linalyl ai/etate are mostly adulterated, much more seldom is the low ester content due tc) im- pf)-fect distillation b\' which a part of the estei' was decompo.sed. The English lavender oil differs from the French tiy a camphor- or cineol-like odor which accompanies it, as well as by its low ester I'on- tent. 8p. gr. 0.885 to 0. 900; «.d = — 1 to — 10°. The solubility is the same as that of the French oil, the amount of linalyl acetate is only 5 to 10 p. c. Composition. According to the earlier works of Saussure^ (1817 — 1882), Proust and Dumas 3 (1888), the ordinary laurus camphor, (.'loHiet), had to l)e considered as a normal constituent of lavender oil. As recent investigations have shown that the oil from Lrivanduhi vera D. (J. contains no cainjihor, the.se statements refer no doubt to oils of other lavender species. ■* The results of Lallemand'"' (I860) and of Bruylants" (1879) in part do not agree with the most recent investigations. Lallemand found a laevogyrate hydrocarbon OioHio (?) boiling from 200 to 210°, and was the first to observe the presence of esters in lavcmler oil. Accordinn- 1) Tlic Hnest oils with a lii^h t-ster i-onteiit inosttv liave a kiwii tint, whereas rectified oils are colorless. To rectify lavender oil is irrational, because this process decomposes in part the princijial constit\ient. viz. the linalyl acetate. .-Vs a result tlie flavor of the rectified oil is Inferior (F.ericht von S. & Co., Oct. 1S'.14. p. :-10i. 2) Ann. Chim. et Pliys., II, 4, p. :;1S; II, 18, p. 273: II, 4;i, p. i.'2.-, ; I.iebig's Annalen. H. \\. 1(;8. 3) Liehip:'s ,\nnalen. C,, p. l'4s. *i In the literature (pnited above, Spain is several times mentioned as the country from which the exiunined oil was obtained. As Is shown in an article published by Charabot in ISP" i Bull. Soc. chim.. Ill, 17, p. H7S) the Spanish oil, of which the oriffin is not known, has different properties and is different in composition. Sp. gr. i) 012— (I.PIH; an = +i:i=2o' to +1(;°2.T; ester content H.1.5— 3.4 p. c. The oils"cont"ainert 44.5 to 'MX: p. c. of alcohols as determined by acetylization. In the his'ber boilins fractions borneol (ni. p. 2il4°l was found. The Spanish oil, therefore, resembles oil ol spike more closely than the oil of la\en) Liebiji's .\nnalen, 114, j>. IVtS. 15) .lonrn. de I'harni. et Chim.. IV, :',0. p. 1:!9. Oils of t}ie Lal)iatae. 605 to Bruylants the oil contains a terpene, L'loHia, boiling at 162°, which yields a solid nionohydrochloride. The principal part (45 p. c. | is said to be a mobile oil, the composition of which corresponds to a mixture of borneol. (JioHisO. and camphor, CioHieO. Ou cooling to — 2."° no solid constituents separated out ; on oxidation with potassium diclironiate and sulphuric acid, ordinary camphor was obtained. This would seem to show conclusively that Bruylants could not have had genuine lavender oil for examination. The most recent investigation of French lavender oil was made by Bertram ami Walbaum.i According to it, the princ-ipal constituent is 1-linalyl acetate, which is present to the extent of 'M) — 45 p. e. Besides linalyl acetate the ester of butyric acid and perha])s also those of propionic and valerianic acids are present in small amounts. The presence of formic acid could not be shown. Linalool is present in lavender oil not only as estei-. but also in the free state. After acetylization, (37 ]). c. of ester were found in an oil which originally contained only 84 p. c. As linalool cannot be quanti- tatively determined by acetylization, the results always being too low, it might be assumed that the ain(junt of linalool present in lavender oil is about as great in the free state as in the form of ester. While an oil distilled by Schimmel & Co. from the dried flowers con- tained no pinene, a small amount of pinene (nitrosochloride, m. p. 102°, nitrolbenzylaniine. m. p. 122 — 128°) was found in ■ the first runnings boiling at 160 — 170° of a larger quantity of French oil. Cineol is like- wise only present in traces. In one case it could only be detected after the linalool contained in the proper fraction had been destroyed by heating with fonnic acid.^ If larger amounts of piTiene can be separated from lavender oil, the suspicion of adulteration with turpentine is justified, especially when supported by the ester determination, the sp. gr., the optical rotation, and the solubility in 70 p. c. alcohol. On the other hand a larger cineol content in the French oil indicates adulteration with spike oil. The linalool is accompanied in lavender oil by a second alcohol CioHisO, geraniol. From the fraction boiling at 110—120° under 13 mm. pressure by treatment with calcium chloride, a.n oil could be separated, from which the diphenyl urethane of geraniol, melting at 82° could be obtained. ^ 1) Journ. f. prakt. Cheju., II, 45, p. .590. 2) Berieht von S. & Co.. Oct. 189.3, p. 2.5. 3) Berieht vou S. & Co., Apr. 1,S98, p. 32. 606 Special Pfirt. The English oil of lavender ha.s been investigated by Bemmler and Tiemann.i From the first runnings of this oil they obtained a tetra- bromide melting at 105°, and thus showed the presence of limonene. The traction boiling at 85—91° under 15 mm. pressure, consisted of 1-linalool, that boiling at 97—105° of 1-linalyl acetate. In the last boiling fractions a sesquiterpene, C15H24, was found but not examined. The English oil differs from the French in its larger content of cineol,^ as well as its low ester content, amounting to only 5—10 p. c. Examination and Valuation. The value of lavender oil depends on its content of linalyl acetate. Although the amount of ester alone is not an nbsolute standard for the quality of the oil, the fineness and value of the oil stands, however, in direct ratio to it, providing, of course, that the oil is a. normal distillate, free from any empyreumatic odor due to careless preparation. Such a case is, however, very unlikely to occur, as with an irrational distillation a part of the ester is destroyed. For this reason a carefully prepared oil must always show a comparatively high ester content. If the high linalyl acetate is partly decomxjosed during the distillation, the free acid acts detrimentally on the linalool and thus influences the odor also in this manner to an appreciable extent. By adulterations of any kind the ester content is of course also lowered. For these rea,sons the quantitative saponification is absolutely necessary in testing the value of an oil. The method has been described in detail on p. 198. In testing for foreign additions, the specific gravity, rotatory power and solubility in 70 p. c. alcohol must be considered. The more common adulterants ai-e tui'pentine oil, cedar wciod oil, and spike oil. Turpentine oil decreases the specific gravity and the solubility in 70 p. c. alcohol. The presence of pinene can also be readily shown (see under Composition). Spike oil does not influence the solubility, but decreases, as it contains but a small amount of linalyl acetate, the ester content. Besides, spike oil differs l)y its larger cineol content. There remains to be mentioned the adulteration of lavender oil with the ethyl ester of succinic acid, which, it is true, has been observed but once.3 It is, however, worthy of mention, as the addition of compara- tively small amounts of this succinic ester to lavender oil, produces a 1) Berichtf, i!5, p. 1186. 2) Bericlit von S. & Co., Oct, 1S94, p. 31. 3) Bericht von S. & Co., Apr. 1897, p. 2.5. Oils of thp Lahiatae. ' 607 high saponification number and thus tlie amount of linalyl acetate is apparently increased. 8 p. of ethyl succinate give the same saponifi- cation number as 18 p. of linalyl acetate. Apart from the large, apparent increase in the ester content, the ethyl succinate is a dangerous adulterant, because it has only a faint odor, which is almost completely covered by that of the lavender oil, and also because it influences but slightly the solubility and rotatory power. The specific gravity of the succinic estei" is, however, much higher than that of lavender oil and may thus indicate its presence. In testing the lavender oil for the esters of succinic, oxalic or similar acids which may here be employed, the property of the acids to forin difficultly soluble salts with barium is made use of. For this purpose about 2 g. of the oil are saponified, the portion insoluble in water separated by shaking with ether and the aqueous solution neutralized with dilute acetic acid. The solution is diluted to .50 cc. and 10 ec. of a cold saturated barium chloride solution added. It is then warmed for two hours on a waterbath and allowed to cool. If a crystalline deposit is formed, the oil is to be considered adulterated, as the acids contained in normal lavender oil, acetic and butyric acids, give soluble barium salts. 348. Oil of Spike. Oleum Spieae. — Spikol. — Essence d' Aspic. ORieiN. Lavandula spica D. C. (L. spica fi L., L. vulgaris ji Lam., L. lati folia Vill., Ger. Spiklavendel), has about the same distribution in the Mediterranean countries as the true lavender. It gTows, however, mostly in the lower mountainous regions, not exceeding 700 m., at an altitude where Lavandula vera T>. G. just begins. The oil is distilled exclusively in southern France in the same manner as lavender oil. 1(30 k. of flowers yield 1 k. or 0.62 p. c. of oil (Lavan). History. As was mentioned under lavender oil (p. (300) tlie dis- tillates of various species of lavender have since antiquity been desig- nated as spike oil. It was not until the end of the sixteenth century that lavendei- oil and spike oil were differentiated. In antiquitj^, probablj^ the Lavandula stoechas L. indigenous to the Mediterranean coast and distinguished by its aromatic, violet-red blossoms, was commonly used for the preparation of spike oil. The spike or stoechas oil mentioned in the writings of Dioscorides, Pliny, Scribonius Largus and other contemporaries was in all probability only aromatized fatty oil, like the ro.se and spikenard oil and other aromatic oils much used in antiquity. 1) .Touni. de Pharm. et <.'him., V. 18. p. .599. 60S ■ Si)eciiil Part. The distilled spike or spikenard oil was probably known in the fifteenth century. Besides cedar (turpentine) oil it is the only distilled oil mentioned by Bruuschwig in his "Destillirliuch" of 1500 as Oleum de Spkn from "Provinz" (Provence). Sakidin also mentioned spikenard oil at the end of the fifteenth century. Valei-ius Cordus mentioned in his Uispensatorium Noricum of 1543 only three distilled oils: turpentine oil, juniper oil and spike oil. Kyff de.scribed in his treatise on distillation published somewhat earlier, the distillation of "Spik und auderen ftirnernen Olen" and added the state- ment that, '-das Spiken- ocler Lavendelol gemeygklich aus der Provinz Fi'a.nkrei(_-h gebracht wird in kleinen g-ltisslin eingefasst und theuer ver- kaufft." In the sixteenth century the several species of laveudei' were cultivated in (lermany and in J^ngland. Gesner used the name spike oil only and described the distillation of tlie sjjike Ifiossonis, whereas Porta at the end of the sixteenth century described also the di.stillation of lavender blossoms and especiaHy emphasized the superiority of the oil from the French lavender. An interesting description of the preparation of the French spike or h=i vender oil is contained in the woi-ks of Deniachy of 177M. In medical works Oleum spiene has ):ieen mentioned as early as the thirteenth century. It was included in the first edition of the Dispensa- toriuni Noricum of 151;-!, and Oleum hivnnilulae is also mentioned together with spike and other essential oils in the 1589 edition. The Pharmacopoea Augustana of Occo, contains up to 1GI3 only Oleum sjiirfie, from that date on also Oleum hivanfluhie. Spike oil is mentioned in the oldest drug and price oi'dinances of German cities. Oleum hivandulne, however, is not found until 15S2 in the Frankfurt (U'dina.nce. The statements of l>emachy and other writers of his time agree with the assertions of later authors, that the s]iikc oil found in commerce in the eighteenth century was probably tudy a distillate or mixture of tnr]ientine and lavender oils. The yield of oil from the distillation of spike and lavender blossoms appears to have been first mentioned by Lewes. i also by Cartheuser.^ The so-called "lavender camiihoi" was observed in 1785 b\' Arezula.,-'' and in 1800 by Pi-oust. The fii-st investigations of lavender oil were made liy 8aussure.+ i| The new Diopeiiautory, 1 T+ii. ;■! Ui'siiltadi. de his exiuTipiiciHM, etc. -1 Elenienta cliyiiiiar, vol. L', |i|i. i:i:i +) .\rmal. de f'hiiii. et Ph.vs., 4. p. HIS; and 149. l:t, p. 27:!; 4^», p. ir>il. Oils of the Labintae. 609 Properties. 8pike oil is a yellowish liquid, of a camphor-like odor, reminding at the same time of lavender and rosemary. The spediic gravity lies between 0.90.0 and 0.91.0. Spike oil is alwaj'^s dextrogyrate. As a rule tlie angle of rotation au is up to + 3°, ra.rely up to + 1°. It is clearly soluble in 2 — .3 and more parts of 70 p. c. alcohol. The saponification number is about 15, corresponding to 5 p. c. of linalyl acetate (boruyl or terpinyl acetate, resp.). CoiMPOSiTiON. The first constituent identified with certainty in spike oil is camphor (Kane,i 1838). This compound does not occur in genuine lavender oil, as was shown in the preiieding article, although the older authors claim to have found it. It is, therefore, highly probable that a, part of the earlier investigations were made on spike oil and not on lavender oil. Besides camphor, Bruylants^ (1879) also found borneol in spike oil. The oil was thoroughly investigated, partlj^ by Bouciiardats alone in 1893, partly in co-operation with Voiry* in 1888. By repeated fractionation a very insignificant amount (0.2 — 0.2.5 p. c.) of an oil boiling- about 160° was finally obtained, which yielded a solid hydro- chloride melting at 129°. On boiling with alcoholic potassium acetate this was decomposed for the gTeater part, and gave dextrogyrate camphene, solidifying in the cold. Whether or not d-pinene is present together with the d-caraphene, could not be definitely shown. Bouchardat believed that the portion of the solid hydrochloride which was not decomposed by boiling tor a short time with alcohohc potassium acetate, was pinene hydrochloride. The fraction boiling about 175°, about 10 p. c. of the oil, solidified in a freezing mixture, and consisted of cineol, CioHisO, of which the hydrochloride and dibromide, CioHi80Br2, were prepared. The portion going over at about 200° was a mixture of 1-linalool, d-camphor and d-borneol. The linalool (b. p. 198—199, «d = — 16°44:'), was converted into geranyl ar-etate by boiling with acetic acid anhydride. The camphor oxime prepared from the camphor had all the properties of the oxime obtained from ordinary camphor. The borneol, after it had been separated from the camphor by means of benzoic acid anhyd- ride, likewise turned the ray of polarized light to the right. Spike oil may also contain terpineol, for Bourchardat obtained dipentene dihydrochloride on conducting hydrochloric acid gas into the 1) .Journ.f. prakt. Chem., l.T, p. 16.3. 2) Chem. Centralbl., 1879, p. 616. Comp. also Lallemand (1860), Liebig's 3) Compt. rend., 117, pp. 58 and 1094. Annalen, 114, p. 198. i) Compt. rend., 106, p. 5.51. 39 610 Special Part. fraction having the boiling point of terpineol. Tlie formation of this hydrochloride cannot, however, be definitely traced to terpineol, as it might also have been formed from linalool or geraniol. The geraniol also has not been positively identified. Hydrochloric acid yielded with the fraction boiling at 145—160° in a vacuum and smelling like geraniol, a liquid hydrochloride of the properties of geranyl chloride. ^ The analysis of the portion of the oil going over at 250°, gave results agreeing with C15H24, which indicates a sesquiterpene. Examination. Turpentine oil, witli which spike oil is probabl.y most often adulterated, is recognized by the lowering of the specific gravity, the diminution in solubility, a.nd, when French turpentine is present in larger amount, by the inversion of the rotation to the left. If the amount of this oil is so small that only a decrease but no inversion of the angle of rotation takes place, while sp. gr. and solubility of the oil appear suspicious, the first -5—10 p. c. going over on fractional distillation should be tested in the polariscope. As with rosemary oil (p. 594) the lowest boiling portions of spike oil are alwaj^s dextrogyrate, while even a small addition of French turpentine oil produces laevorotation. Moreover, with genuine spike oil the amount of the terpenes boiling at about 160° is very small, so that the oil can also be declared adulterated (American turpentine oil, camphor iiil) when at this temperature larger amounts of dextrogyrate terpenes distill over. The a.ddition of rosemary oil is more difficult to recognize. Tliis is, however, much more rarely u.sed as adulterant, as the difference in price is not great. Sp. gr., rotation and boiling temperature of spike and rf)semary oils are about alike, only the solubility in 70 ]). c. alcohol is different. Mixtures of these two oils often dissolve in 2 — 8 parts of 70 p. c. alcohol to form a clear solution, but it becomes turbid on the further addition of 70 p. c. alcohol. Sehimmel & Co.- have shown that spike oil contained more than 30 p. c, ro.seniary oil only up to 15 p. c. of alcoholic ccmstituents which could be determined by acetylizatioii. Umney, 3 therefore, suggests fen- judging the ]iurity of tlie oil and for detecting the presence of rosemary oil, to acetylize the suspected oil, and to reject oils which show a content of less thnii 30 p. c. of alcohols a,s adulterated with 1) Aoeoriiiiiff to Tifinann (Berichte, 31, p. h;!2) Rx-ranyl chloride prepareil in thi.« way is a iiii.xture of different isomeric chlorides and not a definite clieinical vinit. 2) Bericht von S. & Co., Oct. 1894, p. 6.5. 3) CheuilHt and Diniggist, 52, p. 166. Oils of the Labiatae. 611 rosemary oil. It must here be remembered that the alcohohc con- stituents of spike oil consist for the greater part of linalool, and that this body cannot, as is well known, be quantitatively acetylized, as it is partly decomposed with the formation of terpenes. Inasmuch a,s the acetylization result depends on the length of time the acetic acid anhj'dride reacts on the oil, the results obtained can be used for judging the purity of spike oil, only when the exact conditions under which the acetylization gives uniform results have been determined. Furthermore, the limits between whi(;h the apparent alcohol content thus determined varies with normal spike oil, ought to be ascertained by a series of experiments. 349. Oil of Lavandula Stoechas. LiiVcindula stoechas L. is known in Spain as Romero sunto (holy rosemary) (p. 607). Its volatile oil and also that of Lnvandnla dentnta L. is there obtained for domestic use, bj' hanging the fresh, flowering plants with the flower heads downward in bottles, which are sealed and exposed to the sun. On the bottom a mixture of water and volatile oil collects, which is used as a styptic for washing wounds, and also for eruptions. The odor of the oil does not in the least remind of lavender, but is rather more similar to rosemary, having the ca-mplior-like properties of the latter. The sp. gr. of a sample of oil was 0.942, It boiled from 180 — 24.5°; the lower boiling portions contained cineol.i 350. Oil of Lavandula Dentata. The oil of Lavandnhi dentata, L. is very similar to that of Lavandula stoechas L. Its odor reminds strongly of ro.semary oil and camphor. It has the sp. gr. 0.92(3, distills almost completely between 170 — 200° and contains cineol.i 351. Oil of Lavandula Pedunculata. An oil of Lavandula pedunculata (Jav. coming from Portugal, is described by Schimmel & Go.- as follows: "The oil has a difticultly definable, not pleasant odor, and is, therefore, useless for practical purposes. Sp. gr. 0.939; aD= — 44° 54'. It is soluble in an equal part of 80 p. c. alcohol. The high saponification number 111.7 corresponds to a content of 39 p. c. of an acetic acid ester of an alcohol doHisO. 1) Berlcht von S. & Co., Oct. 1889, p. 54. =) Ibidem, Oct. 1898, p. ?,?,. 612 Special Part- On distilling the saponified oil with steam a light yellow liquid came over. The first fraction contained cineol, as was shown by the cineol- iodole compound. The odor of this fraction suggests the presence of thujone, together with the cineol." 352. Oil of Catnep. The oil of Nepeta cataria L. indigenous to Noi'th America and used as a domestic remedy, has a not pleasant, mint- and camphor-like odor. Sp. gr. 1.041.1 353. Oil of Ground-ivy. From the dried herb of the ground-ivy, Neppta glerhoina Benth. (Glechoina hederacea L.), Schimmel & Co.^ obtained 0.3 p. c. of volatile oil. It had a difficultly definable, not pleasant odor, and was dark in color. Sp. gr. 0.92.5. 354. Oil of Sage. Oleinu Salviae.—Salbeiol. — Essence de Sauge. Origin .vnd History. The somewhat shrub-like sage, Salvia officinahs L., is indigenous to the northern countries of the Mediterranean, and is cultivated in manj' countries of moderate climate as a garden plant for medicinal purposes. Tlie plant will grow as far north as the northern part of Norway. Sage appears to have been used as a medicinal herb at the time of the Romans and was one of the plants recommended by Charlemagne for cultivation. In the "Destillirbuch" by Brunschwig of 1500 a distinction is made between large and small sage for the distillation of sage water The distilled oil of sage is first mentioned in the price ordinances of Worms of 1582 and of Frankfurt of 1587 and is included in the 1589 edition of the Dispensatorium Norieum. The distillation of the oil has been described hj Begnini in 1688, and the yield of oil from the leaves was determined by Wedel in 1715 and Cartheuser about 1782.3 In 1720 Geoffroy observed a stearoptene which had crj'stallized from the oil and which he termed sage camphor.* The same substance was again observed by Arezula in 17H9 and described b,y him.f^ The first 1) Berlcht voa S. & Co., Oct. 1891, p. 40. 2) Bericht von S. & Co., Apr. 1894, p. Zi^>. 3) Eleraeuta chyiiiiae, vol. 2, p. 87. 1) Mem. de I'Acad. roy. des sciences de Paris, 1721, p. 163. s) Re-iultado de las experiencias lieclia.s Bobi-e cl alcanfor de Miircia non liceucia. .Segovia, 1789, p. 8. Oils of the Labiatae. 613 examination of the leaves appears to have been made bv Ilisch^ in 1810; whereas the oil was investifjated by Herberger^ in 1829 and by Koehleders in 1841. Preparation. For the distillation of the oil the wild Dalmatian herb, which grows abundantly and is brought into the market in large compressed bales, alone seems to be used. The yield from Dalmatian leaves is 1.3 — 2.5 p. c. German leaves upon distillation yielded 1.4 p. c. of oil. Properties. Oil of sage is a yellowish or greenish-yellow liquid possessing the peculiar odor of the herb while at the same time re- minding somewhat of tansy and camphor, Sp. gr. 0.915 — 0.925 ; «d = + 10 to + 25°. The oil is soluble in two and more parts of 80 p. c. alcohol. Saponification number 107. Composition. The pre.sence of the following substances has been definitely determined: pinene, cineol, thujone and borneol, 1) Pinene, From the laevogyrate fraction boiling at 156 — 158°, Tilden,-' also Muir and Sugiura" obtained a nitrosochloride, Wallach converted the nitrosochloride into nitrosopinene'' (CuiHi.-.NO, m. p. 130°) and the original fraction into dipentene''' (tetrabromide, in. p. 124 — 125°) and thus established the identity of the hydrocarbon present with pinene. With regard to the optical rotation, the statements vary. Muir and Sugiura found the fraction at one time laevogyrate, at another dextro- gyrate ; Wallach found it optically inactive. The fraction, therefore, seems to consist of a mixture of the two optical isomers, in which at times the one, at times the other isomer predominates. 2) Cineol. Fraction 174 — 178° yielded no nitrosochloride. By means of the hydrobrom addition product, Wallach was able to isolate pure cineol. s 3) Thujone (tana,cetone, salviol, salvone), CioHieO. Fraction 198 — 203° was regarded by Muir and Sugiura as having the com- position CioHiaO, later CioHisO and was termed salviol. Semmler in 1) Tronimsdoi-ff'K .Journ. tier Pharm., 20, II, p. 7. 2) Buchner'.s Repert. f. d. Pharm., Hi, p. 1.31. 3) Liebif?'s Annalen, 44, p. 4. 1) Journ. Chem. ,Soc., 1877, I, p. 554; Abstr. .lahreeb. f. Chem., 1877, p. 427. 5) PhiloHoph. Masaz. and .Journ. of Science, V, 4, p. .336. — Pharm. .Journ., Ill, 8, pp. 191, 994; .Journ. Chem. Soc, 1877, II, p, .548; Abstr. .lahresb. f. Chem., 1877, p. 957. — Chem. News, 37, p. 211; .Jciurn. Chem, Soc, 38, p. 292; Ab.^tr. .Jahresb. f. Chem.. 1878, p. 980. — .Journ. Chem. .Soc, 37, p. 678; Chem. News, 41, p. 223; Abstr. .Jahresb. i. Chem., 1880, p. 1080. 6) IJebis's Annalen, 252, p. 10.3. 7) Liebis'H Annalen, 227, p. 289. 8) Liebig's Annalen, 252, p. 103. 614 Sppcial Part. 1892 declared salviol. whicli constituted 50 p. c. of the oil of sage, as identical with tanacetone.i Two years later, however, he expressed his doubt as to their identity.^ By a comparison of the physical properties of the compounds regenerated from their acid sulphite addition products, Schimmel & Co. 3 established the identity of the corresponding ketones from the oils of sage, thuja, tansy and wormwood. Wallach* also obtained identical derivatives from thujone, tanacetone, salvone and absinthol. For the properties and derivatives of thujone see p. 167. 4) Bi>rne(jl. Upon oxidation of oil of sage, R(.)chleder-'"' had obtained camphor which evidently had existed in the oil as such or had been derived from borneol by oxidation. Sugiura and Muir had observed that the higher boiling fractions of the oil separated crystals upon cooling, which resembled camphor but did not agree with it in all of its properties. In order to decide whether camphor is contained in the oil or not, Sehimmel & Co." fractionated an oil which they had distilled from Dalmatian herb, and submitted to a freezing mixture those fractions which ought to have contained the cainphor if present. No solid substance separated. Acetylization, however, indicated the presence of ;i.n alcohol (abt. IS p. c. calculated as CmHisO). A part of the fraction was, therefore, treated with benzoyl chloride. The benzoate was separated and saponified and a .substance corresponding with borneol in all of its properties resulted. After repeated crystallization it melted at 204°. In 10 p. c. alcoholic si^lution it deviated the ray of polarized light ()°2y' to the right. The borneol of oil of sage is, therefore, a mixture of the dextrogyrate and laevogyrate modifications. Camphor could not be found in the oil examined. This does not. however, exclude its presence in other tlum the Dalmatian oils. Acc(jrding to Muir, English oil of sage contains much cedrene, b. p. 260°, some terpene and only traces of oxygenated constituents (?). 355. Oil of Salvia Sclarea. This oil is distilled from the dry herb, or better from the fresh herb of the muscatel sage Salvia selaiva L, Its odor is pleasant, laveuder- like and, after evaporation of the more volatile portions, reminds of ambra. Sp. gr. 0.907-0.928; -/d = -19°22' to -24°1'; saponification number 144, corresponding to 50.4 p. c. of linalyl acetate. Judging 1) Berichte. 25, p. 3350. i) Liebig's Aiinalen, 286, p. 1)3. -■) Berifhtf, 27, p. 895. 5) r.Iebig'.s Amialeii, 44, p. 4. 3) Berifht von ,S. & Co.. Oct. 1894, p. 51. 6) Herioht von S. & Co.. Oct. 1S95, p. 40. Oils of the Lahiatae. 615 from the odor, this ester is a constituent of tlie oil,i but its presen(?.e lias not yet been chemically established. 356. Oil of Monarda Punctata. The American labiate, Monavrla punctata L., commonly known a-s horsemint. j^ields upon distillation about 3 p. c. of volatile oil which is yellowish-red or brownish in color and of a pungent thyme-like and minty odor. Bp. gr. 0.930— 0. 940; slightly dextrogyrate. Upcm prolonged standing thymol separates in large crystals or crusts. Composition. Thymol was discovered in the oil by Arppe- in 184(5. It is present in such quantity that the oil has served for its pre))aration on a large scale. -^ According to Schroter* (1888), the oil is reported to contain .")() p. c. of a laevogyrate h.ydrocarbon, b. p. 170 — 173°, 2.5 p. c. of a dextrogyrate (I), non-crystallizable thymol, and a .substance CioHisO (?), b. p. 240— 2."i0°. The.se statements, which do not inspire confidence, throw doubt both upon the results and the material. From material, identified lij' botanical authority, Schumann and Kremers" obtained an oil which contained as much as (31 p. c. of thymol when assayed according to the iodine method described under oil of thyme. The non-phenol portion of the oil contained cymene, (J10H14. identified Ijy the oxypropyl benzoic acid, m. p. l.'i.'j — 1.56°. Fraction 18(i — 202° contains oxygen and consists possibly of linalool. In addition to thymol, Hendricks and Kremers'' found a phenol fraction which would not solidify upon cooling and possibly contains carvacrol. They also found traces of d-limonene identified by means of its nitrol- benzylamine base melting at 94°. 357. Oil of Monarda Fistulosa. Wild bergamot or Monarda fistulosa L. yields according to Kremers upon distillation an oil similar to that of M. punctata.'' The sp. gr. of a number of oils distilled from the entire plant at different periods from June to September varied from 0.916 to 0.941. Optical rotation is .slightly to the left. The amount of phenol varies from 52 — 58 p. c. The phenol of this .species, however, is not thj^mol but carvacrol. This isomer was identified by means of diearvacrol (m. p. 147 — 148°), carva- 1) Bericht von .S. & Co., Apr. 188ii, i) Am. .Journ. Pharm., 60, p. 113. p. 44: Oct. 1894, p. 38. =) Pharm. Review, 14, p. 223. 2) Liebig'H Aniialen, oS, p. 41. 6) Pharm. Archivew, 2. p. 73. 3) Bericht von S. & Co., Oct. 188.0, 7) Pharm. Rundschau, 13, p. 207; p. 20. Pharm. Review, 14, p. 198. 616 Special Part. crol sulphonic acid (m, p. 58—59°), nitroso carvaerol (m. p. 153—154°) and dinitro carvaerol (m. p-. 117-119°). Other constituents are cymene, identified by means of oxypropyi benzoic acid (ni. p. 156°), and limo- nene, identified by means of its uitrolbenzyla.mine base (m. p. 93°). i Upon steam distillation of the phenol separated from its alkaline solution by acid, in one instance a red substance crystallized in the cooler. Purified by sublimation, it melted at 25(3—2(3(5° and behaved toward alkalies like alizarin. 358. Oil of Monarda Didyma. This oil is presumably similar in composition to that of the two previous oils. Concerning it FliickigerS makes the following statement: "In 1796 Brunn, apothecary in Giistrow, observed a crystalHne deposit (evidently thymol) in the oil from MonnriJ i didyma L., which it seems had been imported from America." 359. Oil of Balm. Oleum Mclissae. — Melisseiiiil. — Essence de Melisse. Orichn and History. The labiate, Melissa officinalis L. is indigenous to the northern Mediterranean countries from Spain to the Caucasus, and is cultivated as a garden plant and for medicinal purposes in Europe and North America. On account of its fragrance, balm was cultivated hj the Greeks, Eomans and Arabs, and during the middle ages in Italy, Germany and Scandinavia. During the period of distilled waters, from the fifteenth to the seventeenth centuries, balm water was a current article. Oil of balm appears to have (!ome into use about the middle of the sixteenth century. It is first mentioned in the ordinance of Frankfurt-on-the-Main for 1582 and in the Dispensatorium Noricum of 1589. Comparable to the distillate from rosemary of the sixteenth century which was the precursor of the Eau de Cologne of the eighteenth and nineteenth centuries, the fragrant distillate from balm, lemon peel and lavender of the seventeenth century developed later into a very popular perfume. It was first prepared by the Carmelite monks of Paris in 1611 and became famous as Eau de Carmelites (Ger. Karmelitergeist). Later the alcoholic distillate was made officinal as Spiritns Melissae coin- positus. The earlier investiga,tions of the oil were made by Schultz in 1739, by Hoffmann about the same time, and by Dehne in 1779. 1) Pharni. Archlree, 2. p. 76. 2) Arctiiv d. Pharm.. •212, p. 4S8. Oils of the Labiatae. 617 The balm oil of commerce is no pure distillate from the balm. It may be an oil of lemon distilled over balm (Oleum inelissne citratnm), or a citronella oil treated in the same way, or merely a fractionated citronella oil. The yield from the herb Melisf^a officinalis L. is so small that the price of the oil would have to be extremely high. An oil distilled from tlie dry herb by Schimmel & Co. was solid at ordinary temperature and contained citral^ as was shown by Doebner's reaction. Later the sauie firm subjected the fresh herb of two varieties of balm to distillation. 2 1) Fresh herb, just beginning to blossom. Yield 0.014 p. c. ; sp. gr. 0.924; ao = +0°30'. The oil had a very pleasant balm odor. 2) Fresh herb in full blossom. Yield 0.104 p. c. ; sp. gr. 0.894; optically inactive. The odor was less pleasant than that of the first oil and distinctly indicated the presence of citral and citronellal. The attempt to prove the presence of these two aldehydes by means of Doebner's reaction yielded no positive result. The resulting acids from both oils began to melt at about 208° and were completely liquified at 225°. Evidentlj' the mixture consisted of the citral com- pound (m. p. 197 — 200°) and the citronellal compound (m. p. 225°). 360. Oil of Pennyroyal. Oleum Hedeomae. — Pennyroyal- oder amerikanisclies Poleiiil. — Essence d'Hedeonia. Origin and History. The oil from the American labiate, Hedeoma pulegioides Persoon is so similar to the oil from the European Mentha pulegium L., that it is frequently substituted for the latter. Pennj'rcyal is found from the Atlantic states to the Rockies. For its distillation very simple apparatus are used and the operation is, therefore, con- ducted in various regions. The bulk of the oil is reporteil as being distilled in North Carolina (Harris 8) and in the southern and eastern sections of Ohio.* The primitive stills, like those used for the distil- lation of sassafras and wintergreen (pp. .397 and 588), consist of a barrel resting on a kettle used as boiler. The boiler is placed over a fire-place dug into the ground and provided with a chimney. The barrel is connected with a tube condenser resting in a trough through which 1) Bericht von S. & Co., Oct. 1894, p, 37. 2) Bericht von S. & Co., Oct. 18U5, p. nH. 3) Pharm. .rourn., Ill, 17, p. 672. i) Comp. Kremera, Proceed. Am. Pliarm. Ah.soc , .3.^, p. ",46.— .J. F. Patton, Proc. Penn. Pharm. Ahb., 1S!)0; anil Proc. Am. Pharm. Assoc, fii), p. 548. ■618 Special Part. cool water flows. The fresh herb is distilled, a ton yielding about 10—12 pounds of oil. The dry leaves i yield about 3 p. c, the dry stems and leaves only l.y p. c. oil. Properties. American pennyroyal oil is a light yellow liquid, of a characteristic minty and sweetish odor and an aromatic taste. Sp. gr. 0.92.')— {». 940; an = + 18 to +22°. It is soluble in two or more parts of 70 p. c. alcohol. By means of this property, adulterations with petroleum, turpentine oil and other essential oils can readily be detected. CoMPOsrnoN. The principal constituent of pennyroyal oil is pule- gone, the presence of which was established by Habhegger^ by meaiis of the hydrated pulegone oxime, CioHniNOH. H2O, m. p. 147°, and by the benzoyl ester of the latter melting at 141°. Kreraers-^ found in the oil heated with potassa two ketones, CioHisO. The one boiled at 168—171° and yielded an oxime melting at 41-43°; the other boiled at 20(j — 209° and yielded an oxime melting at -52°. The latter is possibly identical with menthone. Formic, acetic and isoheptoic acids were also found. 361. Oil of Hyssop. Oleum Hyssopi. — Isopiil.— Essence d'Hysope. Hyssop ciil was formerly used medicinally and is mentioned in the drug ordinances of Berlin for 1574 and of Frankfurt-on-the-Main for l.'jH2. It is distilled from the herb of Hyssopus officinHli.s L.* The yield from the ilry herb is about 0.3—0.9 p. c. The oil has a pleasantly aromatic odor reminding of male fern. Sp. gr. 0.92.") — 0.94; ao H 17 to —23°. It forms a dear solution with 2—4 parts of 80 p. c. alcohol, while with 70 p. c. alcohol even 10 parts will render only a turbid solution. 5 The saponification number of one oil was 1.4, after acetyli- zation 45. The oil begins ti) l:)oil at about 170°; but little jiasses over below 175°, the bulk distills between 200 and 218° and has a strong odor of thujone or thujyl alcohol. An examination by Stenhou.se" was restricted to the analysis of various fractions from which no conclusions as to the composition of i| Bericht von S. & Co., Oct. IS'Jii, p. .^3. 2) Proc. Wi.s. Phann. Assoc, lM',)a, p. 51; .\m. .Journ. Pharni., 65, p. 417. 3| Proc. .im. Phar. Absoc, .S.T, p. 54G ; Am. .Joui-n. Pharm., 59, p. 535 — Pharm Kundschau, 9, p. 130. ■1) Comp. also oil from Origanum vtilgare. 5) (^hoiDist anil Di-ugglHt, 50, p. 218. 8) Liebig's Annalen, 44, p. 310; .Journ. t. prakt. Chemie, 27. p. 255. Oils of the Lahhitae. 819 the oil could be drawn. Besides, the oil examined by Stenhouse appears to have been adulterated with turpentine oil. One of his fractions began to boil at 1G0°, whereas pure oil begins to boil at 170°. Several FreiK^h oils had properties that deviated materially from those of pure oils. The sp. gr. of one of these oils was 0.95 and the angle of rotation + (!) 45°. They had a strong odor of fenchone, thus leading to the supposition that they consisted principally of the first runnings of fennel oil. 362. Oil of Satnreja Hortensis. Origi.v and History. Siitureja horteu.sis L. (Ger. Bobnen- or Pfeffer- kniut) owes its odor and pungent taste to a volatile oil obtained by steam distillation. The yield from the fresh herb is about 0.1 p. c. The oil is enumerated in the Frankfurt ordinance of 1582 among the medicinal volatile oils. Properties. The oil possesses the strong aromatic odor of the plant and a sharp, biting taste. The sp. gr. of the oil distilled from the fresh herb lies between 0.900 and 0.925; '^d = + 0°1' (determined on a single oil); phenol content 88 — 42 p. c. The oil forms a clear .solution with 10 parts of 80 p. c. alcohol. i An oil examined by Jahns^ in 1882 and distilled from the dry herb had a sp. gr. 0,898 ; «d = — 0.62° ; phenol content 30 p. c. Composition. According to Jahns, this oil contains carvacrol, also traces of a second unknown phenol which gives a blue color reaction with iron salts. Of the hydrocarbon fractions, about one-third consists of cymene (b. p. 173^175°; cymene sulphonate of barium). The other two-thirds (b. p. 178 — 180°; sp. gr. 0.855; ao = — 0.2°) consist of a terpene or terpenes as shown by analysis. 363. Oil of Satureja Montana. The oil of .S'. rnoiituna, L. has much the same properties as that of S. hortensis. The two oils cannot be distinguished by their odor. Fresh, cultivated herbi yielded upon distillation 0.18 p. c. of oil. Sp. gr. 0.939; «d=— 2°35'; soluble to a clear solution in 4.5 parts of 70 p. c. alcohol, and in 1.5 parts of 80 p. c. alcohol; phenol content 65 p. c. 1) Berieht von S. & Co., Oct. 1897, p. 6.5. 21 Berichte, 15, p. 816. 620 Special Part An oil examined by Hallepi in 1882 liad been distilled from wild herb growing- on the Maritime Alps in the neighborhood of Grasse. Sp. gr. 0.93942 at 17°; «d = — 3°25'. He found :!5— 40 p. e. carvacrol and a small amount of phenol boiling above 235°. The hydrocarbons boiled between 172—17.'")° and 180—185° and appeared to be terpenes. 364. Oil from Satureja Thymbra. SHtuivja thymbra L. was dedicated to Priapos bj^ the ancient Greeks. In Hpain it is used conmionlj' as a spice and has the reputation of being a stimulant and disinfectant. These properties are said to be due to its volatile oil. 8ucli an oil was obtained from Spain by Bchimmel & Co.^ and examined by them. It had a sp. gr. 0.905. The oil remaining aiter the removal of the thymol (abt. 19 p. c. ) was fractionated. A fraction boiling abt. 1(50° contained pinene (introlbenzylamine base, m. p. 121°); fraction 175° contained cymene ; the following fraction contained traces of dipentene. The fraction above 200° yielded after sajionification borneol and acetic acid which are contained in the oil as bornyl acetate. In composition, the oil is therefore closely related to oil of thj-me. 365. Oil of Origanum Yulgare. Origanum vulgare L. is one of the spice plants of antiquity. The hyssop of I^uther's translation does not refer to a Hvs.iopii.s but to Origanum. The volatile oil was used during the latter part of the middle ages and is mentioned in the German ordinances of the sixteenth century. The yield from the dry herb is 0.15 — 0.4 p. c. The oil possesses a strong aromatic odor and a spicy, bitter taste ; * sp. gr. 0.870—0.910; aD==: — 34.4°.5 According to Kane" (1839) the oil contains a stearo])tene about which nothing is known. The bulk of the oil is reported by him to boil at 1G1°. Jahns''^ in 1880 found two phenols in an oil distilled from the fresh herb. One of these gave a, green coloration with ferric chloride, and is possibly identical with carvacrol; the other gave a violet color. The oil contained not more than about 0.1 p. c. of combined phenols. The French oils of commerce are mostly mixtures of a pennyroyal- like odor which pos.sibly contain not a trace of the genuine oil. 1) f'ompt. reiiil., il4, p. 1,'lz. 5) Airhiv d. Phnnii., 2H1, p. 277. 2) 0.7394 in evidently a printpr'.s error. , p. 1.j7. ■t) Bericht von S. & Co., Apr. IsOl. p. 4',i. Oils of the Lahiatae. 621 366. Oil of Sweet Marjoram. Oleiim Marjoranae. — Majoranol.— Essence de Marjolaiiie. Origix. The fresh, flowering herb of Origanum inajorana L. yields upon distillation 0.3 — 0.4 p. c. the dry herb 0.7 — 0.9 p. c. of oil. The oil of commerce is mostly obtained from Spain. Phoperties. Oil of sweet marjoram is a yellow or o-reenish-yellow liquid of a pleasant odor reminding of the herb and of cardamom. The taste is spicy but mild. Sp. gr. 0.89—0.91; ao= + r, to +18°. The saponifleation number of a single oil was 21.5. As a rule the oil produces a clear solution with 2 vol. of 80 p. c. alcohol. Composition. Oil of sweet niarjora.m has been repeatedly examined. The stearoptene described and analj'zed by Mulder ^ in 18;i9 possibly was terpin hydrate or pinol hydrate. According to Bruylants- (1879) the oil contains ~> p. c. of a dextro- gyrate hydrocarbon CioHie, and 85 p. c. of a dextrogyrate mixture of borneol and camphor. This statement has not been confirmed. Beilstein and Wiegand* in 1882 isolated a terpene boiling at 178°, sp. gr. 0.846 at 18.5°, which absorbed one molecule of hydrogen chloride, without yielding a crystalline compound. Fraction 200 — 220° was analyzed and regarded as a sesquiterpene hydrate, C15H24H0O. The low boiling point, however, renders this conclusion very improbable. According to a recent investigation by Biltz"* (1898), the oil con- tains 40 p. c. of terpenes, principally terpinene (nitrosite m. p. 155^156°); also d-terpineol which, however, could not be obtained crystalline. Fractions 215—218° (sp. gr. 0.930) had the composition CioHigO. Oxidized with permanganate it yielded trioxy hexahydro cymene C10H20O3 (m. p. 129—130°).-'' Further oxidation with cliromic and sulphuric acids yielded the keto lactone, CioHieOa (in. p. (j1°), obtained by Wallach from terpineol. Fraction 215 — 218° must, therefore, be pro- nounced as terpineol. The alcohol is present principally in the free state and only small portions are present in the form of ester. The nature of the substance that produces the peculiar marjoram odor is still unknown. 1) Liebig'fl Ajnalen. .31, p. 69. — .Tourn. f. prakt. Chem., 17, p. 103. 2) .Journ. de Pharm. et Chim., IV, .30, p. 138; Jahresb. f. Pharm., 1879; p. 160.— Chem. Centralbl., 1879, p. 616. 3) Berlchte, 1.5, p. 2854. *) Ueber das iltherische Gel yon Origanum wajorana. Inaug^iir.-Dissertat., Greifs- wald, 1898 ; Beriehte, 32. p. 995. 5) The substance obtained by AVallach in 1893 from inactive terpineol melted at 121—122° (Liebig's Annalen, 275, p. 152). 622 Specia.1 Part. 367. Oil of Cretian Origanum. Oleum Origani Cietici. — Spanisch Hopfenol. - Essence d'Hoiiblon d'Espagne. The carvacrol-containing oils of (several species of Orignnum growing in Mediterranean countries are known in the German market as Spanisch Hopfenol and Kretisch Dostenol. At present there are two varieties in the market whicli differ in properties and composition, the Triest oil and the Smyrna oil. The former is dark in color, has a high specific gravity and a corresponding high carvacrol content. The latter is lighter in color, ha.s a milder odor and a lesser carvacrol content in correspondence with its lower specific gravity. 1. Triest Origanum Oil. Origin. The oil enters the market from Triest. It is uncertain whether the oil is distilled at that place or in the Mediterranean islands which supply the herb. The oil corresponds in all its properties with that distilled in Germany from the drj^ herb of Origanum hivtum Lk. It is probable, therefore, that this is the species yielding the Triest oil. The yield from the dry herb is 2 — 3 p. c. Properties. The oil pos-sesses a strong, thyme-like odor and a pungent, persistent taste. Freshly distilled it is of a golden-yellow color, which upon exposure to air is changed to dark brown to greyish- black. The darkening begins at the surface and gradually proceeds downward. Sp. gr. 0.94 — ().'.)8. On account of the dark color, the angle of rotation in most instances cannot be observed. In a few instances, when observation was possible, the oil was found inactive or a slight laevorotation, less than 1°, was observed. With 8 p. of 70 p. c. alcohol the oil forms a i-len.r solution. The carvacrol content varies from 60 — SH p. c. Composition. The Triest oil was examined by Ja.hnsi in 1879. He showed the pre.sence of carvacrol which previously had been prepared artificially but had not been found in an oil. Properties and derivatives of carvacrol a,re described on p. 177. If the oil is treated with dilute soda solution and the solution of the phenylate shaken with ether, all of the carvacrol can be removed. If the alkaline s(.)lution whi(.'h no longer yields anything to the ether is acidulated, a small amount— about 0.2 p. c — of a second phenol is obtained which produces a violet color with ferric chloride. The non-phenol portions of the oil, after several rectifications over sodium, boiled principally between 172— 17(5° and consist principally 1) Archiv <1. Pharni., 215, p. 1. Oils of the Lahiatae. 623; of cymene as shown by the formation of cymene snlphonic add. The- fact that the fraction when shaken with sulphuric acid developed the- odor of sulphur dioxide and became strongly heated indicates that in addition to cymene other substances, presumably terpenes, are present.. 2. Smyrna Origanum Oil. Origin. The oil is distilled in Asia Minor i from Origanum smyrnaeum L. and enters the world's market from Smyrna. Properties. The oil is of a golden-yellow color and of a mild odor reminding somewhat of linaloe oil or linalool. Sp. gr. 0.915 — 0.945;. aD = — 3 to — 13°. It forms a clear solution with 3 parts of 70 p. c. alcohol and has a carvacrol content of from 25 — 60 p. c. Composition. According to Gildemeister 2 (1895) the Smyrna oil differs from the Triest oil principally as to the linalool which the former contains in appreciable amount. As a result it contains less phenol than the Triest oil. Besides much carvacrol (phenyl isocj^anate, m. p. 140°), but very little of the phenol which gives a violet reaction with ferric chloride is present. Fraction 155 — 163° (ud := — 3° 28') has a remarkably low sp. gr., viz., 0.826 at 15°, thus leading to the sup- position that so-called oleflnic terpenes may be present. Fraction 175° contains cymene (osypropyl benzoic acid, m. p. 156 — 158°; and isopropyl benzoic acid, m. p. 257 — 262°); fraction 198 — 199°,. having a sp. gr. of 0.870 and an = — 15° 56', possessed all of the properties of 1-linalool. The presence of this alcohol was proven by oxidizing it to citral and identifying this aldehyde by converting it into citryl-/5-naphtho cinchoninic acid, m. p. 198—199°. Examination. The solubihty of the oil in 70 p. e. alcohol should be tested, by means of which the addition of turpentine oil and other cheap oils can be detected. Of importance is the determination of the carvacrol content as described under oil of thyme. Oils rich in carvacrol command a higher price than those poor in plienol. 368. Oil of Thyme. Oleum Tliymi. — Tliyniiaiiol. — Essence de Thym. History. The labiate Thymus vulgaris L., which is indigenous to the countries bordering on the Mediterranean, is now cultivated in most countries with a- temperate climate. During the middle ages the 1) This is possibly the same oil which is prepared in Konia In Anatolia in primitiye apparatus and sold in small flasks in the streets of Constantinople as a remedy against rheumatism. Comp. Bericht von S. & Co., Apr. 1891, p. 44. 2) Archiv. d. Pharm., 28, p. 182. <52-t Special Part. distinction between T. vulgaris and T. serpylluiu does not appear to liave always been made. Thougli thyme has always been a rather unimportant remedy, it and the oil of thyme have been otBcinal since the sixteenth century in most medicinal treatises and in drug and, spice ordinances. The oil is enumerated in the Dispensatorium Noricum of 1.589. Thyme-camphor was first observed by Neumann in 1719, and by Cartheuser in 1754. It was examnied and named thymol by Lalle- mand in 1858.1 Obigin. Oil of thjnne is distilled principally from the fresh, flowering herb of Thymus vulgaris L. which grows abundantly in the wild state in the mountains of southern France. The small knotty and woody stems of the thyme are found in clearings and in the shadeless coast districts of the Riviera, also in the mountainous regions of the Maritime Alps up to an altitude of 1,000 m. It is not definitely known what plant yields the Spanish oil of thyme. Inasmuch as it resembles the Crefcian origanuTn oil in properties and composition, it is not improbable that it is derived from a species of origanum. The yield is known for the oil obtained from the cultivated herb from which the commercial oil, as a rule, is not obtained. Fresh Grerman herb yields 0.3—0.4 p. c., dry German herl) 1.7 p. c. of oil : fresh French thyme, cultivated in Germany, yielded 0.9 p. c, dry French herb 2.5—2.(5 p. c. of oil. Propeeties. Both French and German oil of thyme are of a dirty, dark reddish-brown color, of a pleasant, strong thyme odor and a biting, persistent taste. The sp. gr. of a pure (lil is always above 0.900, good French oils having a sp. gr. of 0.905—0.915. Schimmel & Co. observed the sp. gr. 0.909—0.935 on their own distillates. The optical rotation is faintly laevogyrate, but in most instances cannot be observed on account of the dark color of the oil. It is soluble in )<2 part of 90 p. c, and in 1—2 parts of 80 p. c. alcohol; of 70 p. c. alcohol 1.5—30 parts are mostly requisite to form a clear solution. The phenol content of normal oils varies, as a rule, between 20—25 p. c. and in rare instances rises to 42 p. c. The phenol of the French and German oOs is mostly thymol, sometimes, however, carvacrol or a mixture of both. Oil of thyme rectified in tlie ordinary manner readily resumes the dark color of the crude oil. In order to obtain a light j^ellow colored oil with full phenol content special precautions are necessary for its rectification. Many c-onsumers lay unnecessary stress on the lio-ht color 1) Journal de Pliarm. el, Chim., Ill, 24, p. 274; Compt. rend., H7, p. 408. Oils of the Labiatae. 625 of the oil. In southern France such a "white oil of thyme" is produced by distilling the crude oil with several times its volume of turpentine oil. Such an oil frequently contains less than five per cent, from 1—2 p. c, of thymol. This explains why rectified oil of thyme is frequently quoted for less than the crude oil. Spanish oil of thyme is quite different from the French and German. Its color is often dark green, sp. gr. 0.93 — 0.95 ; phenol content .50—70 p. c. (earvacrol but no thymol).. It is also more soluble than either the French or German oils, rendering a clear solution with 2—3 parts of 70 p. c. alcohol. These great differences render it very probable that the Spanish oil is obtained from a different plant. Composition. As the amount of cinnamic aldehyde determines the value of cassia oil, eugenol that of oil of cloves and linalyl acetate that of bergamot, so the amount of thymol (or earvacrol) is indicative of the value of oil of thyme. Although thymol was observed as early as 1719 and therefore belongs to those compounds from volatile oils longest known, its composition was first correctly determined by Lalle- mandi in 1853. By analysis he determined the formula C10H14O, which took the place of the formula CioHi,50,. found by Doveri^ a few years earlier. Occasionally thymol crystallizes from old oils in the cold ; it can be removed completely only by shaking with Ij^e. It melts at 50 — 51° and boils at 282°. Its properties and characteristic derivatives are mentioned on p. 178. Of other constituents Lallemand found cymene, CioHn, b. p. 175°; and thymene, CioHio, b. p. 160 — 165° and laevogyrate. Inasmuch as Schimmel & Co.^ have shown the identity of this hydrocarbon with 1-pinene, the name thymene shcmld be dropped. 1-Pinene occurs in the oil in such small quantities only, that its presence cannot be determined without the use of large quantities of oil. Labbe* in 1898 did not succeed in obtaining a solid hj^drochloride from fraction 155 — 158°. With amyl nitrite and hydrochloric acid he obtained a nitrosochloride melting at 106.5°. Inasmuch as the melting point of pinene nitrosochloride is given as 103°, he concludes that pinene is not contained in oil of thyme, whereas the preparation of the benzylamine base would have removed all doubt. In fraction 165 — 169° 1) Compt. rend., 37, p. 49S ; Liebig's Annalen, 101, p. 119; Ann. fie Chim. et Pliys., Ill, 49, p. 148; Lipblg's Annalen. 102, p. 119. 2) Ann. de Chim. et Phys., Ill, 20, p. 174; Liebig's Annalen, 64, p. 374. 3) Bericht von S. & Co., Oct. 1894, p. .57. *) Bull. Soc. chim.. Ill, 19, p. 1009. 40 626 Special Part. Labbe claims to have found menthene. He olitaiued a nitrosoehloride, ni. p. 113—113.5°, and upon oxidation witli permai)p'a,nate cymene. It is Icnown, liowever, tliat the melting- ])oints of the nitrosochlorides can- not l)e safely used for the identification. The supposed oxidation to oymene is also inconclusive, for cymene is already present in the oil and may have been contained in tlie fraction. Of the more difficultly volatile fractions, the one boiling- between 195—231)°! had a decided odor of borneol and linalool. Inasmuch as their boiling points lie so close, their se]iaration could not lie effected by fractional distillation, but was accomplished by oxidizing- the fraction with chromic acid and distilling the products of oxidation in a vacuum. A part of the distillate solidified and was proven to lie camphor by means of its oxinie melting- at 117 — 118°. The li(|uid portion yielded with sodium acid sulpliite a crystalline derivative from which citral could be regenerate, p. 277; Bericlite, l.T, p. 819. Oils of the Lahiat.ie. 629 a phenol which in alcoholic solution produces a violet color with ferric chloride. 1 The higher boiling fractions (200 — 250°) presumably" also contain sesquiterpenes. An oil examined by Gladstone^ in 1864, which had a sp. gr. of 0.884 and an = — 81.6°, consisted almost exclusively of a hydrocarbon resembling turpentine oil. The explanation is not ditficult, for specific gravity and angle of rotation indicate a very liberal adulteration with French oil of turpentine. 370. Oil of Thymus Capitatus. An oil, distilled from the fresh herb of Thymus capitatus Lk. in the province of Granada in southern Spain, was examined by Schimmel & Co. 3 Its odor was strongly thyme-like, reminding somewhat of origanum. In its composition it closely resembles the oil of Satureja thymhni. Sp. gr. 0.901 at 1.5°; thymol content is small, a-bout 6 p. c. A. liquid phenol is also present, the boiling point of which lies close to that of thymol (carvacrol?). Pinene, cymene, dipentene and bornyl acetate are also present. 371. Oil of Bugle Weed. The dried herb of the American bugle weed, Lycopus virginicus Michx. yields upon distillation 0.075 p. c. of an oil with a characteristic but difficultly definable odor. Sp. gr. 0.924 at 15°.* MENTHA OILS. History. The mints, which are indigenous to temperate climates and some of which are cultivated, yield several valuable and much used oils : viz. oil of peppermint, oil of spearmint, German and American, and oil of pennyroyal, European and American. The mints have the peculiarity of readily forming varieties by differences in cultivation, soil and climate conditions. The.se botanical variations have a rather decided influence on the volatile oils. The varieties of Mentha piperita L. also of M. arvensis D. C. var. piperascens Holmes yield peppermint oil, M. crispa yields the KrauseminzoJ of the Germans and M. viridis the American spearmint oil. Although several mints have been in u,se for culinary or medicinal purpo.ses since antiquity, no well defined distinction is made even in the 1) Archiv (1. Pharm., 212, p. 48.5. 2) Journ. Chem. Soc , 17, p. 1; .rahre.sb. f. Chem., 186.3, pp. 546 anil 549. 3 1 Bericht von S, & Co., Oct. 1889, p. 56. 1} Bericht von S. & Co., Oct. 1890, p. 49. 63(1 SpecUil Part. treatises on distillation of the fifteenth and sixteenth centuries during- whieh period they were extensivelj' used for the preparation of distilled waters. The oils enumerated in price ordinances and older medical treatises are also of uncertain orijrin. Thus the Berlin ordinance of 157-1: mentions Oleum nientlme, the Frankfurt ordinance of 1582 mentions Oleum menthtie. Oleum polemii and (Jleuiii'jnilegii. 372. Oil of Peppermint. Oleum Jleiithae Piperitae.—Pfeffeniiiiizol. — Essence de Menthe Poivree. Origin. As peppermint, Mentha piperita, are designatei.l a liroup of botanically unstable si^ecies, subspecies and varieties of mint that produce menthol or an oil possessing- the properties of peppermint oil. In Europe and North America several varieties are cultivated for the distillation of the oil. The Japanese peppermint is usually not regarded as belonging- to Mentha piperita. It is supposed to be derived from Mentha arvensi.s D. ('. var. Ynperancena Holmes. Okigin and Preparation. Whether or not peppermint was among the mints used during the middle ages can no longer be deternuned. In the oldest German ti-eatise cm distillation the "Liber de arte distillandi" of Brunschwig cjf the year 1500, the following- mints are mentioned as being used in the preparation of distilled waters : Mentha a(iuatica, M. rubra, M. balsamica. M. sarceiiica, and M. rri.sjia, but no distinguishing characteristics are given. Neither is it definitely known whether the kinds of mint used formerly agree with those now in use. As far as known, the only specimens of Mentha piperita whic-h are several hundred years old, are found in the herbarium of the British Museum in London. John Ray.i the English naturalist, had obtained them from the county of Hertfordshire of southern Entiland in 1(106 and described them as Mentha palu.stris. "peper mint.'' The well pre- served spei/iTuens correspoml in all essential characteristii-s with the peppermint which is to-day cultivated in Mitcham, county of Surrey, near London (Fliii-kigerS). The cultivation of peppermint in Mitcham seems to have begun about the middle of the eighteenth century and was of some importance toward the end of the century. Up to l.S()5, however, the distillation of peppermint oil was not conducted in Mit(-ham but in London (Lysons^). The English peppermint industry reached its height about 1850. From that time on American competition caused a decided set-back in 1) Historia plantarnm, vol. Ill, p. 2,S4. 3) Environs of London, 1800, p. 2.j4. 2) Pharniacofi-no^le, ;ir. 726. Oils of the Lahiatae. 631 the production.! On the continent, peppermint was evidently not cultivated earlier for purposes of distillation than in England. Accord- ing to the Leyden botanist David Gaubius, it was cultivated for this purpose near Utrecht in 1770. He also mentions the menthol, the cumphora europaea wenthcW j/iperitkli.s. Meanwhile Linnaeus bad named the plant Mentha piperita. About the same time peppermint was cultivated in Germany. Fol- lowing the example of the London Pharmacopoeia, in which peppermint Fig. 79. Distillation oF Peppermint Oil in Japan. was otficinal since 1721 as Mentha pnperiti.s sapore it was mentioned in medical and botanical treatises. The treatise bj' Knigge- seems to have made it better known in professional circles. In Japan, liowever, the cultivation of peppermint appears to anti- date that of any other country. It is reported to have begun before i| Chemist and DnigRist, Islll, p. 40.5. 2) De nientha piperiti'Je cfjiiimeiitatio. Dissertatio. Eriaagap. 17S0. 632 Specia,! P.'iH. the fUiristian era. Even menthol is supposed to have been known ahnost as long and to have been used medicinally. i The cultivated varieties used in Japan for the distillation of the oil can no longer be traced back to the species from which the,y have been derived. They differ from the varieties used in Europe and America and in their general characteristics are more closely related to the European Mentha arvensis L. and the American M. canacJpn.si.s yar. glabntta Benth., than to M. piperita. A Japanese outfit was described by E. Marx^ in 1890. The arrange- ment, however, is not the same everywhere. It consists of cast iron kettle.s with broad rims (A, I, H, tig. 79), of wooden casks {B) and coolers I 6'). As a, rule tliree apparatus are so arranged that they can be heated by a common fire. The kettles A, I, H are first filled with water. Tlie casks R with perforated bottoms are ])laced over the kettles, filled with dry herb and luted with rims of straw and soft clay. The condensers C are then placed in position and the fire started in F. The vapors saturated with volatile oil condense on the lower surface of the conden.sers (' and collect in the cups AT. From here the mixture of oil and water passes tlirough the bamboo tube L into the receiver 0. The separated water flows through P back into the kettles A, I, H and replaces in part tlie evaporated water. As soon as the water in C becomes hot it is removed by a bamboo syphon G. Sometimes the rims of the kettles are overheated so as to cause a charring of the straw rims. This imparts an empyreumatic odor to the oil which is frequently observable in the Japanese oil. Another description of the Japanese distillation of peppermint with illustrations is given by T. Asahiva-^ wliich, however, agrees in the main with the Hibove. The distillation of peppermint oil on a commercial scale had its origin in Wayne Co., New York, in 181G. It was here conducted on a small scale by individuals and later also in neighboring counties. In 18;J5 the ('ultivation of peppermint was begun in Michigan in St. Josephs Co. and was extended to Ohio and northern Indiana. * For a long time the distillation was conducted in copper stills with direct heat. In 184() sevei'iil of the larger planters and distillers intro- duced steam distillation with large wooden stills, expei'ience havino- shown that the conditions were favorable for this peppermint oil in- dustry. AVith the older stills but 15 lbs. of oil could mostly be obtained 'rom a charge. Steam distilLition from wooden stills allows of the distil- latif)n of 7.") to 100 lbs. of oil per charge without great increase of cost. 1) Pharinacognnsie, 1891, p. 72(>. 2) Miltheil. d. il. (iesell. filr Xai.ur- iinrl Volkerkunde Osta.siena, C, p. 355. 3 1 .TouiTi. d. Pharm. t. Elsass-Lothring-en, 23, p. 314. ■"-) Proc. Am. Pharni. Assoc, 34, p. 121. Oils of the Lahintae. 633 Wherever modern distilling apparatus ai-e not used, two or three vats. are used in connection with each boiler. The plants are paci^ed on a perforated bottom which is lowered by means o! chains to within a short distance of the true bottom. For purposes of discharging the false bottom merely has to be raised. The vat is filled by two men, one throwing in the dry mint while the other stamps it down. \ij admitting some steam from time to time, the herb is moistened somewhat and in better condition to be firmly packed. After the vat is closed steam is admitted from below until the herb is exhausted. The renewal of the peppermint plantation is accomplished in spring by means of roots and sprouts of the previous year's plants. The largest yield of oil is obtained from the plants cut in September. Formerly it was supposed that a larger yield of oil was obtained by distilling the fresh plant. Experience, however, has taught that it is better to let the herb drj' for a short period. ^ Formerly several labiates and composites growing with peppermint were distilled indiscriminately witli the latter and produced a pooi'er quality of oil.- The more, important of these plants were Eria-pj-on canadensis L., Erechthites hienu-ifolia, Raf., Hedeoma pulegioides L. and Ambrosia species (ragweed). Bj more careful cultivation and selection the.se have been largely removed. Aside from the early cultivation in Jn,pan, the first observations of the crystallization of menthol from the oil (peppermint camphor) were made about 1770 by Gaubius,^ by Glendenberg about 17S4,* and by Trommsdorff in 1795. ^ The first examinations of peppermint oil and menthol were made by Dumas" in lH:-{2, Blanchet & SelK in 18-i(5, by Walters in 1839 and by Oppenheim» in 1861 and 1864. Production axd Commerce. In the following list the countries are arranged with reference to the amount of oil produced. America. The principal places of production are in the states of New York, Michigan and Indiana. Whereas formerly the state of New York controlled the market, Michigan has superseded it during the last ten years and produces at present at least four to five times as much. On the other hand the oil from the former state and especially that from Wayne county with Lyons as the market, is still preferred qualitativel.y to the Michigan or "Western" oil. 1) Proc. Am. Pharm. Ah.soc, 34, ji. 3) Ailversariorum varii aTgrumenti liber 121; Amer. Druggifit, Sept. 1886, p. unus, p. 99. 161, and .June 1888: Proc. N. Y. State *) Creli's Chem. Ann., 178.^, II, p. 427. Pharm. As^soc., 1888: Phann. .Journ,, 5} TromniMdorff' s Journ. d. Pharm., .3,p. 120. Ill, 19, pp. H and 4. ">) .A.nnal. de Uhim. et Ph.y.i., 50, p. 232. 2) Proc. Am. Pharm. Assoc, 7, p. 7) LieMg's Annalen, 6, p. 293. 449.— Am. Joiirn. Pharm.. 42, p. 120: S) Ibidem, 32, p. 288. Archiv d. Pharm., 192. jj. 252. 9) Ihidem. 120, p. 3.50: 130, p. 176. 634 Special Part. Oils of the Liihiatne. 885 636 Special Fart. The largest yearlj' production of peppermint oil was reached in 1897 and was distributed as follows. Eastern Michigan 13,000 lbs. Western " 79,000 Northern " 2.5,000 Southern " .55,000 Indiana 32,000 Various localities 10,000 Total 214,000 lbs. Add to this: State of New York 37,000 lbs. Total 251,000 lbs. As the result of this enormous production an entirely unexpected drop in price has taken place, which must necessarily lead to restriction in the peppermint culture. The oldest and best known American trademarks are those of "H. G. Hotchkiss" under which only crude, natural oil is shipped, and "F. S. & Co.," under which rectified American peppermint oil is brought into the market since 1872. Both of these are found in the market exclusively in 1 and 5 lb. glass bottles. Large amounts of crude American oil come mto the market in tins or can.s. The largest purchasers of these are New York wholesale houses who have agents in the producing districts. Japan. The peppermint oil production originally had its seat in the vicinity of Yonezawa, but since a few years has also started in the province Bingo Bitchu — both on Hondo — and reeentty also on the northernmost island Hokkaido (Yezo). The largest production in Japan was probably reached in 1896 with more than 220,000 catties (1 catty = TiO.j g.). This enormous amount was distributed in the different localities as follows : Uzen with Yonezawa as principal place abt. 1,200 piculs Bin^ro " 800 " Bitchu " 150 " Bizen ■■ 50 Aki ■■ 5 " Yamato " 7 " Yauiashiro " 5 " Shinauo " 5 " Surus'a " 5 " Island of Shikokn " 5 Total abt. 2,232 ].)iculs. 1) 1 Piciil = 100 catties = 60.47'.) k., 1 cHtty = 60.5 g. Oils of tlip L.ibiatnp. 637 Here, likewise, the necessary result was a coi-respouding decrease in price and a, restriction in the peppermint cultivation. The production of peppermint oil decreased as a result in 1897 to about 1,40(1 piculs, in 189H to about 1,000 piculs. The principal commercial center for peppermint oil in Japan is Yokohama ; Kobe ranks next in importance. Hamburg has. on account of the splendid steamer connections, lie- come the principal market in Europe for Japan peppei-mint oil. London and Xew York are second and third in importance. The great importance of Hamburg for the entire peppermint commerce is seen fi'om the fol- lowing 'official statistics : Import Mk.i Averase value 18!Mj k. Mk. From the United States aud the Atlantic Ocean .. From Japan " Australia (Mainland).... " China " Great Britain " Spain France (Jtlier import by water 3-1, 190 30,470 ^40 7,060 loo 480.380 303,860 7,480 181,250 1,200 14 10 31 26 12 31,840 24,000 190 8,020 200 210 140 542,130 286,410 3,110 222 080 4,700 2.950 1.470 Total bv water Ii 72,060 974,170 14 64,600 1,062,850 England. The peppermint culture and oil distillation have their seat in Surrey, Hertfordshire and Lincolnshire, in the vicinity of the towns Mitcham, Waddon, West Croyden, Wallington, Carshalton and Market Deeping. The total area under peppermint cultivation in the Mitcham districts is estimated at 300 acres. About 50 acres are planted with the preferred, so-called white mint. The total production of the districts named is estimated at about 20,000 lbs.; statistics do not exist. Not entirely unimportant is the peppermint oil production in France, amounting to several thousand kilos. It has its seat exclusivelj' in the Departement des Alpes Maritimes. The French oil belongs to the better commercial varieties. Germany. In Germany the production of peppermint oil has con- siderably decreased during the last four decades ; in Thuringia it has stopped almost altogether. On the other hand the peppermint cultivation has been started on a large scale in the vicinity of Leipzig. A distillerj^ equipped with modern apparatus is in the midst of the fields and, by means of special purifying processes, a product of superior quality is 1) -Mark = 23.8 cts. 6;w Special Part. Oih of the Labiatae. be >, 640 Special Fart. obtained. The annual production has up to the present not exceeded 400 k. Italy and Russia produce peppermint oils to a similar extent, which are used almost exclusively for home consumption. In Italy the article is protected by a comparatively very high import duty. An estimation of the annual world production of peppermint oil under normal conditions, leads to the following result: North Auipvica abt. itO.UllO k. Japan " 7O,O0U " England " 9,000 " France •■ ;10I)0 " (iermany " 800 " Italy " 600 " Russia " 1,200 " Variou.s other countries " 400 " Total abt. 17-5,000 k. This quantity appears to considerably exceed the world demand. The principal varieties have so decreased in price, that only a re.striction in the production can gradually restore a normal state. Properties. As already mentioned, the peppermint oils produced in the various countries are not obtained from a single botanical species. This explains why the individual varieties of the oil show such a great diversity in properties and (/omposition. For all practical purpo.ses, the odor and taste give an indication of the ijuallty wf the oil. By these properties an experienced connoisseur is able to distinguish between the three principal commercial varieties, the English, American and Japanese. This is of importance on account of the great differences in price. It is to be regretted that the origin of an oil cannot always be definitely recognized by a physii-al examination, it is usually com- pletely impiossible when a mixture of different oils is under consideration. Peppermint oil is colorless, yellowish or greenish-yellow, of a pleasant, refreshing odor and a cooling persistent taste. It is fairly fluid, but thickens and darkens with age. 8pecific Gravity. The specific gravity of the different varieties does not vary greatly, but the differences .-ire, nevertheless, great enough, that sometimes a. conclusion as to the origin of the oil can be reached. The lightest oil is the dementholated Japanese oil with a density of 0.89.5—0.905. The sp. gr. of the English oil lies between 0.900 and 0.910, that of the American mostly between 0.910—0.020. AVith the German oil a sample as high as 0.930 was found. Oils of the Labiatae. 641 Rotation. To a certain extent the rotation of the different varieties is characteristic; it is least with the French (up to — 6°) and greatest with the Japanese (up to —42°) oil. Solubility. The solubility in alcohol of various strengths offers a good means of distinguishing American from English and Japanese oil. English peppermint oil dissolved to a clear solution in 3 — 5 vol. of 70 p. c. alcohol at 20°. With a further addition of alcohol the solution as a rule remains clear, although sometimes showing a slight opalescence, but with a pure oil never a separation of oil drops. The solubilitj^ of the Japanese (dementholated) oil in 70 p. c. alcohol is usually the same as that of the English, often, however, somewhat less. It must be remembered that in this case a normal distillate is not under consider- ation, but rather a by-product of the menthol manufacture, which varies according to the method employed for the preparation of the menthol. Of the American oils the cheap Western oil shows the same solubility as the English; the better oil from Wayne Co., N. Y., is not clearly soluble in 70 p. c. alcohol. Of 90 p. e. alcohol, y^ vol. is requisite for making a clear solution with the latter oil. If larger quantities of this same strength of alcohol are added, there appears sometimes, especially with unrectifled oils, a bluish opalescence, which is undesirable for purposes of liquor manufacture. According to Kennedy i this opalescence is due to a decomposition produced by the light. The air appears not to affect the oil detrimentally in this case, as a long continued passage of the air through the oil did not give rise to this phenomenon. Observations which were made during a distillation of Saxon pepper- mint oil, indicate that the oils are soluble in 70 p. c. alcohol when they have been distilled from the fresh, and insoluble when distilled from the dry, herb. This would explain the differences in solubility of the English and the American oil, inasmuch as it is known that the former is distilled from the fresh, the American (Wayne Co.) from the previously dried, herb. Whether or not other influences play a part, cannot at present be stated. iMenthol Separation in the Cold. The normal Japanese oil is so rich in menthol, that even at ordinary temperature it forms a crystalline mass saturated with oil. American oil solidifies completely in a freezing mixture, while the English as well as the Saxon oil very often shows crystalline separations only after standing for a long while in the freezing mixture. As the two last named oils command the highest 1) Proc. of the Texas State Pharm. Assoc, 1888, p. 37. 41 642 Special Part. price, it follows, that the amount of menthol which can be separated from an oil by coolino;, is not a criterion of the value of a pepper- mint oil. Color Reactions. Numerous color reactions have been suggested for the identification of peppermint oil, of which that produced by acids is the prettiest and most .striking. It .5 drops of American or English peppermint oil are mixed with 1 oc. of glacial acetic acid, a blue coloration will be noticed after several hours, which gradually increase.s in intensity and reaches its maximum in about 24 hours; the mixture with American oil then shows a deep dark blue with transmitted light, and a fine copper-colored fluorescence with reflected light. With the English oil thi-se phenomena are less intense, often only a liglit blue coloration with a faint reddish fluorescence appears. .Japanese oili does not show this reaction, the mixture remaining colorless. Slight warming hastens the appearance of the reaction. The color obtained in this manner is, however, not so pure a blue, but rather of a yiolet shade. Contact with the air is necessary for the reaction. If the air be excluded, no coloration is noticed, even after several da.ys. The reaction is therefore to be considered as an oxidation phenomenon. The reaction i.s very quickly produced when, according to the U. S. Pharmacopoeia, 2 cc. of oil are mixed with 1 cc. of glacial acetic acid and 1 droj) of nitric acid. By this treatment the Japanese oil is also colored slightly violet. The cause of the color reaction is, according to Polenske,^ to be found in a nitrogen-free, volatile body accompanying the oil. The colors which this forms with ai'ids show a characteristic spectroscopic behavior. The body itself is decomposed by light, for an oil which has been exposed for some time to the sunlight no longer gives the color reaction. Other color reactions are produced as follows : .V solution of 1 CO. of oil in .5 cc. of alcohol is heated with 0..5 g. of sugar and 1 cc. of hydrochloric acid. The mixture assumes a deeji blue, violet or bluish-green color. ^ A red color is produced when some chloi-al hydrate and hydrochloric acid are added to French pe|ipermint oil.+ German and English oils are said to be colored light brown by this reaction. The (^aiise of these cohjr phenomena are as little known as the composition of the bodies which produce them. From a practical standpoint but little importance can be attached to these reactions. 1) Phanii. .lourn.. Ill, 1, p. 682; Til, 2, p. :"!21. 2) Arbeiten a. d. kaiserl. (ieauiidheiteamte, Berlin (IS'.IO), IS, p. 522. Pliarm. Zeitung, 35, p. 547. 3 1 Cliemiker-ZeitunK, 13, p. 2(iJ-. 1) ArclUY J. Pharni., 203, p. 2'.); 205, p. 320. • Oils of the Lahintae. 643 CoMPOSiTiox. Menthol, which is found in all varieties of peppermint oil, must be considered as its characteristic constituent. On account of its ready crystallization it was early observed and repeatedly investi- gated by the older and the newei- chemists. The properties and chemical derivatives of this interesting compound have been described in detail on page lio. Menthol occurs in peppermint oils for the greater part in the free state, in smaller quantities in the form of its acetic and valerianic acid ester. A further constituent supposed to be common to all peppermint oils is menthone, which appears to have been first observed by Beckett and Wriglit.i The formation of menthol and other constituents of peppermint oil during various stages in the devehjpment of the plant has been investi- gated by Eugene Oharabot.^ The oils examined were derived from jilants at three different stages of growth ; the first as soon as the inflorescence appeared, and before the formation of flowei- buds, the second when flower bulls were formed, the third when the flowers were fully expanded. Before forma- tion of fiower buds. After formation of tiower buds Flcwering I>lants. Sp. gT. at 18° C Opt. rot. at 18° C Esters (as meiithyl acetate). Combined iiieuthol Free menthol Total nipiithol Menthone 0.9025 —24° 10' 3.7 percent 2.9 " 44.3 '■ 47.2 " 5 -2 " a) leaves. 0.901(5 —2(5° 10.3 percent 8.1 ■' 42.2 " •50.3 " 4.2 " b) inflores- cences. 0.9081 —20° 15' 7.5 percent 5.9 " 29.9 •' 35.8 '• 16.7 " 0.9200 —2° 37' 10.7percent 8.4 32.1 " 40.5 " 10.2 " It will thus be seen tluit at the flrst stage the plant yields an oil rich in menthol, but containing a relatively small proportion of esters, and in which menthone is only present in small quantity; as, however, the development of the green parts of the plant progresses, the proportion of ester,'^ increases, and this esteriflcation takes place in the leaves, for the oil from the inflorescences is less i-ich in esters. Menthone, however, would appear to be tAne&y formed in the flowers, where it increases during the development of the inflorescences, while the pro- portion of the total menthol diminishes. It is concluded, therefore, that, as in the case of lavender, esteriflcation is confined to the chlrjrophyll- tjearing parts, and that menthone is formed in tlie flowers hj the oxidation of menthol. 1) .Ioi>rn. Cliem. Soc, 1870. I, p. 'A. 2) Compt. rend., 1.30, p. 518. 6-44 Special Part. The more recent investio-ations are always confined to a single oil of definite origin. Inasmuch as the differences between the various oils depend without doubt on a difference in chemical composition, the results obtained with one oil i:-annot offhand be applied to another. For this reason the chemical composition will have to be discussed under each individual oil. American Peppermint Oil. There are two varieties of American oil, that from Wayne County on Lake Ontario, in New York, which is considered as the finer oil, and the cheaper and less valued oil distilled in Michigan and Indiana, in Wayne, St. Joseph and Van Buren Counties, and known as Western or Michigan oil. Propektieh. The sp. gr. of the peppermint oil from the state of New York lies between 0.91 and 0.92, the angle of rotation '/d between — 2.") and — 33°. The oil is not soluble in 70 p. c, but in y, and more parts of 90 p. c. alcohol, to a clear solution. In a freezing mixture it solidifies quite i-apidly to a crystalline mass. It contains a total of .50 — (30 p. c. of menthol, of which 40 — i.o p. c. are in the free state and 8 — 14 p. c. as esters. The amount of menthone present is about 12 p. e. The Michigan oil has a less fine odor than the preceding oil. but has the advantage, that it is clearlj' soluble in 4—.") p. of 70 p. c. alcohol. The sp. gr. of the oils so far investigated varied between 0.90.") and 0.913. the rotatory power au between —18 and — 29°. A menthol datermination made on four oils gave the following results: Free menthol, 43.(3— .50.3 p. c; menthol as ester, 4.3—8.5 p. c: total menthol, 48.(3—58 p. c. Two other oils of the same source were, as could be seen from their low total menthol content of 32.6 and 35.8 p. c, adulterated or dementholated. Power and Kleberi have published a very detailed investigation of the constituents of American peppermint oil. The oil had been distilled from the dried herb, free from weeds, collected in Wayne County, New York. The yield was 0.67 p. c; sp. gr. 0.9140; aD = — 32°0'. Menthol as e.ster, 14.12 p. c; free menthol, 45.5 p. c; total menthol, 59.6 p. c. By distillation from a fractionating flask the following fractions were obtained ; Up to 200° 2.6 p. c. 220—225° 19.6 p. c. ■ 200—20.5° 2.4 " 22.5—2.30° 9.0 " 20.5-210° 8.6 " 230-235° a. 6 " 210-21.5° 18.8 - Residue 12.2 " 21.5—220° 24.0 " I) Pharni. Rundschau, 12, p. 157; Arch. d. Pharm., 232, p. C39. Oils of the Lahiatae. 645 • On account of the greater care taken in the collection of the material, and on account of the more perfect distilling arrangements, the oil had a much purer and more pleasant odor than the ordinary commercial oil. In American peppermint oil there have been found so far no less than 17 different, well characterized chemical compounds, a number which has up to the present not been found in anv other oil. The bodies found can be here given with but a brief mention of their detection. For the details and the course of the analysis the original must be consulted. American peppermint oil contains : 1) Acetaldehyde, CH.3COH, abt. 0.0-44 p. c, yielded acetic acid on oxidation. 2) Isovaleric aldehyde, (CH3)2.CH.CH2. COH, abt. 0.048 p. c, b. p. 92°, gave valerianic acid on oxidation. 3) Free acetic acid, CH3COOH. 4) Free iso valerianic acid. (CH3)2. CH. CH2.COOH. 5) Pinene,2 CioHih, inactive, perhaps a mixture of d- and 1-pinene (pinene nitrolpiperidine, m, p. 118°, pinene nitrolbenzylamine, m. p. 128°). 6) Phellandrene. CioHi« (nitrite, m. p. 100°). 7) Cineol, CioHigO, b. p. 174 — 177° (ciueol hydrobromide, cineolic acid, m. p. 196°). 8) 1-Limonene, CioHie, (tetrabroniide, m. p. 104°). 9) Menthone, CioHisO, (conversion into menthol). 10) Menthol, C10H20O, b. p. 215.5°. 11) Menthyl acetate, C10H19O. C2H3O. 12) Menthyl isovalerianate, C10H19O . CoHeO. 13) Menthyl ester of an acid C8H]202, C10H19O. GsHnO. 14) A lactone CioHi802. m. p. 23°, of a stale odor, reminding slightly of borneol. The corresponding oxj^ acid crystallizes from petroleum ether in shining needles, melting at 93°. 15) Cadinene,! C1.5H24 (dichlorhydrate, m. p. 118°). 16) Amyl alcohol, C.5H12O, (acetate). 17) Dimethyl sulphides S(CH3)2. ' "■ Besides these there appear to be present in peppermint oil other higher boiling, unstable sulphur compounds, as during the middle of 1) Bericht von .S. & Co., Apr. 1894, p. 42. 2) First observer] by HaUe.v (Proc. Wisconsin Pliarm. Assoc, 1893, p, 90). 3) Bericlit YOn 8. * Co., Oct. 1891), p. 61. , . , 0-46 Special Part. the rectification of tlie oil, there is frequently noticed a penetrating- odor, reminding of putrifying ruta-baga. The presence of dimethyl sulphide in peppermint oil, is shown as follows : From 50 cc. of the crude oil about 1 cc. is distilled off, aud this poured on an aqueous solution of mercuric chloride. In a short time the formation of a soft skin can be observed at the zone of contact of the two Uquids. On account of its volatihty the dimethyl sulphide collects in the first portions on rectifi- cation of the oil. Oils from which the first runnings of the rectification have been removed, no longer show the reaction. Menthene, CioHis, b. p. 158—160°, which according to Andres and Andreefi occurs in Eussian peppermint oil, could not, in spite of a diligent search, be found in the American oil. Likewise unsuccessful was the search for a terpene CioHie, boiling at 175° and having the properties of Briihl's^ so-called menthene. English Peppermint Oil. The English oil, mostlj^ designated as Mitcham peppermint oil, is very highly valued on acc-ount of its fine aroma and pleasant taste. It is obtained from two varieties, the black and the white mint. The former gives by distillation the larger yield, but the oil from the white mint is considered as superior in quality. Pkopbrties. English peppermint oil has the sp. gv. 0.900 — 0.910, the rotatory power '-(d = — 22° to — 33°. Total menthol, .^.S — b6 p. e. ; free menthol, 50 — 60 p. c. ; menthol as ester, 3 — 11 p. c. ; menthone 9 — 12 p. c. The oils of the two English varieties differ, according to Umuej',8 in their content of menthol as esters. Whereas the oil of the white mint contains 14 p. c. of menthol as esters, the oil of the black mint contains onlj^ 7 p. e. The oil of a black mint cultivated in America had, however, a content of 12.2 p. c. of menthol as esters, from which it follows that the difference in the ester content is not decisive. Umney observed great differences on fractionation of the oil of the white and of the black mint. Black mint. White mint. Below 200° 5 p. c. 24 p. c. 200-205° 27 " 15 " 205—210° 31 ■• 15 ■• 210—215° 22 " 15 •• 215—220° 7 " 13 •• Above 220° 8 " 18 " i| Berichte, S.S, p. 609. 3) PharTii. .lourii., .56, p. 128: r,7, p. 103, -) Berichte, 21, p, l.o7. Oils of the Lahiatae. 647 The color reaction with glacial acetic acid is less intense than with the American oil ; according to Umney the intensity of coloi'ation increases with the amount of esters present. Although the menthol content found by acetylization is higher in the English oil than in the American, often only a slight separation of crystals takes place in the freezing mixture. This behavior makes it probable that besides menthol there are present other alcohols (isomeric liquid menthols?) which are estimated as menthol in the acetylization method. Composition. Fliickiger and Power ^ isolated from the English peppermint oil two laevogj^rate terpenes, boiling at 1(55 — 170° (mixture of pinene and phellandrene?), as well as a dextrogyrate sesquiterpene boiling at 2.55 — 260° (probably cadineue). Unmey^ sliowed the presence of phellandrene by the nitrite reaction and ascertained that the acids combined with the menthol as esters are the same as in the American oil, namely, acetic and isovalerianic acids. He further determined quantitatively the amount of menthone present in the oil. There is no doubt but that with a thorough investigation a great number of the same substances occurring in the American oil would be found. Japanese Peppermint Oil. Pkopbrtibs. The normal Japanese oil is at ordinary temperatures a solid mass of crystals saturated with oil. In commerce occurs the normal oil (nnseparated), the crude menthol, forming a loose crystal mass {crystals), or the liquid oil separated from the latter (oil). The Japane.se oil is the cheapest of the peppermint oils, but cannot be used for all purposes on account of its bitter taste. Normal oil has the sp. gr. 0.895—0.900 at 24°; solidification points +17 to +28°; angle of rotation au^ — 30 to — 42°. It is soluble in 3 — 5 p. of 70 p. c. alcohol. Total menthol, 70—91 p. c. ; free menthol, 65—85 p. c; menthol as ester, 3 — 6 p. c. The liquid oil obtained in the prepar- ation of menthol has the sp. gr. 0.895—0.905, «d = — 26 to —3.5°. It is not always soluble to a clear solution in 3—5 p. of 70 p. c. alcohol. The color reaction with glacial acetic acid described on p. 642 is not given by the Japanese oil, or only to a slight degree. 1) Pharm. Journ., III. 11, p. 220; Archiv d. Pharm., 218, p. 222. 2) Pharm. Journ., 56, p. 123; 57, p. 103. 3) Determined as described on p. 187. 648 Specia.1 Part. Composition. Japanese peppermint oil was investigated in 1876 by Beckett and Wright.i They found in the fraction boiling- at 210—215° of the part remaining liquid on cooling, a body CioHisO isomeric with borueol, which in all probability was menthone. In the fraction boiling at 215—255° they suspected a compound CaoHsnO, which, according to their view, was formed by the splitting off of water from 8 molecules of the body GioHisO. aOioHisO = C30H50O + 2H2O. As this formula is not very probable, it must be assumed that the fraction 24!") — 255° consisted of impure menthol, mixed witli sesquiterpene. Saxon Peppermint Oil. The Saxon peppermint oil is unsurpassed by all other commercial varieties in fineness of aroma and taste. It is the highest priced of all the peppermint oils. As its annual production jimounts to only a few hundred kilos, it plays no important part in the world's market. Sp. gr. 0.900—0.915; «d=— 25 to —38°. The solubility is mostly the same as with the English oil, sometimes, however, a slight opalescent turbidity results on the further addition of 70 p. c. alcohol. Total menthol, 54.7—67.6 p. c. ; free menthol, 46.5—61.2 p. c. ; menthol as ester, 5.7 — 8.2 p. e. ; menthone. 15.7 p. c. On cooling a crystal sep.ar- ation or solidification takes place only after standing for several days in a freezing mixture. 2 German Peppermint Oil. The oil distilled in Gnadenfrei, Silicia, in small amounts, belongs to the best peppermint oils and is similar in its projierties to the Saxon oil. From the refuse, not suitable for medicinal purposes, of the pepper- mint plants cultivated in Colleda, Eingleben (Thuringia) and other places, an oil of inferior quality, accompanied by an unpleasant spear- mint-like oilor, is obtained. Sp. gr. 0.899—0.930; ai3= — 27 to —38°. The oil is usually not soluble to a clear solution in 70 p. c. alcohol. French Peppermint Oil. The peppermint oil produceil in southern France appears to be principally used in France itself. It distinguishes itself by a high sp. gr. and low rotatory power. Sp. gr. 0.918 — 0.920 ; '/.d = — 5° 54' to 8° 20'. A sample investigated was not soluble in 70 ]). c. alcohol. Total 1) .lourn. Chem. Soc, 18715, I, p. P.: .Jahre.sli. t. Chein.. lS7i;. p. S;)7 2| Berloht von S. & Co., 1896, 1. p. .jO. Oils of the LaJjiatae. 649 menthol 43.7—46 p. c; free menthol 35.7—39.4 p. c; esters 7.1—10 p. e.; menthone 8.8 — 9.(5 p. c. The acids combined with the menthol are the same as those in the American and English oil, namely, acetic a.nd isovalerianic acid.i Charabot,! together with C. Ebray, has studied an interesting change in the inflorescence of Mentha piperita, which is known to the cultivators and distillers of south-western France as Menthe hasiJiquSe. This variety of Mentha piperita shows besides the normal inflorescence also some which appear like racemes, similar to the inflorescence of the basilicnm after the petals have fallen off, These changed shoots do not blossom; but rather appear as though carrying seed, although in their place are found only bunches of leaves. A microscopic examination of a section through the base of the changed sprout has shown, that the change is brought about V)y the sting of an insect. The oil obtained from this changed plant has an unpleasant odor and distinguishes itself from the normal oil by a higher sp. gr. and rotatoiy power, as well as by the lower content of menthol and menthone. For such an oil were determined: .sp. gr. 0.924 at 18°; «d ^ +7°; esters, 8.2 p. c; total menthol, 41 p. c; menthone, 3 p. e. Russian Peppermint Oil. The Eussian peppermint oil likewise plaj's no part in the world's market, and like the French, is principally distilled for home consumption. Sp. gr. 0.905—0.910 ; ao = — 17 to —22°, The amount of total menthol determined in a single case was 50.2 p. c. (free menthol 46.8, menthol as ester 3.4). Crystallization took place only after standing for a long while in the freezing mixture. 2 Russian peppermint oil has been investigated by Andres and Andreef.8 Besides menthol, it contains dextrogyrate menthone, probably a mixture of both optical modiflcations, in which the dextrogyrate modiflcation predominates. The fraction 158—160° gave on analysis numbers which indicate a mixture of a hydrocarbon CioHis with a terpene (pinene?). The a.uthors therefore assume the presence of a menthene,* which, however, they were unable to isolate in a pure form. The fraction 173 — 175° contains 1-limonene (tetrabromide, m. p. 102°, nitrosochloride, m. p. 103°, dichlorhji-drate, m. p. 49.5 — 50°. 1) Bull. Soc. chlm.. Ill, 19, p. 117. 2) Bericht von S. & Co., Apr. 1S96, p. .'lO; ibidem, Apr. 1889, p. ST,. 3) Bei-ichte, 25, p. 609; Pharm. Ztsch. f. Russl., 29, p. .341. *) The inenthene, CioHig, resulting by splitting off water from menthol, boils at 167—168°. .... 650 Special Part. Italian Peppermint Oil. The oil distilled in the provinces of Piemont and Padua is noti exported, at least not in apprei:-ial:)le quantities. Sp. gr. 0.911—0.926; ari = —13 to —18°; b. p. 19."j— 222°. In a freezing mixture none or only a slight menthol separation takes jjlace. Total menthol, 44.1—46.6 p. c; free menthol, 3(>.7— 41 p. i-.; menthol as ester, 5.6—7.4 p. c. Bohemian Peppermint Oil. An oil distilled in Bohemia had the following properties: sp. gr. 0.90.5; «D = — 27°22'. Soluble in 70 p. c. alcohol. Total menthol,. •59.9 p. c; ester menthol, 8.7 p. c; free menthol, 51.2 p. c.i Chilian Peppermint Oil. An oil distilled in C)sorno (ChiliJ of the sp. gr. 0.916, had an- intense odor of pennj-roj^al.^ Reunion Peppermint Oil. An oil prepared on the island of Reunion had an odor more of lavender than of peppermint. With iodole it gave Hirschsohn's cineol reaction, had the sp. gr. 0.887, the rotatorj^ power «d = —6° 9', and. was soluble in 4 p. of 70 p. c. alcohol. Examination. For the detection and identification of the numerous- adulterants of peppermint oil it is necessary, above all, to determine the phj'sical constants, as by them the attention is called to grosser adulterations with alcohol, turpentine oil, and other volatile oils. For distinguishing the different varieties the solubility determination in 70 p. c. alcohol is very useful. All peppermint oils are soluble in equal parts of 90 p. c. alcohol, but only a part of them form clear solutions- with 70 p. c. alcohol. The U. S. Pharmacopoeia requires that peppermint oil solidify at — 8 to — 20°. If American oil is allowed to starnl in a good freezing mixture of ice and salt until thoroughly cooled, and then a small crjrstal of menthol added, it will crystallize in a short while to a solid mass. With English peppermint oil a good mentiiol separation usually takes place, but as a rule it does not solidify. The behavior of the other oils in a freezing mixtui-e has been mentioned under their 1) Berlcht von S. & Co., Apr. IKlKi, p. ."jO. 2) Bericht von S. & Co.. Oct. 18!)i, p. IT,. Oils of the Lahiatae. 8B'l description. American oil lias been repeatedly found in the market from whii.'h a part of the menthol had been removed ; the solidification test is therefore of importance for this variety. With the English oil the separation of menthol is hardly profitable as the oil commands a higher price than menthol. Inasmneh as adulterations with other oils decrease the menthol content, a quantitative menthol determination is often of great value. According to Power and Kleber the method is as follows : ^ 20 g. of peiipermiiit oil are heated to boiling with 20 g. of alcoholic normal soda solution (or normal or J^ normal potassa solution) for about an hour, in a flask provided with a reflux condenser (fig. .56, p. 194), in order to decompose the menthol esters. After cooling, the unconsumed alkali is titrated back with normal sulphuric acid, using phenol phthalein as indicator. The saponified oil is repeatedly washed with much water and then heated with an equal volume of glacial acetic acid and 2 g. of anhydrous sodium acetate in a flask provided with a glass-ground tube condenser (flg. .57, p. 195). After cooling, the oil is- washed several times with water and dilute soda solution, dried with calcium chloride and filtered. S — 10 g. of this oil are then saponified, as described above, with 50 cc. oi alcoholic normal soda solution and the excess of alkali titrated back. Eacli cc. of the nrjrmal soda solution corresponds to 0.156 g. of menthol or 0.198 g. of menthyl acetate. In order, therefore, to obtain the percentage of menthol in the original oil (not aeetylized. but freed from ester) it is necessary to deduct 0.042 g. (the difference between 0.156 and 0.198) for every cc. of normal alkali consumed. If, e. g., s g. of aeetylized oil require a cc. of normal soda solution, the total menthol content P (free and ester) can be calculated according to the following formula; a X 15.6 ~.s— (aX 0.012) The result thus obtained does not express exactly the menthol content, inasmuch as it is assumed for purposes of calculation that all the menthol is present as acetic e.ster whereas some of it is combined with isovalerianic acid. The resulting error, however, is so small that it can be disregarded. The amount of menthone is determined in the following manner: After the menthol content has been determined with a part of the saponified oil, another j)art is diluted with twice its volume of ah-ohol and boiled for some time with metallic sodium. Thereby the menthone is reduced to menthol which can be assayed as described above. 373. Oil of Spearmint. Oleum Menthae Crispae. — Kraiiseiiiiiiziil. — Essence de Menthe Crepue. Origin and Prepar.4.tion. Di.stinction is made between three kinds of spearmint oil, American, German and Rus.sian. The American oil is 1) Pharm. KiindBChau, 12, p. 1U2. 652 Special Part. distilled in New York and Michig-an from the fresh hei-b of Mentha, viridis L. The herb is cultivated to a not inconsiderable extent, as much as 12,000 lbs. of oil being obtained in the two states mentioned. i In England (Miteham) also some oil is distilled from the same plant. The German oil is distilled in small amounts, in Thuringia only, where spearmint is cultivated for medicinal purposes. The waste resulting in the process of drying is used for this purpose. The plant cultivated is the Mentha, erispa L. which is regarded as a cultural variety of M. aquatica L., whereas .1/. %'nidis L. is probaljly a r-ultural variety of M. silvestris L.2 The botanical source of the Russian oil is not known. Propekties. American and German spearmint oil resemble each other so clo.sely that no distinction is made in commerce. The oil is a colorless, j^ellowish, or greenish-yellow liquid and possesses the char- acteristic, penetrating and disagreeable odor of spearmint. With age and upon exposure to the air, the oil becomes viscid and darker. The American oil has a sp.gr. of 0.920—0.940 and «d = — 36 to — 48°. It is soluble in equal parts of 90 p. c. alcohol, but the solution is rendered turbid upon the addition of more solvent. An oil distilled by Fritzsche Bros, had somewhat different properties. The spearmint had been cultivated on the factory grounds at Garfield, N. J., and was just in blossom wlien distilled. " The yield was 0.8 p. c. The oil had a sp. gr. of O.9S0, consequentlj' higher than that of the ordinary oils; «D = — 42° ;!<)'. The odor was quite different from that of the conmiercial oil, not at all minty or pennyroyal-like, but reminded distinetlj' of carvone. Upon rcohobating the aqueous distillate a con- siderable amount of oil heavier than water was obtained. It is possible that in the distillation of the commercial oil a part of this heavy oil is lost, thus accounting for the lower specific gravity. ^ After the first harvest toward the close of July, a second was made early in October. The yield from the fresh herb was only 0.18 p. c. The odor of this oil was less delicate, its specific gravity and rotatory power were lower, viz. 0.9(31 and an = —37° 20'. Nevertheless, this oil was still heavier than the commercial oils, though no fraction was obtained heavier than water.s Composition. According to Kane* the oil of Mentha viridis is sup- posed to contain a crystalline constituent, but none of the later 1) Bericht von S. & Co., Oct. 1S96, p. 4.5. y) Pliarinacognosie, Hrd eil., p. 727. — See also i>. t'>2\). 3) Bericht von S. & Co., Apr. 1897, p. 49. *) .Tourn. f. prakt. Chem., 15, p. 163; Liebig's Aunalen, 32, p. 28i3. Oils of the Labmtae. &5S, investigators observed such a substance. Gladstone ^ found carvone in spearmint oil. With sulphuretted hydrogen he obtained a solid com- pound which upon treatment with alkalies yielded an oil of the com- position C10H14O. This turned the plane of polarized light as far to the left as dill carvone turned it to the right. Gladstone gave to this substance the inappropriate name of menthol. From German spearmint oil Fliickiger^ in 1875 obtained l-carvone of low rotatory power. Bej'er,^ on the other hand, found in 1888 that the angle of rotation of the cai'vone of the German oil is as great as that of carvone from dill and caraway oils. The amount of carvone in spearmint oil was determined by Sehreiner and Kremers* as 56 p. c. According to Trimble ^ spearmint oil contains a terpene boiling at 160 — 167.5°, according to Beyer a laevogyrate hydrocarbon boiling at 168 — 171°. Briihl* concludes from the statements of Gladstone that d-pinene is present. According to Gilman '^ the oil contains 1-linionene and probably 1-pinene. To w-hich constituent the oil owes its char- acteristic odor is not yet known. Russian spearmint oil is reported to be distilled in large quantities but it is principally consumed in Russia. It differs from the American and German oils by its stale odor reminding but slightly of spearmint. Specific gravity and optical rotation are much lower than of the first two varieties, viz.", 0.883 8—0.885; au = — 23°12' at 17°. The oil under examination gave a clear solution with 2 parts of 70 p. c. alcohol and had a saponification number of 25.9. It was shown to consist of 50—60 p. c. of l-linalool.9 Fraction 196—200°, with «d = — 17°37' at 17°, upon oxidation j'ielded citral (citryl- j-naphtho cinchoninic acid, m. p. 197°). Fraction 170—175° (aD = — 24°54'), which constituted about 20 p. c. of the oil, yielded the iodole reaction (iodole-cineol, m. p. 113°) for cineol ; and also yielded a nitrosochloride melting at 100°, thus indicating the presence of 1-limonene. The highe.st fraction yielded carvone hydrosulphide melting at 210 — 211° ([«]d^ — 36°0', at 17° and in 5 p. c. chloroform solution). The amount of l-carvone in Russian spearmint oil is estimated at 5 — 10 p. c. The difference between American and German spearmint oil on the 1) Journ. Chem. Snc, 25, p. 1 ; ') Proc. Wis. Pharm. Assoc, 1893, p. 53. .Jahresb. f. Chem., 1872, p. 816. There also seems to be an alcohol CioHigO 2) Berichte, 9, p. 473. present as indicated by the CaCl2 compound 3) Archlv d. Pharm., 221, p. 283. and analysis of the regenerated oil. Unpub- *) Pharm. Review, 14, p. 244. lished results of L. Sumner. E. K. 5) Am. Journ. Pharm., 57, p. 484. s) Bericht von S. & Co., Apr. 1889, p. 23. 6) Berichte, 21, p. 156. s) Bericht von S. & Co., Apr. 1898, p 28 65-1- Special Part. one hand, and Kussian oil on the other, lies principally in the linalool content of the latter accompanied by a small percentage of c-arvone. Examination. For the detection of adulterations Kremers and Schreineri suggest the carvone assay of the oil according to the method previously' described. 2 As principal adulterants cedarwood and gurjun balsam oils are taken into consideration. Both of them have about the same specific gravity as spearmint oil; both are also laevogyrate. Individually these oils can be added to the extent of H)—l'> p. c, com- bined however in much larger quantity before being detected Ijy the determination of physical constants. To determine the carvone (/onteiit of oils thus adulterated is not feasable because the boiling points of carvone and the sesquiterpenes are too close together. The oxime method alluded to above also yields results that are too low. This is attributed to the cii'cumstance that the sesquiterpenes when distilled with water vapor carry some of the carvoxime over and retain it in solution. Qualitatively the jiresence of the two adulterants can be ascertaineil by Wallach's sesquiterpene reaction (p. 124). The test is maile with the oily distillate obtained in the carvone assay. 374. Oil of Watermint. The dry herb of Mentha aquatic;) L. yielded upon distillation 0.34 p. c. of volatile oil of a, yellowish-green color and pennyroyal-like odor.3 Sp. gr. 0.880; „d = — 2°14'. 375. Oil of Mentha Arvensis. From the dry lierli of Mentlui arvmsin L. 0.22 p. c. of oil was obtained, (^p. gr. O..S.",7 ; '/d = — 2°44-'. 376. Oil of Wild Mint. Mentha canadensis L., which grows wild in North America, yielded upon distillation an oil of reddish-yellow ccilor the odor of which reminded of pennyroyal. The yield from the dry herb was 1.2:! p. c* Sp. gr. 0.948 at 15°,* 0.927—0.935 at 20° ; s «d = + 16° 11' to -f 20° 32'. It forms a clear solution with twic-e its volume of 70 p. c alcohol.* According to Gage,'' the oil contains pulegone, the presence of which was determined by means of the bisnitroso compound suggested 1) Phiirin. Iteview, 14, p. 244. 4) Berioht vun S. & Co., Oct. 1893, p. 4j 2) See under caraway oil p, ,">ri4. =) Pharm. Review, 16, p. 412. 3) Bei-iclit von K. & Co., Oct. 1889, p. 55. Oils of the Lahiatae. 655 Ijj Baeyer. The melting- point of the compound, not mentioned by Baeyer, is 81.5°. Besides pulegone, this oil contains small amounts of thymol or carvacrol. 377. Oil of European Pennyroyal. Oleiiiu M'eiithae Piilegii. — Poleiiil.— Essence de Poiiliot. ORittiN AND History. European pennyroyal (Ger. Polei) is derived from Mentha pulegium L. {Pulegium rulgare Mill.) or its hybrid varieties, and has lieen used medicinally since the middle ages and possibly earlier. The distilled Oleum pulegii is mentione(i in the price ordinance of Frankfurt for l.")82 and appears to have been used medieinallj' like the plant and its distilled water in the sixteenth and .seventeenth centuries. The commensal European oil of pennyroyal is distilled in Spain, southern P^ranee and Algiers from the fresh herb. The Spanish oil is favored on account of its greater purity, whereas the oil from the two ■other countries is less reliable on account of being frequently adulterated. Properties. European pennyroyal oil is of a yellowish or reddish- vellow color and of a strong, aromatic, minty odor. Sp. gr. 0.930 — 0.960; '/-D = +17° to +23°. It forms a clear solution with 2 and more parts of 70 p. c. alcohol. Inasmuch as the addition of turpentine oil renders the oil less soluble, this test is a. valuable one. Turpentine oil also lowers the boiling temperature and the specific gravity. Composition. European pennyroyal oil has a boiling temperature -of limited range. Up to 212° about 5 p. c. pass over; the bulk of the oil, abt. 80 p. c, distills over between 212 — 216° and consists of a ketone, CioHieO, named pulegone by Bei'kmann and Pleissner.i The properties and derivatives of this compound, which boils at 221 — 222° iwhen pure, are described on p. 1(59. The oil examined by Kane- in 1839 cannot have been a pure oil, neither can the fraction 183— 18.")°, the composition of which agreed -with either of the formulas CioHinO or CioHisO, have consisted of pulegone. • Eussian Pennyroyal Oil. The only reference concerning this oil is by Butlerow^ in 1854. According to him it is distiller! from the herb of Pulegium micrtinthum Claus, growing on the steppes of southern Russia-, especially near 1) Liebiff's Aunaleii, 262, p. 1. 2; Liebig'H Annalen, 32, p. 286; .loiirnal f. prakt. Chem., 15, p. 160. ^) .Jalu-esb. L Chemie, 18.54:, p. 594. 656 Special Part Sarepta and Astrachan. Sp. gr. 0.934. It begins to boil at 202°, the bulk coming over at 227°. It has the composition OniHieO and pre- sumably consists principallj' of pulegone. 378. Oil of Patchouly. Oleum Foliorum Patchouli. — Patchouliol. — Essence de Patchouli. Origin and Peepabation. Genuine patchouly, Pogosteinon patchouli Pellet, is cultivated principally in the Straits Settlements, in Penang, also in the province Wellesley. It is either directly distilled or dried and brought into commerce from Singapore. Comparatively little herb i,s produced on Mauritius and Reunion. i Attempts to cultivate it have been made in Paraguay,^ also on the West Indian islands Dominica, Guadeloupe and Martinique. No appreciable amounts, however, seem to be produced. Formerly a considerable amount of the drug was also supplied by Java, but in recent years this source of sup];)ly has given out entirely. The botanical origin of the plant from Java is not yet known. 3 The drug shipped from Calcutta and Bombay is of poor quality, containing a la,rge amount of stems and yielding an inferior distillate.* The herb cultivated in Assam (Silhet and Khasia mountains) is obtained from Microtaena cymosa Prain^ {Pleetranthuti patchouli Clarke) and probably enters commerce via Calcutta. This would explain the difference of this commercial variety. Whether the herb exported from Bombay is derived from Pogosteinon ]jatchouli is not known. Concerning the cultivation and the distillation J. Fisher of Singa- pore makes the following report : " "The variety selected for cultivation i.s known locally as Dhelum Wangi, which was originally obtained from a small island south of Penang. called Rhio (probably one of the Dindingsl. Tlie soil most suitable is a rather stiff cla.y, containing- only a small iterceutage of silica. Land of this description i& found near the coast (containing traces of marine deposits), and is planted in rows of 4 or 5 feet apart. The plants are propagated by cuttings struck iu the open air. which, until rooted, are sheltered from the sun by pieces of cocoa- nut shell. The harvest is made in dry weather, and when the sun has drawn up the dew from the leaves; the tops and green parts of the plant are taken off, rejecting all yellow and decayed leaves, and as much as possible the woody stems. The selected parts are then dried in the shade, under large sheds (as the sun would draw out the perfume), and to ensure evenness in drying they are spread on bamboo racks, allowing the air to penetrate from beneath. 1) Bericht von 8. & Co., Oct. 1890, p. 86. 4) Bericht von S. & Co., Apr. 1887, p. 25. 2) Bericht Ton S. & Co., Oct. 1887, p. 24. s) Odorographia, vol. 1, p. 297. 3) Pharm. .Journ., 56, p. 222. Oils of the LahiatAe. 657 During tliis process they are frequently turned over, and when so far dried as to leave just sufficient moisture to permit of a sli>?ht fermentation they are piled in heaps and allowed to heat gently ;i after this they are again spread out and dried — but not to absolute dryness — and are immediately distilled. The addition of about 25 p. c. of ibe wild herb Dhelum Outan is said to increase the fragrance of the distillate. The distillation is effected by passing steam, generated in a boiler apart, through the leaves in the stills. The pressure of steam is not allowed to rise above 20 lbs., the yield under these conditions beiiig about Yi oz. per pound of leaves; by high-pressure steam the yield would be a little increased, but rank in quality. The stills are sometimes jacketed, and, by i)assing a separate current of steam into the jacket conden- sation in the body of the still at the commencement of the operation is avoided. "2 The bulk, however, of patchouly oil, which i.s used exclusively for perfumery, fS probablj' distilled in Europe. With the perfect equipment there in use, the yield is as high as 4 p. c. The purchase of patchouly herb requires considerable care inasmvich as it is frequent!}' adulterated. The most common adulterant is the leaves of Ocinium bcisilicum L. var. pilosuin (Family Labiatae) known as Ruku by the Malays. The peculiar odor of these is lost entirely in the presence of patchouly leaves. Frequently the leaves of Urena, loba.ta L. var. /iimiutu (Family Malvaceae) are also found, which are called Perpulat by the Malays. It is a weed common in cocoanut plantations. Other adulterants are the leaves of Plectranthus fructi- C08US, of Lavatem albia and of Pavonia weldenii (Paschkis'^). In addition to these foreign herbs, which sometimes make up 80 p. c. of the bales, as much as ~>0 p. c. of sand and earth and up to 35 p. c. of moisture have I'ecently been found. Properties. Patchouly oil is a yellowish or greenish-brown to dark brown liquid from which crystals occasionally separate upon standing. The odor of the oil is exceedingly intensive and persistent. Sp. gr. of pure oils distilled in Europe varies from 0.970 to 0.99.J ; ajj varies from — ~)0 to — 68°. The oil renders a clear solution with equal parts of 90 p. c. alcohol which as a rule remains clear upon the addition of more alcohol. Occasionally, however, the solution becomes turbid upon the addition of 2 volumes, but this turbiditj^ disappears when as much as 4 — -"i volumes have been added. 1) Inasmuch as the fresh jjatchouli herb is odorless, it is to be assumed that the oil is formed during this process of fermentation. 2) Further interesting communications concerning the cultivation and distillation of patchouly on the .Malaccan peninsula from the pen of Wray, curator of the govern- ment museum at Perak, are to be found in the Kew Bulletin for .June 1889 and are reproduced in the detailed account in Sawer's Odorographia, vol. 1, pp. 293 — 308. 3) ZeltHchr. des fist. Apt. Ver., 17, p. 41.5; Pharni. .Journ., Ill, 11, p. 813. 42 65S Special Part. Of the imported oils many possess the same properties, some, how- ever, diil'er materially. Of a number of oils imported from Singapore the sp. gT. lies between 0.957 and ().9G5 ; «d varied from —44 to —50°. These oils were soluble in not less then 3 or 7 volumes of 90 p. c. alcohol. Whether these were adulterated or not cannot be determined at present. They mu.st, however, be regarded as suspicious, for by the addition of cedar wood oil or cubeb oil to patchouly oil distilled in Europe, oils of the just enumerated properties were obtained. Composition. Concerning the substances that produce the character- istic odor of patchouly oil nothing whatever is known. Thus far. but two constituents, which are inessentia,l as far as the odor is concerned, have been isolated, namely patchouly alcohol and cadinene. The patchouly alcohol, formerly known as patchouly camphor, occasionally separates upon prolonged standing and therefore, first attracted the attention of chemists. Gal i in 1 869 proposed the formula C15H28O, Montgolfler- in 1877, CioH^aO. The latest investigation is by Wallach* (1894) who introduced the more rational term patchouly alcohol. Patchoul}- alcohol. Ci.oHsoO. crystallizes in transparent, colorless, hexagonal prisms whii.-h end in six-sided pyramids and melt at 5(3°. It is strongly laevogyrate, [«]d^ — 118°.- The elements of water are so loosely bound that even weak dehydrating agents such as hydrochloric acid, sulphuric acid and acetic acid anhydride in the cold, or acetic acid, potassium acid sulphate or zinc chloride with the aid of heat, form the hydrocarbon C15H24. This patchoulene boils at 254 — 256°, has a sp. gr. 0.939 at 28° and has a cedar-like odor. By the exchange of halogen for the hydroxy grou]) of the patchouly alcohol very unstable halides result which at once lose the elements of hydrogen halide. The entire behavior of patchouly alcohol seems to indicate that it is a tertiary alcohol (Wallach). In fractiim 270° Grladstoiie+ found a sesquiterpene similar to that obtained from oil of cubeb. In the highest fraction he found a portion the vapors of which were blue, the so-called azulene or coeruleine which also occurs in other oils. According to Wallach, ^ the oil is rich in cadinene, Ci.-,H24, the hydrochloride of which melted at 117 — 118°. 1) Corapt. rend.. 08, p. 40P> ; Lieblg's .innulen, l.'iO, p. 374. ■•!) Compt. rend., 84, p. 88. 3) LlebiK'B .Vnnalen. 1279, p. 394. M .lourn. Cliem. Soc, 17. p. 3: .Tahresb. f. rhemic, isca, p. 5) Llebig'H .Annalen, 238, p. SI. Oilfi nftbp Lubiatae. 659 379. Oil of Dilem. As Dilew the Malays desiji-nate a number of plants with patchonly odor. The leaves from Java distilled by Sehimmel & Co.i were identical with the "flowering- patchonly herb" of the botanical garden at Bniten- zorg- and, according to Holmes, s are derived from Pogontemon ronio- ,sus Miq, These dilem leaves upon ilistillation jdelded 1 p. e. of oil, the odor of which resembled that of patchonly oil, bnt was mnch finer. It i.s yellowish-green, rather viscid, sp.gr. 0.960, and boils between 250— 800°. i Upon distillation of the flowering patchonly leaves acetone was observed. 3 An oil di.stilled in Buitenzorg liad a green color and an odor similar to that of patchonly, the intensity of which was agreeably subdued l)y an anise-like by-odor. iSp. gr. 0.9(31; ^u^ — ;!2°17'.-t 380. Oil of Sweet Basil. Olenin Basilici. — Basilicumol.— Essence de Basilic. History. Oil of sweet basil appears to have been in use during the middle of the sixteenth century. It is enumerated among the oils of the Frankfurt price ordinance for 1.5H2 and in the Dispensatorium Noricum of 1589. Tlie distilled water was userl as early as the flfteenth century. Ohigin. Oil of sweet basil is distilled in southern France and Spain, occasionally also in Germany from the fresh herb of Ocimum Imsili- cuin L. The yield from the German herb is only 0.02 — O.Ol p. c. On Reunion also oil of sweet liasil is distilled. The differences in properties and composition of this oil, however, render it probal)le that some other species or variety of Ocimuin is used. Properties. French and German oil of .sweet basil are yellowish, of an aromatic, penetrating odor reminding of estragon. The sp. gr. varies from 0.905—0.980; «d from — (3 to — 22°. It is soluble in 1—2 parts of yo p. c. alc-ohol. The Reunion oil differs from the French in having a camphor-like by-odor, also a higher sp. gr., viz. 0.945 to 0.987. Whereas the French and German oils are laevogyrate, the Reunion oil is dextrogyrate, «d = + 7° to +12°. The Reunion oil as a rule is soluble in 7 or more parts of 80 p. c. alcohol. In some instances 3 parts will suffice to produce a clear solution. 1) Bericht von S. & Co., Oct. IKSH, p. 42. '^) Pharni. .Tourn., .56, p. 22.3. 3) Verwla^ omtreiit rten Staat van s'Landa I'lantentuin te Buitenzorff, 1S94-, p. 4:3. 1) Ibidem, 1893, p, 55. 660 Special Fart. Composition. Bonastrei in 1881 found in oil of sweet basil a solid constituent, the so-called basilicum camphor. An analysis made by Dumas and Pelig-ot^ in 183-") agreed with the formula C10H22O3, i. e. with terpin hydrate. In all probability this substance was formed by the addition of water to pinene or linalool. The French oil was ex- amined more recently (1897) by Dupont and Guerlain-^ who found as principal constituents methyl chavicol and linalool. Of similar composition is the German oil as shown by Bertram and Walbaum^^ (1897). The lowest boihng- fraction contains cineol-' (cineol iodole, m. p. 112°). P'raction 215° contains methyl (.-havicol (homo- anisic acid, m. p. 8.")°). Judging from the methoxy detei'mination, the oil contains 24 p. c. of this compound. Fraction 200° was of an alcoholic nature and probably contains linalool which was found in the French oil. Neither the (lerman nor the French oil contains camphor. In the Reunion oil Bertram and Walbaum found: 1) d-pinene (pinene nitrolbenzylamine, m. p. 128°); 2) cineol (hydro brom cineol, iodole cineol, m. p. 112°); 8) d-camphor (camphor oxime, m. p. 118°); 1) methyl chavicol, which constitutes the bulk of the oil. It was identified hj means of its oxidation to homoanisic acid and anisic acid, also bj^ inversion into its isomer anethol. Judging from a methoxy determination according to Zeisel's method, the Reunion oil contains (J7.8 p. c. of methyl chavicol. Linalool was not contained in this oil. From a small sample of Reunion oil Dupont and Guerlain obtained a crystalline substance, m. p. 6-1—65°, the amount of wliich was too small for investigation. The oil from a large leaved variety of 0. basilieuni known to the natives as Seln.sih Meknh, contained 80—40 p. c. of eugenol." 381. Oil of Mosla Japonica. According to Shimoyama'^ (1892), Moslit japonicn Maxim, which is indigenous to Japan yields, when dry, 2,18 p. c. of a reddish-brown, laevogyrate oil, the specific gravity of which is 0.820 (?). It contains 44 p. c. of thymol and a fraction 170— 1M0°, probablj- cymene. ^) .Jourii. cle Phann.. II, 17, ii. G47. 2) Liebig'K Aunalen, 14, p. 75. 3) Compt. renrl., 12+, p. ;!l)0: Bull. Snc. cliiin.. Ill, I'.t, p. l.jl. i) Archiv d. Phann., 285, p. 170. = ) The pi-e.senfe of cineol in oil ot sweet basil was previousl.v demonstrated by Hir.schsohn in 1S93 by means of the iodole reaction ( Pharm. Zeitschr, t. liussl., 32, p. -tl9). 6) Annual report of the botanical garden at Biutenzorg, ISiiS p 28- Bericht von S. & Co., Apr. 1900, p. 5. J) Apt. Ztg-., 7, p. 4:19: .fahresb. t. I'harni., ls<)2, p. 46,5, where the plant is named .Mosula, whereas Hart wig (Ilie neuen Ai-zneidrogen aus deni Pflanzenreiche, p. 220) designates it Morula, Oils of the Labiatae. 661 382. Oil of Dittany. The dry herb of the North American Cunila mariana L. yields 0.7 p. c. of a reddish-yellow oil, sp. gr. O.Olij, the odor of which resembles oil of thyme. A preliminary investigation shows it to contain 40 p. c. of phenol, probably thymol.^ 383. Oil of Lophantus. The oil of L'lplntntus anisatus Forst. has a pure, pleasant anise odor, reminding somewhat of the honey-like odor of Solidago odora Ait. Sp. gr. 0.948 at 20°; «i, = — 7°10'.2 384. Oil of Pycnanthemum Lauceolatutn. The odor of the oil distilled from the herb of Pycnanthemum lan- ceolatum Pursh 3 is scarcely to be distinguished from that of American pennyroyal oil. Sp. gr. 0.918*— 0.9:56 5 at 15°; 0.914—0.933 at 20°; aD= — 0.566° to -f 11. 083°, 8 According to Correll " it contains 7 — 9 p. c. of carvacrol (carvacrol sulphonic acid. m. p. 56 — 57°, dicarvacrol, ra. p. 145 — 147°). The oil deprived of phenol distills between 180 — 230°. The analysis of fraction 220—230° (.sp. gr. 0.922 at 20°, ['/.]d = + 14.88°) corresponded with the formula CioHkiO and indicated the presence of pulegone. Its identity with pulegone was established by Alden " by means of the pulegone oxime hydrate melting at 151°. The molten oxime, after having been allowed to cool, then melted at 117 — 118°. The melting point of the pulegone oxime hydrate of Beckmann and Pleissner melts at 156 — 157°, that of the normal oxime of Wallach at 118°. 385. Oil of Pycnanthemum Incanum. The dried herb of the North American labiate, Pycnanthemum incanum Michx. yields 0.98 p. c. of a reddish-yellow oiK with a strongly aromatic odor, sp. gr. 0.935. It produ/es a clear solution with twice its volume of 70 p. c. alcohol. 1) Bericlit von S. & Co., Oct. 1893, p. 44; comp. al.so Millemann, Am, .lourn. Pharm., .38, p. 495. 2) Bericht voa S. & Co., Apr. 1898, p. ,58, 3) Pycnanthemum Linceolatum and Pycnanthemum linifolium were formerly regarded aH one species and described as Thymus virginlciis L. ^) Amer, ,Tourn. Pharm,, 66, p, 6,5, 5) Pliarm, Review, 14, p, 32, 6) I'harm, Review, 16, p, 414, 7) Bericht von S. & Co,, Oct. 1893, p. 45, W>2 Special Purl. 386. Oil of Fabiana Imbricata. Kunz-Kra,usei obtained from the ethereal extract of the leaves of Fahhina imbriccitn Ruiz et Pavon, by Bteam distillation and shaking out the distillate with ether, a small amount of volatile oil. Upon distillation a small fraction came over at 180°, the principal fraction boiling at 27.")°. Upon analysis this fraction had the composition 0.541^900+ and was called fabiaiiol. 387. Oil of Chione Glabra. ObiCtIN. On account of the aromatic odor of its flowers, Chione glabra, a tree belonging to the Ruhhu-eae. is known as Violette on the West Indian island Grena(]a. On P(.)rto Rico it is known as Palo bianco. The wood and the bark possess an unpleasant, faecal odor which gradual!}' disappears when exposed to the air. Preparatiox and Properties. Distilled with water vapor the bark, according to Paul and Cowiily^ yields l..j p. c. of a light yellow (jil which i.s heavier than water and which, when cooled t\ Miiller, Archiv d. Pharm., 9.5 aH46), p. L'^S. 2) Joiirn. Chem. Soc, 17, p. 1; .Jahresb. f. Chem., 1803, p. ~>i'i. 60i Special Part. Thuring'ian root, Schimmel & Co. obtained 0.5—0.9 p. c, from Dutch root about 1 p. c. of oil. The strongly acid aqueous distillate contains valerianic acid which presumably is formed from the bornji valerianate of the oil during the process of distillation. Properties. When fully distilled, oil of valerian is a yellowish-green to brownish-yellow liquid which is slightly acid, and possesses a pene- trating, characteristic, not unpleasant odor. Old oil is dark brown and viscid. It has a strongly acid reaction and, on ac(/ount of the la7'ge amount of free valerianic acid it contains, has a disagreeable odor. The stearoptene which occasionally separates from old oil consists of borneol. As a rule tlie sp. gr. varies from 0.93 to 0.96. Abnormally light were the oils of Oliviero mentioned under '"Composition.'' They were distilled from the fresh roots of plants growing wild in the Departements Vosges and Ardennes. Their sp. gr. is given as 0.880 — 0.912 at 0°, corresponding to a density 0.87."i — 0.900 at 15°. Oil of valerian is laevog-yrate, ao^ — S to — 13°. Acid number = 2(» — 50; ester number = 80—100; saponification number = 100— 150. Composition. Although oil of valerian has been examined repeatedly since the beginning of this century,' its composition has become known but comparatively recently through the inve.stigations of Bruylants^ in 1878 and Oliviero* in 1893. Of the con.stituents valerianic acid, which derives its name from the plant, is longest known. It was also known that upon oxidation of the oil camphor results. For the .systematic investigations of the oil the esters must first be saponified so that the acids which otherwise result during the process of fractionation do not act on the terpenes and terpene alcohols. The saponified oil begins to boil at 155° and up to 100° a liquid passes over which in its jjhysical properties corresponds to 1-pinene. but which consists of two terpenes. By passing dry hydrogen i-hloride into this fraction a ' solid dextrogyrate hydrochloride results, which when boiled with potassium acetate is in part decomposed to 1-eamphene. The part not affec^ted consists of laevogyrate pinene hydrochloride. i| Trommsdorff (1MI)9). Tromm.sdurft"s .lourii. d. Pliariii., Is, 1, p. .^ ; Llebig's .\n- rialen, 6 (18.^3), p. 176, iind 10 (18.34), p. 218. — Ettling (18341, ilMd.. 9," 40. — Gerhardt &, Cahours (1841). Ann. de Chim. et Phys.. Ill, 1, (j. (50. — Roehleder (1842), Liebis's Annalen, 44, p. 1. — Gephardt (1843), ibid., 4.5. ]). 2',t, and .Journ. f. prakt! Ciiem., 2T (18421, p. 124. — Pierlot (184.T). Ann. do Chim. c't I'hvs., Ill, 14, p. 29,'-> and m (18.59). p. 291. ■-'I Herichte, 11, ji. 4:52. 3) Conii)t. i-end., 117, p. 109(j; Bull. Soc. chim., III. 11, p. l;5ll; 13. p. 917. Oils of the Valerianaceai'. 665 The lowest fraction, therefore, consists of 1-camphenei and 1-pinene. Oliviero is of the opinion that "citrene" (?) is also present, but furnishes no positive proof. When that portion of the oil which distills under ordinary pressure above 180° is distilled under reduced pressure, fraction 130—140° under 50 mm. pressure largely solidifies on a(.'eount of the 1-borneol ]5resent. This alcohol is present in the oil as esters of formic, acetic, butyric and valerianic acids, the largest part being combined with valerianic acid. According to Gerock- (18!)2), the oil contains about 9.5 p. c. of valeri- anic acid ester and 1 p. c. each of the esters of the other three acids. Fraction 132 — 140° (50 mm.) probably contains terpineol, which could not be isolated in the crystalline state. The formation of dipen- tene dihydrochloride, however, renders its presence probable. Fraction 160 — 165° (50 mm.) contains a laevogyrate sesquiterpene, C15H24, and fraction 190° a substance Ci.^HaeO which, judging from its behavior to benzoic acid anhydride and hydrochloric acid, is an alcohol. From the water obtained in washing the oil after saponification, Oliviero obtained a crystalline alcohol of the formula C10H00O2. It is strongly laevogyrate and melts at 132°. According to Fliickiger,3 the highest fractions (300°) are blue in color. Basing his claims merely on an elementary analysis, Bruylauts* supposes fraction 285 — 290° to contain bornyl ether or bornyl oxide C10H17. .C10H17. an assertion still wanting proof. Mexican Oil of Valerian. A Mexican valerian root, probably derived from Valfviaria mexicanii D. C. was distilled by Schimmel «&: Co." The distillation yielded only a clear water from which no oil separated. Only after cohobation of the aqueous distillate an oily liquid with disagreeable odor and sp. gr. 0.949 at 15° was obtained. It was optically inactive and when shaken with soda solution was dissolved with the exception of a few flakes. Titra- tion with alcoholic potassa yielded as acid number 415, corresponding to 89 p. c. of valerianic acid hydrate C.-,Hio02 + H2O. 1) The f;laini made by Oliviero that the oils of valerian imrl spike are the first in which camphene has been found is not correct. The occurrence of camphene in citronella oil and ginffer oil \v>\h reported iu the Bericht of Schimmel & Co. of October 1893, pp. 11 and 22. The first publication of Oliviero (also that of Bouchardat on oil of spike) appeared in the Comptes rendue dated December 2.3, 189.3. 2) .Tourn. d. Pharm. f. Elsiss-Lothringen, 19, p. 82, 3) Archiv d. Piiarm,, 209, p. 204. 4) Berlchte, 11, p. 4.52, 5) Bericht von S. & Co., Apr. 1897, p. 47. 666 Spechil Part. Mexican valerian root, therefore, yields scarcely a ti-ace of volatile oil, but only free valerianic acid. Inasmuch as the root has a strong odor of the acid, it is to be supposed that it is contained as such in the root and is not formed during- the process of distillation. 390. Oil of Kesso Root. Orichn axd Preparation. Japanese valerian root is not derived, as was first supposed, from P:itiuii;h scHhiosaefolin Link, but from VnlerhinA oifieimilis L. var. fingustitolin iliq.. which is known as Ke.sso or Kanokoso in Japan. Upon distillation it yields S p. c. of oil and is. therefore, much richer in oil than the common valerian root. Properties. Tne odor of the (iptically laevog-yrate oil is barely distinguishable from that of valerian oil. The oil, however, is much heavier, having a sp. gr. of 0.990 — 0.99(3. Composition. In composition also kesso oil closely resembles valerian oil for it contains almost all constituents found in the latter. In addition it I'ontains kessyl acetate which causes the higher specific gravity (Bertram and Ciildemeister,' 1S90). When kesso oil is distilled a first fraction is obtained that is strongly acid, has the disagreeable odor of decayed cheese and contains acetic and valerianic acids and probably valerianic aldehyde. Fraction 15.") — l(>()°i5 .strongly laevogyrate and like the corresponding fraction of valerian oil contains 1-pinene (nitrosopinene. m. p. 101°) and l-camphene^ (isoborneol, m. p 212°). Fraction 170 — 1,S0° contains dipentene (tetra bromide, m. p. 12H°). It is questionable whether this terpene is an original constituent of the oil or whether it is formed by the action of the acids on pinene or teqiineol. The borneol oi. kesso oil. like that of valerian oil. is laevogyrate and is present as acetate and isovalerianate. Bornyl formate found in oil of valerian is not contained in kesso oil. Terpineol was identified by the formation of di])entene dihydriodide (m, p. 7(j°) frcnii fraction 200 — 220°. Other reactions, more characteristic for terpineol, could not be applied on account of the borneol which is difticult to remove. Fraction 2(;o — 2.S0° had a decided sesquiterpene odor l)Ut did not yield a solid hydrochloride. The liigiiest boiling fractions contain in addition to a. blue oil, the acetate of an alcohol (Ji+Il24t>2, the kessyl acetate. 1) .Archiv d. PhiiDii.. 22S, p. 48:i. -'j .Journ. f. pvakt. ('hem.. II. 4VI. p. IS. Oils of the Valeriauaefa^e. 667 Kessyl acetate, Ci4H2302COCH;3. is a viscid liquid wiiicli does not solidify at —20°. Under 15—16 mm. pressure it boils between 178 and 179° ; under atmosperic pressure at about 300° with slight decom- position ; aj3 = — 70°<)'. Kessj'l alcohol, C14H24O2, crArstallizes in iai'^e. well formed crystals of the rhombic system. It is odorless, insoluble in water, readily soluble in alcohol, ether, chloroform, benzene and petroleum ether. It melts at 85° and under 11 mm. pressure boils between 155 and 15(3°, under ordinary pressure between 300 and 302°. Its alcoholic solution is laevogyrate. Upon oxidation with potas.sium bichromate and sulphuric acid a substance with two hydrogen atoms less is obtained, which crj'stallizes in thick needles melting at 104—105° and turns the plane of polarized light to the left. 391. Oil of Valeriana Celtica. The small Valeriiina celtica L. of the Styrian alps formerly yielded a drug known as Spica celtica. (Ger. Alpen.vpik. celtischev Sp>ik). The root yields upon distillation 1..5 — 1.75 p. c. of volatile oil of a strong odor reminding more of Roman chamomile and pat(.'houljr than of valerian. 8p. gr. 0.9G7; boiling temperature 250 — 300°.' 393. Oil of Nardostachys Jatatnansi. The rhizomes of Nardostachys JHtiimnusi D. (J. {Piitrinia jatiimansi Wallich) and of N. grnutJiflom D. C, (Family Vfilerinnaceae) which are intligenous to the Himalaya mountains of northern India have an odor reminding faintly of musk but luore strongly of patchouly. On account of its fragrance this root was highly prized during antiquity and was used for perfuming ointiuents and fatty oils Later other roots were used as substitutes, notably' that of Ferula surnhul Hook. fil. (p. 576) and still later that of Valeriana celtica L. (see above). According to Kemp- the root of Narclosta.chys jatainansi D. C. yields upon distillation 1 p. c. of a volatile oil of light yellow color. Sp. gr. (t.!)748 at 22°; «„ = - 19°5'. 393. Oil of Dog Fennel. " Eupatorium foeuiculaceum Willd. (Family Compositae) known as dog fennel on account of its fennel-like leaves, is found along tlie Virginia coast and in other southern states of North America. An oil 1) Bei-icht von S. & Co.. Oct. 18S7, P- ■■!'>• 2) Pharniacdffraphia indica. vol. 2, p. li87. 668 Special Part. distilled in Florida from the entire plant was light in color and had an aromatic, pepper-like odor not at all resembling fennel. Sp. gr. 0.935; «D= + 17°50'. It contained a large amount of phellandrene.i 394. Oil of Ageratum Conyzoides. This oil was distilled in the Botanical Garden at Buitenzorg. The presence of methyl alcohol in the aqueous distillate was observed. Sp. gr. 1.015 at 27.5°: optical rotation —5.5° (in 200 mm. tube). It boils at about 26(»° and probably contains sesquiterpene. 2 395. Oil of Golden Rod. In the United States ea,st of the Rocky Mountains there are found about fifty species of Solklngo known as golden rod, some of which are so common as to be regarded as weeds. Several possess more or less aromatic properties. The oil of golden rod so-called is derived from SoUfhigo odora Aiton. It has a strongly aromatic, but not especially pleasant odor and a sp. gr. of ().i)G;i.« The fresh, flowering herb of Solidago canadensis L. jnelds 0.68 p. c. of oil. It is of a hght yellow color and has a very agreeable, sweetly aromatic odor. Sp. gr. 0.859; «d = — 11° 10'.* This oil contains about 85 p. c. of terpenes, especially pinene with some phellandrene and dipentene, possibly also limonene. The higher boiling poT'tions consist of borneol (total 9.2 p. c), bornyl acetate (3.1 p. c.) and cadinene. It is remarkable that this golden rod oil should so closely resemble, as to composition, the pinene needle oils of an entirely different family. ^ The odor of the oil of Solidago rugosa Mill, is said to resemble that of origanum oil. 396. Oil of Erigeron (Fleabane). Oteniii Erigeroiitis.—Erigeroiiol. — Essence d'Erigeron. Origin. Erigeron eaniideusis L. is a very common weed which is known in America as fleabane, horseweed or butterweed. It is frequently found in peppermint fields. The fresh herb jnelds upon distillation l».2— 0.4 p. c. of oil which finds limited medical application in the United States and which was made official in the U. S. Pharma- copoeia of 1890. 1) Bericht von S. & Co., Apr. ISW), p. 70. i) Ibiileni. Apr. 180-t, p. 57. 2) Ibiderii, Apr. 1SH8, p. 57. s) Hericht von S. & Co., iVpr. 1897, p. 5:',. 3) Ibidem, Out. 1891, p. -tO. Oils of the Compositne. 069 Properties. When fresh, erigeron oil is a colorless or light yellow, mobile liquid, and possesses a peculiar aromatic, persistent odor and a somewhat prickly taste. Exposed to the air it rapidly resinifies and becomes viscid and darker. Sp. gr. 0.830—0.870; «D = + r)2°.i With an equal volume of 90 p. c. alcohol it forms a clear solution. Composition. Erigeron oil boils almost completely at IT-j'^ (Power^) and consists very largely of d-limonene. Vigier and CloezS (1881) prepared a dihydrochloride, which Beilstein and AViegand^ (1882) found to melt at 47 — 48°; Wallach^ (1885) prepared the tetrabromide melt- ing at 10-4 — 10.5°; Meissiier" (1893) the nitrosochlorides, and from the '.i-iiitrosochloride the benzylamine base melting at 90 — 92°. In fraction 20."> — 210° Hunkel"^ found terpineol which he identified by meg-ns of its nitrosochloride and the nitrolpiperidine base melting at l.-)9— 160°. 397. Oil of Blumea Balsamifera. The semi-shrub-like composite Blumea Imkiimifera D. C. is indigenous to India and is found from the Himalayas to Singapore and in the Malay Archipelago. It likewise grows in the Islands Hai-nan and Formosa. In Hai-nan and in the Chinese province Kwang-tung con- siderable quantities of the so-called Ngai camphor, Ngai-fen, are obtained from it by distillation. From Hoi-han on Hai-nan annually 15,000 lbs. are said to be exported. The crude Ngai cam])hor is rectified in Canton and is then called Ngni-p-'ien (Holmes §). In Burma, also this camphor is prepared. » Ngai camphor is u.sed in China for ritualistic and medicinal purposes. It is also added to the better qualities of India ink.^" Formerlj^ this camphor was rarely brought to Europe. In 1895 Schimmel & Co. obtained a sample in the form of a yellowish-white,- crumbly mass consisting almost entirely of 1-borneol.ii (See p. 143.) The identity of Ngai camphor with 1-borneol was first established in 1874 by both Plowman 1^ and Fliickiger.i'^ i| Bericht von S. & Co., Oct. 1894, «) Biichner's Neiies Kepert. f. d. Phfirni., 7H. 28, p. .321; Hanbnry, Science Papers, 1S76, -'I Phariii. Rundschau, .■), p. 201. p. .394. •i) .lourn. de Pharni., V, 4. p. 236. if' ) Pharmacognosie, 1891 , p. l.jS: Phar- •i) Berichte, 15, p. 28.54. macographia, 1879, p. .518. = 1 Liebig'K Annalen, 227, p. 292. n) Bericht von S. &Co., Apr. 1894, p. 74. fi| .4mer. .Journ. Pharm., 6.5, p. 420. 12) Pharm. Journ., Ill, 4, p. 710; Neues 7) I'harm. Rundschau. 13. p. 137. Repert. f. d. Pharm., 23, p. 325. 8) Pharm. .Tourn., Ill, 21, jp. 1150. 13) Pharni. .Tourn., Ill, 4. p. 829. 070 Spi-cial Fart. 398. Oil of Blumea Lacera. BlnniPri lacpiH D. C. is a perennial plant which iss widely diHtributed in India. It possesses a strong camphor-like odor and is therefore used by the natives against flies and other insects. Dymocki obtained by the distillation of I.IO lbs. of fresh, flowering herb about 2 oz. of a light yellow oil, sp. gr. 0.9144 at 26.7° and ..(D = — (>()°. 399. Oil of Helichrysum Stoechas. The oil of the flowering herb of Helichrynum stoechas D. C. is used in Spain as a remedj' against di.seases of the bladder and kidneys. It has the odor of inferior coniferous oils and about three-fourths boil between 155 and 17(t°, the remaining fourth between 170 and 26n°. Pinene is probably the principal constituent. ^ 400. Oil of Elecampane. Olenni Heleiiii. — Alantol. — Essence de Racine d'Aunee. OHKiiN AND Hlstohy. Upon distillation of elecampane, the root of Inula helpniuin L., with water vapor, 1 — 2 p. c. of a solid, crystalline mass permeateil by some liquid oil is obtained. Aqueous distillates were used medicinally during the middle ages. Oleum radicis lielenii is first mentioned in the Frankfurt ordinance of 1582. Oil of elecampane is used principally for the preparation of alanto-lactone, the helenin of Gerhardts (1839). Composition-. Oil of elecampane consists almost entirely of alanto- lactone with which are mixed small amounts of alantolic acid, alautol and a. sulistani'e (CoHsOfx. the helenin^ of Kallen." /O Alanto-lactone Ci+HooC | was formerly regarded bv Kallen as CO alantolic; acid anhydride. Bredt and Posth recognized its character as lactone and changed the name correspondingly. 1) Phai-m, .Journ., Ill, 14, p. DM."). 2) Bfricht von S. & Cci., Oct. 1889, p. ,">4. 31 Ann. de Chini. et Pli.ys., II, 72, p. ll.;3; anil III, 12, p. 188. — Liebig's Ann.tD = — 2()°.i 403. Oil of Roman Chatnotnile. Oleum Chainoiiiillae Romanae. Oleam Aiithemidis. — Roinisch Kaiiiilleiiol. — Essence de Caniomille Roiiiaine. Oeic;l\ and History. Anthemis nohilis L. occurs wild only in scattered districts of western Europe. In Europe and America it is cultivated as garden plant and for commercial purposes. Occasionally it escapes cultivation. Owing to the similarity of several .species of Anthenii.s, Chrysanthemum and Matricaria it is not known what plant was designated as Anthemis by the writers of antiquity. In the German treatises on distillation the common chamomile seems to have been preferred for medicinal purposes, whereas in England the Roman cliamomile was almost exclusively used as chamomile flowers. Distilled oil of Roman chamomile is first mentioned along with Oleum chamomilhie rulg-ai'is in the price ordinance of Frankfurt for 1587. Peeparation. Up to quite i-ecent times Roman chamomile wa,9 cultivated to a considerable extent in the neighborhood of Leipzig, but has been dropped for several years because no longer profitable. At the present time the oil is distflled principally in Mitcham near London, where the plant is cultivated and where it also grows wild. The dried flowers yield about 0.8—1 p. c. of oil. Properties. Freshly distilled Ronmii chamomile oil has a light blue color, which under the influence of air and light changes to greenish and brownish-yellow. The odor is strong but pleasant, the taste burning. Sp. gr. O.OO.'") to 0.915, «d = + 1 to +3° (Umney,^ 1895). The oil has usually a faintly acid reaction, saponification number 250—300. As a, rule it forms a clear solution with (> parts of 70 p. c. i| Bericht von H. & Co., Oct. l.s'.)4, p. 73. 2) Pharin. Joiira., Ill, 25, p. S)i9. Oils of the Cornpositae. 673 alcohol. A lesser solubility is occasionally due to a larger paraftin ■content, and does not necessarih^ indicate adulteration. Composition. The oil of Roman chamomile consists principally of a mixture of esters of butj^ric acid, and the isomeric angelic and tiglinici- acids which are present as esters of isobutyl, amyl a,nd hexyl alcohols. Angelic acid was discovered in the oil by Gerhardt^ in 1848, and has thus become readily accessible to chemists. The other statements by Gerhardt concerning the presence of angelic aldehyde and a terpene boiling at 175°, chaniomillene, have been shown to be wrong. Demar(;ay3 in 1873 showed that angelic acid is not free but com- bined with butyl and amyl alcohols. He supposed that he had found valerianic acid, but this was not verified by later investigators. More detailed examinations of the oil were made by Fittig and Kopp"t in 1876 and by Fittig and Kobig^ in 1879. Kopp saponified the oil and isolated and identified the acids, whereas Kiibig fractionated the oil and examined the various fractions. The two investigations, therefore, supplement each other. Upon repeated fractionation, five large fractions are obtained : 1) 147—118°; 2) 177—177.5°; 3) 200—201°; 4) 204—205°; 5) above 220° decomposition sets in and atiout one-third of the oil remains in the residue. Fraction 1, b. p. 147 — 148°, contains an ester of isobutyric acid, probably that of isobutyl alcohol, C4H7O . OC4H9, with which is mixed a small amount of a hydrocarbon. In the lowest fraction of the acids, 150 — 160°, after separation of the alcohols, a white amorphous powder separated which was not isolated in a pure state but which, judging from its properties, consisted of methacrylic acid CH2 :C(CH3)C00H. The first fraction of the non-saponified oil, therefoi'e, may be regarded as an ester of this acid. Fraction 2 consists of fairly pure angelic acid isobutyl ester, C5H7O . OC4H9. The isobutyl alcohol obtained from it boils at 107—108°, the angelic acid melted at 45°. Fraction 3, b. p. 200 — 201°, consisted of a colorless, rather viscid oil having the odor of chamomile. Upon saponification it was resolved 1) It 18 doubtful whether tiglinlc acid is contained a.s such in the oil or is formed from the angelic acid. 2) Compt. rend., 26, p. 225; Ann. de Chim. et Phys., Ill, 24, p. 96; LielMg's Annalen. 67, p. 2.35; .Journal f. prakt. Chemie, 45, p. 235. 3) Compt. rend., 77, p. .360; ibid,, 80, p. 1400. *) Berichte, 9, p. 1195; ibid,, 10, p. 51.3. ■ 5) Liebig's Annalen, 195, pp. 79, 81 and 92. 43 <574 Special Part. into inactive amj^l alcohol of fermentation, C5H12O, b. p. 129—180°, and anf;-elie acid. It, therefore, consists of angelic acid amyl ester, C5H7O.OC5H11. Fraction 1 consists of a mixture of the amyl esters of angelic and tiglinic acids. Fraction 5. The portion above 220° was saponified with potas.sa. Among the volatile acid.s, tiglinic and angelic acids were found. The oil distilled from the lye was separated into a smaller fraction, 152 — 15:)°, and into a larger one, 218. -5— 214. .5°. Fraction l.'J2 — 1.")8° upon analysis revealed itself as a hexyl alcohol' which upon oxidation yielded a capronic acid. VanKomburghi showed in 1886 that this acid is identical with methyl ethy] propionic acid, and that the alcohol, which was also prepared synthetically, has the formula C2H.5(CH3)CH . CH2 . CH2OH. The methyl ethyl propyl alcohol of Eoman chamomile oil boils at 154°, has a sp. gr. of 0.829 and is dextro- g,yrate, [«]d = +8.2°, whereas the sj-iithetic alcohol is optically inactive. The oil contains about 4 p. c. of this hexyl alcohol. Fraction 218.5 — 214.5° is a colorless, viscid liquid of camphor-like- odor, which does not distill without decomposition under ordinary pressure. It is isomeric with camphor, having the formula C'ioHibO, and was named anthemol. The acetate of this alcohol boils at 234 — 23(1°, and upon saponifiieation yields the original alcohol. Chromic acid destroys the alcohol entirely, dilute nitric acid oxidizes it to ])-toluic and terephthalic acids, also a more soluble acid, possibly terebinic acid. There remains to be mentioned that Naudin- obtained from the- flowers of Roman chamomile, by the extraction with petroleum ether a parafBn, "anthemene", CisHaa, which melted at (;8— 64°. 404. Oil of Anthemis Cotula. Dpon distillation of the fresh flowers of Anthemi.s cotula L. and shaking the aqueous distillate with ether, Hurd^ in 1885 obtained 0.013 p. c. of oil. The entire fresh plant, when treated in like manner,, yielded 0.01 p. c. of a reddish oil with acid reaction and bitter taste;, sp. gr. 0.858 at 26°. Upon cooling a crystalline acid separated, whicli melted at 58° after puriflcation. The same acid was obtained upon saponification of the oil. The saponified oil boiled between 185—290°' and left a residue of 20 p. c. 1) Rue. lies Trav. chiiri. des Paye-Bas, ,",, 2) Bull. Scic. cliim., II, 4,1, p. 4:I°, boils at 204° and deviates the ray of polarized light as far to the left, ([«]d^ — 83.1°) as ordinary camphor does to the right. Feverfew cultivated in the neighborhood of Leipzig yielded 0.068 p. e. of oil, sp. gr. 0.960. At ordinary temperature a considerable quantity of liexagoual crystals separated, which, when recrystallized from petroleum etlier, melted at 203—204° and consisted of 1-borneol, £«]d^ — 36°. Camphor was not to be found in the oil.s It seems probable that the oil examined by Dessaignes and Chautard also container! borneol besides camphor, for the mother liquor from the crystals, after treatment with nitric acid, j'ielded more camphcjr. It is but rational to assume that the furthei- amounts of camphor obtained after the treatment with nitric acid owed their origin to the borneol present. According to Chautard* the oil further contains a terpene boiling lielow 200°, which did not yield a solid derivative with hydrogen •chloride; and a liquid dextrogyrate constituent boiling above 200° which contained more oxygen than camphor. In connection with the oil mentioned above, Schimmel & Co. obtained the saponification Tiumber 131 which indicates a, rather high ester content. 412. Oil of Tansy. Oleum Tanaceti. — Raiiifarnol. — Essence de Taiiaisie. Oeigix and History. Taiiacetum vulgareL,. {Clirvsanthemum taiiH- cetum Karsch) is found wild in most European countries, likewise in the Atlantic states of North America, and is also cultivated. It is one of the strongly aromatic composites. The oil, which is especially contained 1) l-Camphor occurs also in one other oil, namely in oil of tansy. 2) .Tourn. f. prakt. Chem., 45, p. 4.5. 3| Bericht von S. & Co., Oct. 1894, p. 71. i) .Journ. de Pliarrn., Ill, 44, p. 13; Jahresber. f Chemie, 185.3, p. 555. 680 Si>eei,il Part. in the flowers, has been used as an anthelminthie since the middle ages. In the United States the leaves und flowers are oificial. The distilled water from the flowers and leaves was a common remedy during the sixteenth and seventeenth centuries. The oil is first mentioned in the price ordinance of Frankfurt for 1582 and in the Dispensatorium Noricum of 1589. The oil was first examined by Per.sozi in 1841. Pebpabation. Fresh, flowering tansy yields upon distillation 0.1 to 0.2, dry herb 0.2—0.8 p. c. of oil.^ The commercial oil is obtained principally from North America. It should be noted that the oil from different sources varies somewhat. Pkoperties. Oil of tansy is a yellowish liquid, which becomes brown under the influence of air and light. The sp. gr. of the oil from fresh herb is 0.925—0.940, that from dried herb 0.955; an = + 30 to +4.5°. The American oil, when pure, forms a clear solution with 3 parts of 70 p. c. alcohol. An oil distilled in Germany gave no clear solution with 70 p. c. alcohol. An English oil from cultivated tansy ^ had but little resemblance, as- to odor, to ordinary oil of tansy but resembled oil of rosemary and had a decided odor of camphor ; upon evaporation of the oil a delicate- ambra odor was finally developed. Its camphor c-ontent was so large- that a part of it crystallized out at 0°. Very remarkable was its optical behavior for it was .stronglj' laevogj^rate, «d^ — 27°. Composition. The bulk of oil of tansy consists of thujone or tana- cetone to which the oil owes its characteristic odor. It was first isolated in a pure state by Brujdants* in 1878. If the oil is shaken according- to his directions with an equal volume of sodium acid sulphite solution and two parts of alcohol, a compound CioHieO.XaHSOs is formed upon prolonged standing, from which the pure thujone can be separated by means of soda. That this substance, which Bruylants regarded as- an aldehyde and named tanaeetyl hydride, is a ketone and identical with the thujone isolated by Wallach from thuja oil, was showa by Semmler.5 Properties and derivatives of thujone are described on p. 167. 1) Compt. rend., 13, p. 436; .lourn. tUr prakt. Chem., 25, pp. 55, (iO. 2) The yield mentioned by LepplR (Berichte, 15, p. 10S8, Ref.), viz.. 1.49 p. c. from the flowers and 0.66 p. c. trom the herb can not well refer to the oil obtained by- dietillation. .1) Bericht von S. & Co., Oct. 1895, p. 35. i) Berichte, 11. p. 449. 5) Berichte, 25, p. 3343. Oils of the Coinj/ositae. 681 Fraction 203 — 205° upon oxidation with eliromic acid yielded a small amount of camphor. Brujlants supposed that this fraction contained the alcohol CioHisO corresponding to thujone and regarded the camphor as its oxidation product. Inasmuch as it is now known that thujyl alcohol does not yield camphor, this ketone must be regarded either as a constituent of the oil or as a product of oxidation from some substance other than thujyl alcohol. Persozi (1841), also Vohl^ (1853) had observed that the oil, after having been oxidized Avith chromic acid, contained camphor. Persoz did not answer the question whether this camphor was contained in the oil as such or whether it was a product of the oxidation. In order to decide this question Sehimmel & Co. removed the thujone as completely as possible by shaking with bisulphite solution, and fractionated the remaining oil. At 205° the distillate congealed partly in the receiver. The crystalline mass was separated by suction and cryistallized from 80 p. c. alcohol. Odor and other properties indicated a mixture of camphor and borneol. For their .separation Haller's method 3 was employed and a relatively large amount of camphor with little borneol obtained. The camphor was identified by means of the oxime melting at 116°. The optical properties showed that it was not the common dextro camphor, but the very rare laevo camphor. The amount of borneol was too small to determine its rotation. It remains to be determined whether thujyl alcohol is contained in the oil, its presence being probable according to Bruylants ; also whether the terpene of Bruylants, boiling about 160°, is pinene or camphene. According to Peyraud,* oil of tansy is exceedingly poisonous. In animals it produces a condition similar to rabies, la rage tanacetique. 4-13. Oil of Tanacetum Balsamita. The fresh, flowering herb of Tanacetum balsamita L. yielded upon distillation 0.064 p. c. of oil.s The odor is agreeably balsamic, but little charactertstic, reminding of tansy. Sp. gr. 0.943—0.949; aD = — 43°40' to — 53° 48'; sap. number = 21. In the cold, paraffin-like crystals are formed at the surface. The oil was not soluble in 80 p. c. alcohol. With 1—2 parts of 90 p. c. alcohol, however, it gave a clear solution, but this was rendered turbid upon the addition of more alcohol, white flakes (paraffin?) separating. The oil boiled between 207—283°. 1) Compt. rend., 13, p. 4.3« ; Liebiff'e 3) Compt. rend., 108, p. 1808. Annalen, 44, p. .313; .Journ. f. prakt. -tl Compt. rend., 103. p. .')2.5. Chem., 25, p. .3.'j. ^) Bericht von S. & Co., Oct. 1897, p. 66. 2) Archiv d. Pharm., 124, p. 16. ■682 Special Part. 4.14. Kiku Oil. Kiku oil is distilled in large quantities in the western part of Japan from tlie leaves and flowers of Pyrethmm iudicum Cass. (Jap. Ahura- Kuku). The production in 1887 amounted to about 1,400 k. It is used as a popular remedy.^ The oil of the leaves is colorless and has a camphoraceous odor reminding somewhat of eucalyptus. Sp. gr. 0.885; boiling temperature 165-17.'"i°. The oil of the flowers is likewise colorless and has an unpleasant odor. The first fraction distilling at about 180° has a pleasant odor, the higher fractions are camphoraceous but not agreeable. 2 415. Oil of Artemisia Vulgaris. Avtemishi vulgaris L. (Ger. Beifuss) is a common weed found along hedges and roadsides and contains volatile oil in all its parts, the root yielding 0.1 p. c., the' herb 0.2 p. c. The root oil is greenish-yellow, butyraceous, cry.stalline.s It has a nauseating, bitter taste, first burning then cooling. The oil from the herb is but little chara^teristii:' as to oilor. Hp. gr. 0.007. According to an observation made in the laboratory of Schimmel cV: t'o. it contains cineol. 416. Oil of Estragon. Oleum Draciiiiciili. — Esdrag:oiiol. — Essence d'Es ragon. Origin. Estragon oil. which is used in the preparation of aromatic vinegars, is di.stilled from the fiowering herb of Arteniisi;i drneunculus h. The dry herb yields 0,2.5—0.8 p. c. ; the fresh herb 0.1—0.4 p. c. Properties. Estragon oil is a c(.(lorless to yellowish-green liquid of peculiar, anise-like odor and strongly aromatic, but not sweetish taste. The sp. gr. varies greatly, 0.900—0.945. An oil distilled from the diy Thuringian herb had a sp. gr. of but 0.890. The oil is dextrogyrate, «D = + 2 to +9°. It is soluble in 10 parts 'of 80 j). c. alcohol. Composition. Estragon oil was first examined by Laurent* in 1842. Upon oxidation he obtained an acid melting at 175° which he termed ■dragonic acid. Gerhardt^ (1844) ili>v ISSS, p. +(;. 2) Berlcht von S. & Co., Apr. 1887, p. :!7. 3) Bretz & Elienon, Taschenbuch fiir Cheinikpr und Apotheker, lS2(i, p. 61. *) Liebip:'.'^ Anualen, +4, p. 31,8. 5) Conipt. rend., I'.t, p. 489; I,iebiff'H .Vnnalen, ,^^2, p. 401. Oils of the Compositae. 683 and showed that estragon oil behaved toward reagents hke anise oil, and concluded that the two oils were identical. Since then anethol was regarded as the principal constituent of estragon oil. AVhen in 1892 Schimmel & Go. found methj'l chavicol (p-niethoxv alljd phenol), the isomer of anethol (p-methoxy propenyl phenol) for the first time in a volatile oil, viz. oil of anise bark, the e.stragon-like odor attracted attention. This suggested a new investigation of estragon oil which showed that the bulk of this oil consists of methyl chavicol.' Upon energetic oxidation, methyl chavicol like anethol yields anisic acid, milder oxidation with permanganate, however, yields homoanisic acid. The statement by Gerhardt that the acid obtained by the oxid- ation of anise oil was anisic acid was correct, but his conclusions were wrong. Somewhat later ( 1898 ) Grimaux 2 likewise found methyl chavicol in estragon oil and named it estragol. The properties and derivatives of methyl chavicol are described on p. 179. In addition to the inactive methyl chavicol, e.stragon oil con- tains several other constituents to which the optical activity of tlie oil is due, but these have not yet been examined. 417. Oil of Levant Wortnseed. OriCtIN. The unexpanded flowers of A rtewivin inaritinui var. t^tecli- manni are used as a popular anthelmintic. The bulk of the levant wormseed is u.sed in the manufacture of santonin, whereby the oil was obtained as by-product. Since the manufacture of this by-product has been dropped the price of the oil has risen and its <-onsumption decreased. To this circumstance should be added that the principal constituent of the oil, the cineol or eucalyptol, can he hwA pure and at a low price. The yield varies from 2 — 8 p. c. Properties. Oil of levant wormseed is a yellowish liquid possessing the camphoraceous odor of cineol, but also the unpleasant by-odor characteristic of the drug. Sp. gr. 0.915—0.910. The oil is slightly laevogyrate. Composition. Up to 1881 oil of levant wormseed had been repeatedly examined but the results were unsatisfac-tory because they were more or less contradictory, particularly those pertaining to the dehydration products of the constituent CioHigO. Whereas Vcilckel^ 1) Bericht von S. & Co., Apr. 1S!)2, p. 17. 2) Compt. rend., 117, p. lOSH. 3) Liebis's Annalen, 38. p. 110: 87, p. ;-112; 89, p. .8,-|S, 684 Special Part. (1841, 1853 and 1854), Hirzeli (1854), Kraut and Wahlforss^ (1864) and Graebes (1872) claimed that phosphoric acid anliydride produced a hydrocarbon CioHie, Faust and Homeyer* (1874) showed that this hydrocarbon "cynene" was identical with cymene, CioHi4. These con- tradictory points, however, were cleared up by two contributions published at almost the same time, viz. those of Wallach and Brass ^ and Hell and Stiircke." Wallach and Brass were the first to isolate the oxygenated con- stituent in a pure state, by making its hydrogen chloride addition product and decomposing this with water. This substance, which they called cineol, is dehydrated by hydrogen chloride or benzoj^l chloride yielding a terpene, cynene, which later was termed dipentene. They also showed that dipentene under the influence of concentrated sulphuric acid or phosphorus pentachloride yields cymene. This explains the contradictorjr statements of earlier chemists who according to the streng-th and character of the dehydrating agents obtained a mixture in which either dipentene or cymene predominated. In addition to cineol, the oil contains an unknown hydrocarbon, either a terpene or cymene, the boiling point of which lies very close to that of cineol ; also an oxygenated substance boiling higher than cineo and optically laevogyrate. 418. Oil of Wortn-wood. Oleum Absynthii. — Wermntol. — Essence d'Absyntlie. Obi&in and History. Artemisia absinthium L. is indigenous to many European countries and has been introduced into North America. For commercial purposes the plant is frequently cultivated. The distilled oil of wormwood was known to Porta about 1570, who called attention to its blue color. It was first examined by Hoffmann in 1722 and recommended by him for medicinal purposes. It was also examined by Geoffroy (1721), Kunzemiiller (1784), Buchholz (1785), and Margueron (1798). In the price ordina-nces it occurs in that of Frankfurt for 1587, also in the Dispensatorium Noricum of 1589. Peepakation. Whereas the French oil formerly controlled the market, it is now replaced more and more by the cheaper but less ') Jahresb. f. Chemle, 1854, p. .591; *) Berichte, 7, p. 1429. 1855. p. 655. 5) Liebig's Annalen, 225, p. 291. 2) Lieblg'e Annalen, 128. p. 293. 6) Berichte, 17, p. 1970. 3) Berichte, 5, p. 680. Oils of the CoinpositHe. 685 prized American oil from New York (Wayne Co.), Michigan, Nebraska and Wisconsin. Similar in quality to the P^rench are the Spanish and Algerian oils, also the oil prepared in small quantities on Corsica. The Russian oil which for a time was to be had, has again disappeared from the market. The consumption of wormwood oil has decreased considerably, due possibly to tlie toxic properties of the oil to which attention has been directed. From the fresh herb cultivated in Germany ^ p. c. of oil at most is obtained, which at first is dark brown, the color changing to green after prolonged exposure to the air. Properties. Oil of wormwood is a somewhat viscid liquid of a dark green or occasional blue color. It has the not pleasant odor of the plant and a bitter, grating and persistent taste. Sp. gr. 0.92.5 — 0.9.5.5. On account of the dark color the angle of rotation cannot be determined. Inasmuch as the pri^lcipal constituent of the oil, the thujone, is strongly dextrogyrate, the oil itself must be dextrogyrate. The oil is soluble to a clear solution in 2—4 p. of 80 p. c. alcohol. CoMPOSiTiox. The first chemiiral examination of the oil was made by Leblanci in 1845. After repeated rectification over lime, he obtained a principal fraction boiling at 205° whicli had the composition CioHieO. By treating this with phosphoric acid anhydride he obtained a hydro- carbon CioHii. These results were confirmed by the later investigations of Cahours2 (1847), Schwanerts (1863) and Gladstone* (1864). Beilstein and Kupffer^ (1873) called the substance CioHieO absynthol •and identified its dehydration product with cymene. Thej' also verified Gladstone's statement that the high fraction 270—300° is identical with the corresponding fraction of oil of chamomile. By washing the various fractions with aqueous potassa, Beilstein and Kupffer obtained an acid, the barium salt of which indicated acetic acid. The identity of absynthol with tanacetone or thujone was pointed out by Semmler" (for properties .see p. 167). Fritzsche Bros.'^ recently examined an oil distilled in their Garfield laboratories. The thujone was removed as completely as possible by 1) Compt. rend., 21, p. 379; Ann. de Chim. et Phys., Ill, 16, p. 3.S8 ; Chem. CentralW., 1846, p. 62. 2) Compt. rend., 2.5, p. 72.5. ' • 3) Liebig's Annalen. 128, p. 110. 4) Journ. Chem. Soc, 17, p. 1: Jahresb. f. Chem., 1863, p. 549. 5) Liebig'8 Annalen, 170, p. 290. 6) Beriehte, 25, p. 3350. Comp. also ibid., 27, p. 895, and Bericht von S. & Co., Oct. 1894, p. 51; and Wallach, Liebig'.? Annalen, 286, p. 93. 7) Bericht von S. & Co., Apr. 1897, p. 51. 686 Special Part. means of sodium acid sulphite solution and alcohol, and the remaining oil saponified with alcoholic soda. The saponified oil was distilled with water vapor, but a viscid residue remained which was only partly soluble in ether. The portion not soluble in ether proved to be the sodium salt of an acid which was identified with palmitic acid by means of its melting point and the analysis of its silver salt. Of the volatile acids acetic and isovalerianic acids were identified. The saponified oil was distilled in vacuum and the lower boiling portions fractionated under ordinary pressure. A small fraction 1-58 — 168° resulted in which the presence of phellandrene was demonstrated. An attempt to prepare pineue nitrosochloride resulted in the formation of the characteristic blue color and a few crystals were obtained, but the amount was too small to make possible the identification of pinene.i Fraction 200 — 203° was found to consist of thujone which cannot be removed completely from the oil b\' means of the bisulphite. It was characterized bj' means of the bisulphite addition product, also by its tribromide melting at 121 — 122°. Neither of these comi)Ounds could be obtained from the following fraction 210 — 21.5° which was shown to be of alcoholic nature bj' means of aeetylization and subsequent saponifi- cation. Careful oxidation with chi'omic acid converted it almost completely into thujone, thus demonstrating the presence of thujyl (tanacetyl) alcohol. In tlie higher, fairly large fraction 260 — 280° the presence of eadinene was demonstrated by means of the hj^drochloride melting at 117 — 118°. By saponification of the original and of the acetylized oil it was shown that the oil contains 17.6 p. c. of thujyl acetate ( = i;5.f) p. c. of thujyl alcoholj and 24:. 2 p. c. of total thujyl alcohol (free and combined). Oil of wormwood, therefore, consists of the following substances : 1) thujone, CioHkiO; 2) thujyl alcohol, CioHisO, free and combined with acetic, isovalerianic and palmitic acids; 3) phellandrene and possibly pinene; 4) eadinene; .">) blue oil, the elementary composition of which has not yet been definitely determined. ExAMi.\.\TiON. Oil of wormwood is principally adulterated with turpentine oil. Inasmuch as oil of wormwood itself contains but little of this terpene, its presence is readily ascertained. If a first fraction of 10 p. c. is distilled over, this should be soluble in 2 p. of 80 p. c. alcohol. 1) Wright (1874) (Pliarm. ,Journ., Ill, 5, p. 2;t3) found tivo hydrocarbons in the oil. the one boiling at 1 r;0°, the othiT between 170—180°. Brilhl 11888) (Berichte, 21 p. 1.j6) is of the opinion that the i.hysical prfjiierties mentioned by Gladstone indicate d-pinene. Oils of the Compositae. 68T 419. Oil of Artemisia Gallica. According to Heckel and Schlagdenhauffen ^ (1885). Artemisia gallica Willd., which is' widelj^ distributed throughout France, contains- besides santonin 1 p. c. of volatile oil. In its preparation a small amount of a crystalline substance (camphor?) was obtained. Concerning- the composition of the oil nothing is known. AZO. Oil of Artemisia Barrelieri. The oil distilled from the flowering herb of Artemisia barrelieri Bess, is used in Spain as a popular remedy against colic, and hysteric and epileptic attacks. It is also said to be used in the preparation of Algerian absynthe. The odor is pleasant, strong, aromatic and reminds strongly of tansy.i^ Sp. gr. 0.923. It boils between 180—210° and consists almost entirely of thuione,^ thus explaining its similarity to wormwood and tansy. If it could be obtained in large quantities it would be admirably suited for the preparation of pure thujone. 4-21. Oil of Artemisia Glacialis. The dry herb of Artemisia glacialis Li. (Genepi rJes Alpes) (Ger. Alpen- beifuss, Genepikraut) yields upon distillation 0.1.5 — 0.3 p. c. of volatile oil with a strongly aromatic odor. Sp. gr. 0.964 at 20°. It boils- between 195 and 310°. At 0° it solidifies to a butyraceous mass due to the presence of a fatty acid melting at 16°.* 422. Oil of Fireweed. Erechthitis hieradfolia Eaf. is frequently found wild in burned forest districts, hence the name. According to Todd^ its sp. gr. is 0.845 — 0.855, according to Power" 0.838 at 18.5°. It is either dextro- or laevo- gyrate, aD = — 2to +2°.« According to Beilstein and Wiegand '' (1882) the oil con.sists princi- pally of a terpene boiling at 172°, sp. gr. 0.838 at 18.5° which absorbs a molecule of hydrogen chloride without forming a crystalline derivative. Fraction 240—310° also has the elementary composition CioHio. The fractions boiling above 190° are, according to Power, polymerization, products due to boiling. 1) Compt. rend., 100, p. 804. s) Am. .Tourn. Pharm., 59, p. .312. 2) Bericht von S. & Co., Oct. 1889, p. ,=;.3. ») Pharm. Rundschau, 5, p. 201. 3) Bericht von S. & Co. Oct. 1894, p. 51. 7) Berichte, 15, p. 2854. 4) Bericht von S. & Co., Apr. 1889, p. 4.3. 688 Special Fart. 423. Oil of Petasites Officinalis. PetHsites offlcinaM Moench, (Ger. Pestwurz), yields upon distillation 0.1 p. c. of volatile oil which does not form a clear solution with even 10 parts of 90 p. c. alcohol. Sp. gr. 0.944; Hs)x (b. p. under ordinary pressure 250—253°). According to its boiling point it might be a sesquiterpene, but for such its sp. gr., 0.8733 at 22.8°, is low (sp. gr. of all known sescjuiterpenes 0.90 — 0.92) The principal constituent of the oil is an oxygenated, specifically heavy substance boiling at 169 — 171° under 21 mm. pressure. The oil also contains a substance which separates in white, shining laminae upon cooling. 438. Oil of Sphaeranthus Indicus. The composite Spha,erantlws indicus L. with its ro.se-like odor is used iu India as a medicine. According to Dymock* (1884) it yields upon distillation a dark red, viscid oil which is ratlier soluble in water. From 150 lbs. of the fresh herb about )i oz. of oil was obtained. OIL OF UNKNOWN BOTANICAL ORIGIN. 439. Oil of Anise Bark. As anise bark 8cliimmel & Go. obtained in 1891 a bark from Madagascar,^^ whii-h resembled massoj^ bark in exterior appearance, but differed materially as to odor. The aroma, was more anise- than estragon-like, a.nd reminded somewhat of safrol. The supposition of tlie importer that it is the bark of the star-anise tree is not probable, iuiismucli as Illicium veruin does not occur on ^ladagascar. It mav be the bai-k of another species of Illicium, possil)ly of /. parvitioium Michx., which is reputed to have a sassafras-like odor. Upon distillation the 1) Bericht von S. & Co.. Apr. 1892, p. 41. 4) Phariii. .I.iuni., 111. 14, p. 085. 2) Bericht von S. & Co , Apr. 188'.), p. 44. 5) Berioht von S. & Co., Apr. 18112, p. 40. 3) Chemiker-Zeituna, 18, p. 1158. 0;7,s of Unknown Origin. B®! anise bark yielded 8.5 p. c. of a light j'ellow oil of anise-like odor but without a sweet taste. Sp. gr. 0.969; ao = — 0°46'. In addition to small amounts of anethol, the oil consisted largelj^ of methyl chavicol, which had been prepai-ed artificially by Eykman. 430. Oil of Quipita Wood. This Venezuelan wood is of a light color, dense in texture but not very hard, and enters commerce in billets several meters in length and 5 — 2<) cm. in diameter. The thicker stems have a thin, wliite outer bark and somewhat resemble birch stems; the bark of the younger stems is grayish-brown. Upon distillation of the rasped wood, Schimmel & Go.i obtained 1 p. c. of a light yellow oil, with terebinthinate odor. Sp. gr. 0.934 ; a-D = — 34° 31'. Saponification number of the original oil 2.9; after acetylization 40.2. This shows that in addition to a small amount of ester there are alcoholic constituents in the oil. 1) Bertcht von S. & Co., Oct. 1896, p. 7.5. BIBLIOGRAPHIC NOTES. Those who desire further information than that liere given concerning the writings mentioned in the historical chapters of this work, or about their authors, may consult the historical appendix to Fliickiger's Pharmacognosie des Pflanzenreiches and the works there mentioned. The translator desired to make these bibliographic notes more complete, but time did not permit to do so at present. Aetius. a Christian physician, born in Amid, now Diarbekr, on the upper Tigris, who was educated in Alexandria. Between 540 and 550 he wrote a medical treatise in sixteen books or section. The following editions are referred to in the historical chapters of this work : Aetii medici graeci ex veteribu.s mtdicitiae totrabiblos. Editio Aldina. Veneti 15-ljT. Aetiu.s '';8t;8Aia larpiKa EKKaiSe.Ka\ Libri medicinales sedecim. Editio Aldina 1533. Anschutz, E. and H. Reittbr. Dr. Anschiitz was in 1895 Professor of Chemistry at Bonn, when Dr. Reitter was laboratory assistant. Die Destination unter verinindertem Druck im Laboratorium. Zweite neu bearbeitete Autlage. Ein Bd., pp. IV, 86. Verlag von Fr. Cohen, Bonn, 1895. Arabian Physicians. The writings of the Arabian physicians and scientists are preserved principally in a collective edition printed in Venice in 1502. The following works are contained in this volume: Uni Joannis Mesne Liber de consolatione medicinarum simplicium et cor- rectione operationem earuni canones universales: cinn expositione preelaris.simi medici magistri Bondini de leiitiis felicitur JTicipiunt. Additiones Petri Apponi medici clarissimi, et Franci.sci de Pedemontium. .Joannis Nazareni filii Mesne Grabaddin medicinarum parti(^ularium incipit. Antidotanum Nicolai cura expositionibns. et glossis clarissimi magistri Platearii. Bxpositio Joannis de Santo Araando supra antidotarrii Nicolai incipit feliciter. 694 BibUognipliic Notes. Tractatiis de synonymiw quid pro quo. Liber Servitoris seu libri XXVIII Bulcliasin Beu-aherazern : translatus a Simone Jannensi: interfirete Abraamo Judeo Tortuosienzi. Uni Saladini de esculo Servitati priucipis Tarenti physici priricipaliH com- pendii aromatiorum opus feciliter incipit. (iuae omnia supradicta hie tinem liabeiit ad laudam dei. Veueti iuijiressa anno Domini 1502, die 2;i .Tunii. The oldest single editions of these works date up to 1471, about the time of the introduction of the printing of books. AsKiNSON, Geoeg-e Wm. Manufacturer of perfumes. The following works are of A. Hartleben's ehemisch-technische Bibliothek. Die Fabrikatiou der atherisclien Oele. Anleitung zur Dar.stelluug der atherischeu Oele nach den Methodeu der Pre.ssuug, Destination, Extraction, Deplacirunn-, Maceration und Absorption, etc. Zweite vermehrte und verbesserte AuHage. Eiu Bd., pp. VIII, 215, rait 80 Abbildungen. A. Hartleben's Verlag, Wieii, 1887. Die Parfumerie-Fabrikation. Vierte, vermehrte und verbesserte Auflage. Ein Bd., pp. 376, mit 35 Abbildungen. A. Hartleben's Verlag, Wien, 1895. AvENZOAR. (Avei-rhoes, Averroes. ) Abul-Welid Muhammed Ben Ahmed Ibn Roschd el-Maliki was born (1126) and educated in Cordova. A famous Arabian philosopher and physician. Of his numerous work.s the following is referred to on p. 10. Liber Theizir Dahahiiodana Vahaltadabir prooemium Averrhoi Cordubensis ab Jaoobo Hebraeo. .inno 1281. Colliget Veneti 1553. Ayurvedas. See Snsruta. Bergmann, Torbern. Swedish chemist, born 173.''i, died 1781. De primordiis chemiae. Upsala 1779. Editio Hebenstreit. Lipsiae 17S7. Historiae chemiae medium seu obscurum aevura. Editio Hebenstreit. Lipsiae 1787. Bessonius. Jacobi Bessonii, De absoluta vatione extvahendi aquas et olea ex medica- mentis simpHcibus a quodam erapirico accepta et a Bassonio locupletata, experimentis confirmata. Tiguri 1559. — French edition, Paris 1573. BoERHAAVE, Hermann. ]5orn 1668 near Leiden. Since 1709 Pro- fessor of medicine, botany and chemistry at Leiden. Died there 1738. Elenienta chemiae, (juae anniversario labore docuit, in publicis, privatisque scholis, Hermannus Boerhaave. Tomus ]irimns, qui continet historiam et artis theoriam. Tomus secundus. qui continet o])erationes chemicas. Lugduni Ba- tavorum 1732 — Londini 1732 et 1735 — Parisii 1732, 1733, 1753 — Lipsiae 1732 — Basileae 1745 — Veneti 1745 et 1759. Bihliograpbh' Notes. 695 BORNEMANN, GeORG. Die fliichtigen Oele des Pflanzenreichs, ihr Vorkommen, ihre Gewinnuiig und Eigenschaften, ihre niitersnchuug und Verwenduiig. Ein Bd., pp. XII, 441, mit eineni Atlas von 8 Foliotafeln, enthaltend 83 Abbildiingen. Verlag von B. V. Voigt. Weimar 1891. Bruivfels, Otto. 1488 — lij34. Carthusian friar, then teacher in Strassburg, died a,s city physician in Basel. Spiegel der Arznei. Strassburg 1532. — Reformation der Apotheken. Strpss- burg 1536. BRUNSCH\n&, HiEROXYMUs. About l-t.oO— 1.530. Born in Strassburg, physician. Liber de arte distillandi. For the complete title see title pages of both volumes on pp. 23 and 25, rejiroduced half size. BURGHART, G. H. Die znm allgemeiuen Gebrauch wohl eingerichtete Destillirkunst. Auch die Bereitung verschiedener destillirter Wasser und Oele. Von G. H. Burgliart. Breslau 1736. — Neue Auflage mit vieleii Zusatzen von .J. Christian Wiegleb. 1754. Das Brennen der Was.ser, Oele und Geister. Wohleingericlitete Destillirkunst und neue Zusatze. Von G. H. Burghart. Breslau 1748. Gartheuser, Joh. Friedr. 1704 — 1769. Professor of medicine, botany and chemistrj' at the University of Frankfurt-on-the-Oder. His contributions on volatile oils are contained in the following works : Fundamenta materiae medioae. Franeofurt. ad Vladr. 1738 and Paris edition 1752. Elemenca Chymiae dogmatieo-experimentalis, una cum synopsi Materiae medicae selections. Halae 1736. Editio secunda priore longe eniendatior. Dissertatio chymico-physica de genericis quibusdam plaiitarum prineipiis hactenus neglectis. Francof. ad Viadr. 1754. Editio secunda ] 764. Dissertatio physico-chemica medica de quibusdam Materiae medicae subjectis exarat. ac publice habet nunc iter, resus. Francof. ad Viadr. 1774. Dissertationes noniiullae selectiores physico-chemicae ac medicae. varii argu- menti post novam Instrationem ad prelum revocat. Francof. ad Viadr. 1778. Pharmacologia theoretico-practica praelectionibns academicis accommodata. Berolini 1745. Charaka. See Susruta. CoRDUS, Valerius. Born 1515 near Erfurt, died 1544 in Rome. See pp. 27 and 80. His lectures on Dioscorides were published after his death and reedited by Conrad Gesner with the following title: In hoc volumine coutinentur Valerii Cordi Simesusii Annototiones in Pedaera quae extant omnia. Ex nova interpretatione. Jani-Antonii Saraceni, Lugduni Medici, Francofurti 1578 and 1598. A Latin tran.slation of the Dioscorides' "Materia Mediea'' had appeared as early as 1478, and a Greek edition about tlie same time in Colog'ne. A later edition of Dioscorides' "Materia Mediea" which has been used in this work is the edition of Prof. Curtius Sprengel. It constitutes volume 25 of Kiihn's collection: "Medieorum yraecorum opera quae extant," and consists of two parts. The first part contains: "De Materia mediea libri quinquae" ; the second part: "Liber de venenis eorumque precautione et medicamentione'' (pp. 1 — 888), and "Commen tarius in Dioscoridem" (pp. 3-40 — 675). DisPENSATOKiuM Brandenbukgicum. The eilition of 1698 was con- sulted. See p. 81, footnote 8. DisPENSATORiuAf NoRicuM. See CorduB and Gesner. Fluckiger, F. a. Born May 15, 1828, in Langenthal, Switzerland, died Dec. 11, 1894, in Bern. Professor of Pharmacy and Pharmacog- nosj at Strassburg from 1878 — 1892. Pharmacognosie des PflaTizenreiches. Dritte Aufiage. Ein Bd., pp. XVI, 1117. Yeriag von Hermann He.yfelder, Berlin, 1891. Fluokiger anu Hanbuky. Pharmacogi-apliia, a liistory of the principal drugs of vegetable origin me t with in Great Britain and Britisli India. Second edition. One vol., pp. XX, 803. Macmillan & Co., London, L879. FouRCROY. A. F. Born 1755. died 18<)9. An influential French teacher of cliemistry. S.ystenie des coiuiaissances chimiques, et de leur applications aux phenomenes de la nature et de I'art. Paris 1801. FuoHS, Lbonhari). 15(11—1566. Professor of medicine in Ingolstad and Tiibingen. De coinpouendovuni miscendorumque medicauieutoruui i-atione. 1549. Bibliographic Notes. 699 FucHS. Kemaclius. Born 1510 in Limburfj-, died 1587 in Brussels. Reraaolii Fiiohsii, Historia omuiuin aqiiarum, quae in commune hodie practicantium sunt usu, vires et recta destillatidi ratio. Yeneti 1.542. — Parisii 1542. Galenus. Born 1:51 in Perg-amon, educated in Smyrna. Alexandria and Rome as physician. Died between 201 and 210. His numerous writings have been edited by Kiihn under the title: t'laudii Galeni Opera omnia, in 20 Bandeu, Lipsiae 1821—183.3. Special mention ma.y liere be made of De simplicium medicamentorum temperaturis et facultatibus libri XI. Gebeb. Abou Moussab Dschafar al 8ofi, known in western countries as Geber. was active as Arabian physician and scientist during the second half of the eighth century. In addition to the original writings of Gelier which were written in Arabic, a number of works which evidentlj' were wi-itten later in the Greek and Latin languages, have been attributed to him up to a com- paratively recent date. The apocryphal character of these later works has recently been proven by M. Berthelot ("Introduction a I'etude de la chimie des anciens et du moyen-age." Paris, 1889; also "Revue des deux mondes," Sept. 15 and Oct. 1, 1893). Some of the works written by Geber or at least attributed to him and referred to in this book are : Gebri "de alcliimia libri tres." Argentorati arte et impeiisa. To. Griegningeri anno 1529. Gebri "Snmma perfectionis magisterii." Ex bibliotheca vatieana exemplari. Gedani 1682. Alcliimiae Gebri Arabis libri exciid. Joh. Petrins, Xiirenibergensis. Bernae 1545. Gesnee, Conrad. (Euonymus Philiatrus.i) Born 1516 in Ziirich, died there in 1565. Studied in Bourges. Paris and Basel. Was city physician and later Professor of the natural sciences in Ziirich. Edited the works of Cordus (see Cordus). More important than these "Annotationes" is the following: Thesanrus Euonymi Philiatri, -de remediis secretis; liber physieus. medicns et partim etiam chymicus et oeconornicus in vinorum diversi saporea apparatur: mediciB et pharmacopolis oninibu.s praecipue neeessariu.s. Tigur. 1552. Liber I- De de.stillatione ejusque differentiis in genere. Auctor est Conradus (iesnerus. Tiguri.^ 1) The peeiidnnym of Gesner is pos.sibly derived from Euonymus (Ger. Pfaffenhiitchen) and pbillatros. ((^I'Aos iaTp6%) friend of medicine. 2j Another reference contains after the sentence ending \vith "necesHariii.s" the following data: Tignri l.'."2 — I>ngduni 1.5.57— l.»i66 — Franeof. 157.S. 700 fiiblio/fraphic Notcf.: A German edition appeared in 1555 under the title; "Eiu kostlicher theurer Schatz des Euonynnis Philiatrus, darinuen behalteii sind vil heymlicher gutter stuck der arzney. fiinieiiinilic-h aber die art und eygeii- schatften der gebranuten wasseren und olen, wie man dieselbigeu bereiten solle: desgleychen yeder wasser^n und iilen art und eygenschafft. nutz und branch. Item alles rait schonen lieblicheii figurlinen angezeigt unnd Item wie man mancherley weyn bereiten solle, audi den abgestandenen durcli liilff der gebranu. ten wasseren, gewiirtzen unnd anderley materi widerumb helffen moge fur die augeu gestellt, ganz lustig, nutzlich und gilt alien Alcliemisten, haushalten, insbesonders den Balbiererern, Apothekern und alien liebliabereu der Arztney. — Erstlich in Latin beschrieben durch Euonymum Philiatrum, unn newlich ver- teutscht durcli Johannem Rudolphum Landenberger zu Ziirich : vormals in Teutsche sprach niemals gesahen. Getruckt in Zurich bei Andrea und .lacobo den Gessneren gebriider im jar als man zalt von(Jhristi unsere-< fTeylands geburtl555.'" For more than a century this work was frequently reprinted and translated. The English translation by Moroyng appeared in 1559 under the title : New book of distillation called the treasure of Euonynius, London 1559, 1564—1565. A French translation appeared in 15.55 in Lyon. In 15H8, after the death of Gesner, this volume was reprinted with a second volume (also written by him and published by Caspar Wolf in the original Latin in 1565) translated into German by Jacob Niischeler. The title of this second volume is : Ander Tlieil des Schatzes Euonymi von allerhand kiin.stliche[i und bewerten olen, wasseren und heymlicheii Arzrieyen, sanipt ihrer ordentlichen bereytnng und dienstlieheii Figuren. Erstlich zusammeii getragen durch Herrn Doctor Cunrat Gesner, Demnaoh von Capar Wollfen der Arzneyen Doctor. Zurich: in Latin beschrieben und in Truck gefertiget, jetzt aber newlich von Johann Jacobo Niischeler Doctoren, in Tiitsche Sprach vertolmetschet. I."i8:i. Glauber, Johann Rudolf. 1604— 166y. A representative of techni- cal chemistry during the iatrochemical period. Joh.anni Rudolphi Glauberi Furni novi pliilosophici oder Be.schreibung der nen erfundenen DestiUirkun.st. Amsterdam 164-8 — Leiden ]64s — Prag 1700. Ghen, F. a. C. 1760—1798, studied pharmacy, was professor of chemistry at Halle. Founded with Gilbert the Annalen derPhysik in 1798. Gren'a Grundriss der Cheniie nach den ueuesten Entdeckungen entworfen und zuin Gebrauch akademischer Vorlesuugen eingerichtet. Halle 1796. Hanbury, D. Born Sept. 11, 1825, died March 27, 1875. Phar- macist and writer on numerous pharmacognostical subjects. Science Papers. Edited with memoir by Joseph Ince. One vol., iip. XI 543. Macmillan & Co., London, 1876. Pharmacographia — See Fliiekiger. Bibliogvajihic Notes. 701 Heusler, Fr. For several years Professor Wallach's assistant at Gottingeu, later Privatdocent at Bonn. Die Terpeiie. Braunschweig 1896. Reprint from the new "Hand worterbuch der Chemie." Published by Vieweg und Sohn, Braunscliweig, 1896. HiEZEL, HeiXRICH. Die Toiletten-Chemie. Leipzig 1861. Hoefer. Histoire de la ehiinie. 2nd ed. 1866. HOFFMAXN, Fr. Born 1660 in Halle, died 1742. Professor of medicine in Halle. A representative of the phlogistic school of chemistry. Frederid Hoffraannii, Opera omnia physico-medica. Denuo revisa. correcta et aucta. In sex tomos distributa. Genevae 1740 — 1761 — Veneti 1745, 17 Volumina — Neapel 1753, 25 Volumina. Fr. Hoffmannii Opera omnia physioo-medica. Supplementuni secundum. Geneve 1760. Ibn Khaldun. Notices et extraits des manuscripts de la bibliotheque im[)eriale a Paris. 1862. JOANNI KhENANI, Medici, Solis e puteo emergentis; sive dissertationis chyraia technice practica, materia lapidis philosophici et clavis operum Paracelsi, qua abstruea impli- cantur deflcientia supplentur. Francofurti 1613. Pars 1. Theoremata chymio technica. Kliemoxt, J. M. Vienna. Die .synthetischen und isolirten Arom.itiea. Verlag von Eduard Baldamus, Leipzig) 1899. Kopp, Hermann. Born 1817 in Hanau, studied under Liebig, and since 181:1 Professor at Heidelberg. Known as physical chemist and author of several historical treatises : Geschichte der Chemie, 1843—1847. Entwickelung d. Chem. in der neueren Zeit. 1873. Beitrage zur Geschichte der Chemie, 1869 — 1875. Larhus. See Scribonius Largus. Leais, William. The new Dispen.satory : Containing the theory and practice of pharmacy, a description of medicinal simples, according to their .virtues and medicinal qualities, the description, use and dose of each article, etc. Intended as a, correction and improvement of Quincy. London 1753. LoNicER, Adam. 1528—1586. Adami Loniceri. der Arzney Doctor und weiland Ordinarii Primarii Physici zu Francfurt am Meyn, Krijuterbueh und kiinstliche Conterfeyungen der Bau- men, Stauden, Hecken, Krautern, Getrayde, Gewiirzen und niitzlichen Kunst zu 702 Bibliographic Note.s. destillireii, ... — Auf das allerfleissiRSte iiberseheii, corrigirt und verbeBsert durch Petrum Uffenbacliium, Oi'diii. Pliysirus in Francfurt am meyii. Ulm, anno dei 1551, 1573 und 1589. Adami Loniceri, Krauter Buch und kiinstlicbe Conterfeyungen saninit der schonen und ntitzlichen Kunst zu destillii'en. Von Petrus Uffenbach in's Teutscbe iibertragen. Ulm 1703. LuLLUs. Ea3'munilus Lullus. born about 1285 of famih' of Spanish nobility, alchemist, was killed as missionary in Africa in 1315. Eaimundi LuUi, "Experiinenta nova" in Manget's Bibliotheca chemica curioaa. Genf 1702. Matthiolus. Born 1501 near 8iena. studied medicine in Padua, body physician of Emperor Maximihan II, succumbed to the pest in Trient in 1577. Petri Andreae Matthioli, Opera (juae extant omnia. Supplementum : De ratione destillandi aquas ex omnibus plautis: et quomodo genuini odores in ipsis aquis conservari possint. Basilae 1505. Maier, Julius. Dr. Julius Maier, Die atherischen Oele, ihre Gewinnung, cbemischen und physikalischen Eigenschaften, Zusammensetzuug und Anwendung. Verlag von Paul Neff. Stuttgart. 1867. MiERziNSKi, Stanislaus. Die Fabi-ikation der atherischen Oele und Riechstoffe. Berlin 1872. Die Riechstoffe und ihre Verwendung zur Herstellung von Duftessenzeu, Haarolen, Pomaden, Kieclikis.sen etc., sowie anderer kosmetischer ilittel. Siebente Auflage. Ein Bd., pp. XX, -V-M, mit 70 Abbildungeu. Verlag vou B. F. Voigt, Weimar, 1804-. (Sechster Band von Xeuer Schauplatz der KiiTiste und Handwerke.) Mesue, the Younger. Yahya ben Masawaih ben Hamech ben Ali ben Abdallah, body physician of the Chalifa el-Hakim in Cairo, died about 1015 when more than 90 years old. His "Antidotarium" was the most renowned pharmaceutical treatise of the middle ag-es. Mesue. Antidotarium sen Grabaddin medicainentorum com]iositoruui libi-i XII. Editio Veneti 1502. Mesui?, Sirajilicia et composita, et .antidotarii noveiu ].)osteriores seetiones adnotationes. Venetiae 1002. Neumann, Caspar. Born l(;8:i, died 17:!7. Apothecary in Berlin. His work on distilled oil is contained in the second volume of his Cliymia raedica dograatico-experimentalis, oder Griindliehe mit Experimenten bewiesene Medicinische Chenu'e. Herausgegeben von llirist. Heinr. Kessel. 4 Bande. Ziillichau 1719-1755. Bibliographic Notes. 708 NoNus Theophaxus. Body pliysician of Emperor Michael VIII in Constantinople. Nonus Theophaiuis. Editio Bernardi. Pi-aefatio ad Synesius de febribus. Amstelodami, 1749. Comp. Synesius. Occo, Adolph. Second halt of sixteenth r■entu^3^ author of the famous Augsburg Pharmacopoeia. Pharmaeopoea seu iledioainentarium pro Republica Augustana. Author Adolphus Occo. Augusta Yindelicorum 1564. Ortolff. Adolph Megtenberger or Meydenberger, also Ortolph or Ortolff von Bayeruland, born 14.")(), author of the first pharmacopoeia in Germany. Ortloff von Bayrland. .Vrzneibucli. Hie fahet an eyn biiclielin von mariiger- iey Artzeney. Mainz 1485. Pharmacopoe.4. Augustana. See Occo. The editions of 1580, 1597 and 1640 were consulted in preparing the list on p. 32. Philippe. Histoire des i\pothicaires. One vol., pp. VII, 452. A la Direction de Publicite Medicale, Paris, 1853. Translated into German bj' Ludwig. Philippe & Ludwig, Geschichte der Apotlieker. 1858. PlESSE, S. The Art of Periunierie. London 1862. Plinius. Cajus Plinius Secundus, born in the year 28 A. D. near Como, died in the year 79 near Stabiae (Castellamare) at the time of the famous eruption of Vesuvius. Compiled the natural scientific information of his time in 47 books. Most references in this work are to the following edition : Plinii Secundi Naturalis Htstoriae libri 37. Recognovit atque indicibus in.struxit Ludovicus .Janu.s. Lipsiae 1859. Littr^. 2 vols. Paris 1877. PoKTA. Giovanni Battista della Porta, 1537 — 1615. A Neapolitan nobleman, known especially for his re.searches in physics. Job. Baptistae Portae, Neapolitan), Magiae naturalis libri viginti, in quibus scientiarum naturaliuni divitiae et deliciae denionstrantur. lam de novo, ab omnibus niendis repurgati, in lucem prodierunt. Romae 1565. Antwerp. 1567. Editio: Hanoviae 1019. Liber decimus: Destillat, destillata ad fastigia virium sustoUit.i Power, F. B. See Schimmel & Co. 1) other editions are Romae 156.3, .\iitwerriiae 1.tB4 and ;i.")07, Ravennae 1565, Hanoviae 1619. 704- Bihlingra])bic Note.i. Pkice Ordinances. See also p. 31. ■•Ita sunt Tiomina medieinarum siinpliciuin sive inaterialium quae ad apotheoam requirentur. In genere et in specie." Prof. F. A. Fliiekiger under tlie title "Die Frankfurter Liste." Register alles Apothekischen Simplicien und Compositen, so in den beiden Messen zu Frankfurt am Maiu durch Materialisten, Kautfleut, wurzeltrager, Krautler und durch die Apotheker daselbst verkanft werden. Frankfurt a. M. 1 .=382. Reformatio oder erneute Ordnuug der lieilig Reichsstadt Frankfurt a. M., die Pflege der (iesundheit betreffend. Den Medicis, Apothekern und Materia- listen zur Naclirichtigung gegebeu. Darneben den Tax und Werth der ArzTieieii, welche in den Apotlieken allda zu finden. 1587. Ehases. Abu Bekr Muhammed Beu Zakerijja el-Raze. Born and educated in Raj, at one time director of the hospital in Bagdad, author of numerous works, called the Galen of his time. Died 923 or 932. Das Buch der Gelieimnisse des Abij Bekr Ben Zakarija Er-Razi. Fleisclier's Catalog No. 266. Leipzlger Stadtbibliotliek. Codex K. 215. Extracts of Rhases' writings and the unimportant illustrations of several Arabian distilling apparatus were published in 1878 bj^ Prof. E. Wiedemann in vol. 32 (p. .57.5) of the Zeitsehrift der deutschen morgenlandischen Ge.sellschaft. Reiff. Walther Hermann Rjff, during the first half of the sixteenth century surgeon in Strassburg. H. Gualtherus Ryff, New gross Destillirbucli, wohl gegTiiiideter kiinstheher Destination, sanipt underweisung uud bericht, kiiustlich abzuziehen oder Sepa- riren die fiirnembste destiilirte Wasser, kostliche aquae vitae, Ciuintam essentiam, heilsarae oel, Balsam und dergieychen vielgiiter Abziige. Reelit kiinstlich und viel auff bequeme art dann bislier. auch uiit bequemerem Zeug der Gefiiss und Instrument, des ganzen Destillirzeugs von Kreuteru, BItimen, Wurzein, Friichten, Gethier uniid andernn stucken, darinnen natiirlicbe feuohte unud Elementische krafft, einfacli oder mancberley gestalt vermischt und conqionii-t; durch H. Gualtherum Ryff, Medicum & chirurgum Argentinensem, getruckt zu Frankfurt a./m. bei Christian Egeriolff's seligen Erben im jar 1556. Reforrairte deutsche Apotliek. FraTikfurt a./M. 156.3. Saladinus Asoulanus. Italian physician. Wrote, probably between 1442 and 1458, a rather remarkable pharmaceutical treatise entitled: Compendium aromatiorum Saladini, princi]iis Tarenti dignissimi, inedici diligenti, correctum et -emendatuni. Bouonae 1488. Editio Veneti 1471, 1488 and 1502. Sancto Amando. Expositio Joaiiuis de Sancto Amando supra Antidotarium Nicolai incijiit felioiter. With the edition of Mesue's works. Veneti 1502. BibKogTnphic Notes. 705 Sawer, J. Ch. OdorogTaphia, a natural liistory of raw materials and drugs used in the perfume industry. Oue vol., pp. XXIII, 383. Gurney, Jackson, London 1892. Second series 1894. Rhodologia. A discourse on roses and tlie odor of rose. One vol., pp. 93. W. .1. Smith. Brighton 1894. ScHMiEDEH, Che. G. Geschichte der Aleheniie. Halle 1832. ScRiBOXius Largus. Roman physician of the first century of the Chri.stian era, who in the year 48 accompanied the Emperor Tiberius Claudius to Britannia. Scriboui Largi, Compositiones medicamentorum. Editio Schneider. ScHiMMEL & Co. Since Januarj- 1877 the firm of Schimmel & Co., Leipzig, has published a report on volatile oils, at first annually, since 1880 semi-annually. The character of this report was at first com- mercial, but soon became scientific as well until it became a. semi-annual repertory of everythinfj- pertaining to volatile oils. The title of the German edition is : Berjcht von Schimmel & Co. (Iidiaber Gebr. Fritz.sche) in Leipzig. Fabrik ather. Oele, Essenzen und chemischer Praparate. April and October. Since Oct. 1890 an English translation is also published: Semi-Annual Report of Scliiinmel & Co. (Fritzsche Brothers). Leipzig and New York, The title of the French edition which appears since Oct. 1896 is : Bulletin Semestriel de Schimmel & Cie (Fritchzse Freres). Leipzig and New York. In 1893 this firm published : The factories of Schimmel & Co., Leipzig — Prag and Fritzsche Brothers, New York— Garfield. Text by Professor ]^r. F. A. Fliickiger— Bern. An elegant work with 32 heliogravure plates. The text gives a brief account of the history of the volatile oils. A year later the New York branch published a Descriptive catalogue of essential oils and organic chemical preparations compiled b.v Frederick B. Power, Pli. G., Ph, I)., Director of the laboratories of Fritzsche Brothers, at Garfield, N. J. ScHOLTZ, Max. Die Terpene. Sonderabdruck, pp. 189—246. SusRUTA. The name, possibly pseudonym of the author i^ of a book on health Ayurvedas of Sanskrit literature. It was formerly supposed that this book had been written centuries before Christ, but it is now not I) Hippocrates has been suggestefl. 4.S TOG I_lihliogr,iiihic Notes. placed back farther than the twelfth century of the present era. It was translated into (lernian by Hessler between 1844 and 1855 in Erlangen. The Chanika. is a similar older.treatise possibly of the eighth century. Susrutas Ayur-vedas, id est medicinae systema a venerabili D'haiivautare demonstratum a Susruta discipulo compoeituin. Nunc primum ex Sanscrita in Latiauin sermonem vertit, iiitroductioiiem, annotatioiie.s et rerutii indicem adjecit Dr. Fr. Hessler, I<;rlangae 1844. The Susruta, or System of luedicine, taught by Dhanvantai-i and composed by his disciple Susruta. Published by Sri Madhusudaua-Gupta, Prof, of medicine at the Sanscrit Colleg'e at Calcutta. Calcutta 18.35. 2 vol. With regard to the age of these woi'ks consult : Lassen, Indtsche Alterthumskunde. 1. Aufl., Band 2, p. Ci.51. J. F. Royle, An essay on the antiquity of Hindoo medicine. London 1837.. Deutsche Ausgabe von Wallach und Heusinger, Das Alterthum der indischen Medicin. Cassel 1889, p. 4.5. Allan AVebb, The historical relations of ancient Hindoo with Greek medicine. Calcutta 18.50, ]). 45. Zeitschrift der Deutsch. Morgenltind. Gesellscli. Bd. 30 (1876), p. 617; also Bd. 31, p. 647. Synesuts. Born 375 in Cyrene, a disciple of Hypatia in Alexandria, elected Bishop of Ptolemais in 410, alchemist, died 415. Synesii Tractatus chymicus ad Dioscoridem. In Fabricii biblia graeca. Tom. 8. Theophrastus. Born 370 or 392 B. C. in Eresos on the island of Lesbos, disciple of Aristotle, died betweeii 288 and 28G in Athens. Theophrasti Eresii opera, quae supersunt omnia. Historia plantarum. Editio Wimmer. Parisii 1866. Ulstad, Philipp. Professor of medicine in Niirnberg during the first half of the sixteenth century. Philippi Ulstadii, patris nobilis Coelum Philoso)>borum sen liber de secreti.s naturae, id est: quomodo non solum e vino, sed etiam ex omnibus nietallis, fructibus, radicibus, herbis etc. Quinta essentia, sive a(ina vitae, ad conser- vationem humani corporis educi debeat. Argeutor. 1526 und 1528 — Lugduni 1,540 und 1553 — Parisii 1.543 — August. Treboc. 1 553 — Francofin-ti 1600. The title of the German edition is: Dess Edlen und Hocherfahrenen Herrn Philipin Flstadii von Niirmberg Biichlein von Heimligkeiten der Natur, jctzund verdeutischt. Frankfurt am Mayn 1551. That of the French edition wliic/li appeared in 1547: Le Ciel des jihilosophes on secrets de la nature. Paris 1547. Bibliographic Notes. 707 VicTORius Fatextixus. The Bolog-na physician and professor BeDnedetto Vettori was born 1481, died 15(31. Victorii Fayeiitiiii, Practicae magiiae de morbis curaiidis ad tirones. toiiii duo. Veneti 1562. Tom. 1, cap. 21. fol. 111. ViLLAXOVus. Little is known about Arnaldus Villanovus as to nativity. AYas physician in Barcelona during the second halt of the thirteenth century, suffered shipwreck on his way to Avignon to Pope Clemens V about the year 1813. Alchemist. Arnold! Villanovi Opera omnia. Veneti l.'i0.5. Liber de vinis. Arnoldi Villanovi Breviarium practicae, proeminm in operis omnibus cum N. Taurelli in quos libros aiuiotationibus. I'asiliae 1587. WixTHER, JoHAXx. Bom 1187 in Andernach, died 1571 as professor of medicine in Strassburg. Guintheri AndernacivLiber de veteri et nova medicina turn cognoscenda turn facienda. Basiliae 1571. Zeise, H. Born 1793 in Holstein, died 1863, apothecary in Altona. Beitriige zur Nutzanweiidung der Wasserdampfe. Pamphlet. Altona 1826. — Arch. d. Phai-m. Bd. 16 (1828), p. 69. Zeller, Ct. H. Apothecary. Studien iiber die atherischen Oele. I. Heft. Des chemischen Theils erster Abschnitt. Landau 1850. — II. Heft. Die physischen und chemischen Eigen- schaften der officinellen atheri.schen Oele. Stuttgart 1855. — III. Heft. Die Ausbeute und Darstellung der atherischen Oele aus officinellen Pfianzen. Stuttgart 1855. ZosiMOS of Panopolis, an encyclopaedic writer of the fourth century and one of the principal authorities of the alchemists. "Et quid plura moraraur? Unus Zo.simos Panopolites libro Trept opyavuiv Kal KaixLvuiv loculente ad oculos nobis sistit antiquoruni ilia vasa de.stillatlonibus accommodata; postquam enim jussisset candidatos artis id agere ut ipsis ad manus esset /3tVos viXiKos (roiXrjv 6(TTpaKtvo^ XoTras Kat ayyo? (tt€vo<;tovov^ mandassetqiie (.ttI a.Kpa tojv o-ioAj^riov PiKov-i viXov fxcyaXovi iraytls (Tn-'Wivai, tra jXTJ paywiiv awo Trj'i I'tip/ji.rj'; Tov v8aT05, tandem, ut clarius sese explicit, ipsas vasornm figuras appingit, quarum nonnullas licet rudiori manu exaratas ex bibliotheca regis ehristianissimi, et ilia D. Marci Venetiis, libuit hie in gratiam curiosorum adjicere." (0. Borrichius "Hermetis Aegyptiorum et chemicarum sapientia" ab Hermanni C'onringii animadversionibus vindicata. Hafniae 1671, p. 156.) A detailed account of Zosimos' discussion on distillation is found in Hoter's Histoire de la chinue. 2. Edit. 18G6. Tom 1, pp. 2(31—270. INDEX. Abelmosclius nioschatus, 501 Abies alba, 252, 259 balsamea, 251, 252 canadensis, 251, 263 cedrus, 279 excelsa, 259 fraseri, 251 peetinata. 252, 259 leginae anialiae, 260 sibiiica, 265 Abietene, 254 Abietineae, 22(i Absinthium, 684 Absynthe, 684 Absynthol, 685 Abura kuku, 682 Acaroid resin oil, 305 Acetylization, 194, 202 Acid number, 193 Acids, 174 Achillea ageratum, 676 eoronopifolia, 075 millefolium, 675 mosehata, 075 nobilis, 075 Acorus calamus, 301, 303, 304 spuriosus, 304 Adulterations, 199 Ageratum eonyzoides, 068 Argumen fruits, 400 Ajowan oil, 557 Ajwain. 557 Ajxvan, 557 ka-phul. 557 Alantol, 670 Alantol, 670 Alantolaetone, 070 Alantolic acid, 070 Alcohol as adulterant, 200 Alcohols, 127, 148 Aldehyde assay, 196 determination, 196 in cassia oil, 388 Aldehydes, 149 Alembic, 52 \'oyageant, 67 Alliaria officinalis, 409 Allium cepa, 300 sativum, 305 ursinmn, 300 Allolemonal, 286 Allspice, 509 Alljd cyanide, 412 Almond oil, bitter, 430 Aloe barbadensis, 304 Aloe oil, 304 Aloe vulgaris, 304 Aloewood oil, 421 Aloexylon agallochum, 421 Aloysia citriodora, 593 Alpenbeifufsol, 587 Alpenspik, 607 Alpinia raalacensis, 313 ■ ■ nutans, 313 officinarum, 312 Altiugia excelsa, 421 Amandes am6res, 430 Ambrosia artemisitolia, 072 Ambrosia oil, 072 American wormseed oil, 349 710 Index. Aiuomum iuigustifolium, 319 aromaticum, 318 cardamomum, 317 nielegueta, 318 zingiber, 313 Amygdalin, 438 Amygdalus communis, 437 Amyris balsamifera, 480 linaloe, 492 Anacardiaeeae, 218, 490 Analysis of oils, 98 Andromeda leschenaulti, 590 Andropogon eitratus, 285 ivarancusa, 282, 294 laniger, 299 murieatus, 289 nardus, 282, 291, 294 odoratus, 299 Andropogon oils, 22, 294 Andropogon schoenanthus, 281, 294, 299 Aneth, 578 Anethol, 179 Anethum foeniculum, 504 graveolens, 578 sowa, 579 Angelic aldehyde, 073 Angelica anomala, 573 archangalica, 570 herb oil, 573 Japanese oil, 573 japonica, 573 levistieum, 509 oil, 570 refracta, 573 root oil, 573 seed oil, 570 Angelikakrautol, 573 Angelikasamenol, 573 Angelikawurzelijl, 570 Angelique, 570 Angiopteris eveeta, 225 Angostura bark oil, 459 Angosturarindenol, 459 Anis de la Chine, 353 Siberie, 353 Anisebark oil, 090 Anise ketone, 100, 502 Anisijl, 358 Anise oil, 558 Anisic aldehj'de, 157 Anisrindenol, 090 Anonaceae, 215, 302 Anthemene, 074 Anthemis cotula, 074 nobilis, 072 Anthemol, 674 Anthophylli, 513 Anthranilic acid methyl ester, 592 Anthriscus cerefolium, 541 Apfelsinenschalenfil, 471 Apiol. 181, 548 Apiiim graveolens, 545. 547 petroselinum, 547 Aplopappus discoideus, 507 Aplotaxis auriculata, 089 lappa, 089 Aqua ardens, 227 naphae, 480 sabinae, 274 vitae, 20 Aquillaria agallocha, 421 Araceae, 213, 301 Araliaceae, 219 Arbor vitae, 207 saguisen, 303 Arbutus laurifolia, 589 Archangelica ofBcinalis, 570 Aristolochiaceae, 214, 346 Aristolocliia clematitis, 349 reticulata, 348 serpentaria, 348 Arnica flower oil, 089 Arnica montaiia, 688, 089 Arnica root oil, 088 Arnikabluthenol, 089 Arnikawurzeliil, 688 Aromatic balsams. 24 waters, 20. 21. 27 Aromatized fatty oils, 22 Aronie, 35 Artanthe geniculata, 321! Artemisia absinthium, 084 barrclieri, 687 dracunculus, 682 galliea, 087 Index. 711 Artemisia glaeialis, 687 maritima var. steclimanni, 683 vulgaris, 682 Asafetida oil, 574 - Asafoetidaol, 574 Asantcil, 574 Asarabacea, Canadian, 347 Asaret, 346 Asarol, 348 Asarum camphor, 340 Asarum canadense, 347 europaeum, 340 Ase fetide, 574 Ashanti pepper oil, 322 Aspic, 007 Aspidium filix mas, 225 Athamantha oreoselinum, 377 Athanor, 02 Atherosperma moschata, 309 Aucklandia costus, 689 Aunfe, 670 Aurade, 482 Aurantiaceae, 460 Aurantine, 254 Aurantium amarum, 473 dulce, 471, 483 Austra camphene, 45, 110 Australene. 45, 100 Azulene, 078 Backhousia citriodora, 538 Badanifera anisata, 353 Badiane, 353 Badiyan, 353 Baldrianijl, 003 mexikanisches, 665 Balm oil, 610 Balm of Gilead fir, 204 Balneum arenae, 54 Mariae, 54, 57 per cinerem, 57 Balsam copaiba oil, 445 Balsam fir, 204 Balsamkrautol, 081 Balsaniodendron kafal, 488 Balsam of fir, 204 Balsam of Gilead, 264 Balsam Peru, 449 Balsams, aromatic, 24 Balsamtannennadelol, 264 Balsam tolu, 448 Bilrenklauol, 581 Barlauchol, 306 Baros camphor, 502 Barosma species, 457 Barras, 247 Biirwurzel, 568 Basil oil, 059 Basilic, 659 Basilicumijl, 659 Basil, sweet, 659 Baume de copahu, 445 tolu, 448 Bayberry oil, 331 Bay oil, 510 Beifussol, 682 Beilschmiedia obtusifolia, 392 Bellidiastrum osmitoides, 071 Benzaldehyde, 157 Beuzaldeliyde cyanhydrin, 440 Benzoelorbeerstrauchol, 405 Benzoin odoriferimi, 405 Benzyl acetate, 591 Benzyl alcohol, 444, 591 Benzyl cyanide, 453 Benzyl mustard oil, 453 Bergamot oil, 473 Bergamotte, 473 Bergarnottol, 473 Bergaptene, 475 Bergpetersilienol, 577 Betel, 326 Beteliil, 326 Betelphenol, 328 Betel oil, 326 Betulaceae, 214, 331 Betula lenta, 331, 588 Betulase, 333 Beurre de violettes, 308 Biglovia venata, 500 Birch, black, cherry, sweet, 331 Birkenrindenol, 331 Bisabol myrrh oil, 487 Bisabolene, 487 Bitter almond oil, 21, 430 Bitterfenchelol, 507 712 Index. Bitterfeniiel, old of wild, 507 }3ittennandelol, 430 Bitter orange oil, 473 Bitterweed, 072 Bituminous oils, 35 Biyakushi, 573 Black birch oil, 331 Black pepper oil, 320 Black spruce oil, 204 ]Mue gum tree, 520 Blumea balsaiuifera, 009 lacera, 070 Bohnenkrautiil, 019 Boiling point, determination of, 188 Bois de cedre, 270 citron de Gaj'enne, 493 citron de Jlexique, 492 gaiae, 453 Rhodes, 502 rose, 592 rose femelle, 493, 592 rose mfile. 493, 592 jaune, 493 Boldobliltterol, 308 Boldo leaf oil, 368 Borga cananga, 303 Borneo camphene, 110 camphor, 143, 502 camphor oil. 502 Borneol, 143 Boronia oil, 457 Boronia polygalifolia, 457 Boswellia carteri, 489 Boxing of turpentine orchard. 243 Brai, 248 Brassica juncea, 409 nigra, 409 Brazilian nutmeg, 401 Bromine addition method. 192 Brown peppermint tree. 530 strings? bark, 534 Brunnenkressenol. 417 Buccubl.'itterol. 457 ^ Buchu oil. 457 Buco, 457 Bugle weed, 629 Bulnesia sarmienti. 353. 453 Burseraceae, 217. 480 Buiscra species, 492 , ■- Butterweed, 008 Butyl mustard oil, 408 Cabrinoa wood oil, 447 Cade oil, 273 Cadinene, 123 , . Caesalpinia sappan, 448 Cafe bravo, 369 Cajeput oil, 528 Cajeputene hydrate, 521 Cajejautol, 521 Calamus herb oil, 303 ; Calamus, Japanese, 304 Calamus oil, 22, 301 California bay tree, 404 Callitris quadrivalvis, 207 Calmuskrautol. 303 Calmusol. 301 japanisches, 388 Camel-grass oil, 299 Camomille, 070 Romaine, 072 Camphene. 45, 40, 110 Campherholzol from Venezuela. 395 Camphol alcohols, 46 series, 40 Camphora europaea menthae pipe- ritis. 031 Camphor. 39. 4], 143. 148, 227. 270, 270, 320. 340, 370. 408. 482. 502, 008. 012 artificial. 40, 42, 43, 108. 228 Baros, 502 Borneo, 502 Laurus. 104 liquid. 41 ilalay, 502 nil, black. 374 Borneo. 502 heavy. 377 light. 377 white. 374 olefinic. 542 seeds. 317 Sumatra, 502 wood oil. Venezuelan. 39.5 Camphorogenol. 377 Index. 713 Canada balsam oil, 251 mint oil, 654 snakeroot oil, 347 Canadian asarabaeca, 347 Cananga odorata, 302 Canaiium microcaipum, 421 spcr-., 49) Canella alba, 500 Canellaceae, 218, 500 Canelle de Ceylan, 377 feuilles, 381 Chine, 381 Canelo, 394 Cannabene, 334 hydride, 338 Canabis gigantea, 338 indiea, 337 saliva, 337 Capaviapene, 394 Capairapiol, 394 Caparrapi oil, 394 Caprifoliaeeae, 221, 003 Caraway oil, 550 Carbon disulphide, 181, 412 Carbonyl oxygen, determination of, 190 Cardamome, 315 Cardamom oil, 315 Bengal, 318 Cameroon, 319 Ceylon, 315 Korarima, 319 Malabar, 310 Siam, 317 C'ardamomum majus, 319 Carlina acanlis, 090 Carline thistle, 090 Carqueja oil, 447 Carre. 247 Carrot oil, 583 Caruni ajowan, 557 carvi, 550 petroselinum, 547 Carvaerol, 177 , determination of, 554 Cai'vene, 554 Carvi, 549 Carvol, 100 ■ Carvone, 100 Carvone, determination of, 554 Caryophyllene, 125 Caryophylli, 512 Caryophyllus aromaticus, 513 Cascarilla oil, 495 Casearille, 495 Cassia, 382 buds, 382, 390 caryophyllata, 393 ^ chips, 378 '. ., ,, leaf oil, 390 lignea, 390 oil, 382 stearoptene, 385 twigs, 390 Catinga de negra, 309 Catingueira, 369 Catmint, 612 Catnep, 012 Cedar camphor, 148, 270 Cedar leaf oil, 278 Lebanon, 279 , red, 270 , Siberian, 265 , white, 278 Cedarwood oil as adulterant, 199 from Juniperus virginiana, 270 Cedrate oil, 477 Cedratier ordinaire, 477 Cedrejaune, 493 Cedrelawood oil, 494 Cedrene, 126, 614 C'edrol, 148 Cedro oil, 477 Cedrone, 350 Cedro ordinario, 477 Cedrus libani, 279 Celeri, 545, 547 Celery root oil, 547 seed oil, 545 Celtischer Spik, 667 Cevadilla seed oil, 304 C'ej'lon cinnamon oil, 377 Chaerophyllum sativum. 541 Chamaecyparis obtusa, 209 Chamomile oil, 672 , German, 676 714 Index. Chamomilla, 072 romana, 072 Champaca oil, 353 Chavibetol, 328 Chavica betle, 327 officinarum, 322 loxburghii, 322 Chavicol, 179, 328 C'heken leaf oil, 508 C'henopodiaeeae, 215, 34!) Chenopodium ambrosioides, 349 var. anthelmiiitita, 349 L'benopodium oil, 349 Cherry birch, 331 laurel, 442 Chervil, 541 Chione glabra, 662 Chios turpentine, 490 Chloroform as adulterant, 202 Chrysanthemum chamomilla, 076 parthenium, 678 tanacetum, 079 Chula, 282 Cicily, sweet, 583 Cicuta maculata, 550 virosa, 549 Cieutene, 550 Cidreira melisse, 309 Cineol, 175 assay in eucalyptus oils, 528 C'innamie aldehyde, 157 Cinnamomum camphora, 371 cassia, 377, 382 culilawan, 392 kiamis, 391 loureirii, 391 oliveri, 392 whigtii, 392 zeylanicum. 377, 381, 382 Cinnamon oil, 21. 377 Cinnamon leaf oil, 381 Cinnamon root oil, 381, 382 Circulation, 56 Circulatoria, 56 Cistaeeae, 218, 505 Cistus spec, 505 Citral, 149 assay, 470 Citraptene, 468 Citreiie, 113, 467 Citriodora aldehyde, 286 Citriosma apiosyce, 369 enjabana, 309 oligandra, 369 Citron camphor, 468 Citronella aldehyde, 294 Citronella oil, 291 Citronella], 154 Citronelle, 291 Citronellic aldehyde, 294 Citronellol, 135, 294 Citronellone. 294 Citronenijl, 405 Citrus aurantium, 401. 471, 483 beiganiia, 4()1, 473 bigaradia, 4(il, 473, 480, 484 luyrtifolia, 479 sinensis, 479 deeumena, 461, 480 limetta, 478 vulgaris, 478 limonum. 401. 405 madurensis, 461, 479 medica, 4(il. 477 var. acida, 461 nobilis, 479 Clove oil. 512 bark oil. 393 stem oil. 510, 518 Coca leaf oil. 453 Cochlearia, 407 armoracia, 408 olticinalis, 407 Coerulein, 077 Cognac oil, 498 Colophene, 40 Colophony, 22S Color reactions, 192 Conuniphora spec, 4S6, 488 Compositae, 221, 067 Comptonia asplenifolia, 331 Comptonia oil, 331 Condensation, 51. 58. 94 Congealing point, determination of. 187 Coniferous oils. 220 Conima resin oil, 492 Index. 715 Conimene, 492 Constituents of oils, 97 Convolviilaceae, 220, 592 (,'onvolvulus floridus, 592 scopaiius, 592 Copahu, 493 Copaiba balsam, 445 , African, 440 oil, 445 as adulterant, 199 Copaifera species, 445 Copaivabalsamol, 445 Coriander oil, 541 Coriandrol, 129, 542 Coriandrum sativum, 541 Cortex caryophyllati. 393 culilabani papuanus, 405 Costuswvirzelol, 089 Cress, garden, 406 water, 417 C'retian origanum oil, 622 Crocose, 307 Crocus sativus, 307 Croton eluteria, 495 Cvucifevae, 210, 400 Ciyptocaria nioschata, 401 oil, 401 pretiosa, 402 Cuban pine, 242 Cubeba officinalis, 322 Cubebe, 322 Cubebene, 120 Cubeb camphor, 148 Cubeb oil, 322 Cueurbita, 52, 54 Cuminic aldehyde, 157 C'umaric aldehyde methyl ether, 157 Cumin oil, 544 Cuminuni cyminum, 544 Cunila mariana, 001 Cupressus sempervirens, 209 Curcuma longa, 310 oil, 310 zedoaria, 311 zerumbet, 311 Cus-cus. 289 Cusparia trifoliata, 459 C'vmene, 104 Cymol, 104 Cypress oil, 269 Cypress camphor, 270 Cypres, 209 Damascenine, 352 Damiana leaf oil, 506 Daucus earota, 583 Destillationsbucher of the 16th cent., 23-37. Destillatio panis, 57 per aseensiun, 18, 28, 35 per descensum, 18, 28, 35, 36, 00, 02 per ventrem equinum, 57 solis. 57, 62 Dhelum outan, 657 wangi, 656 Diatomic series of terpenes, 40 Dicypellium carj'ophyllatum, 393 Digger pine, 254, Dilem oil, 059 Dill apiol, 181, 579 Dill oil, 578 East Indian, 579 Diosphenol, 458 Dipentene, 110 Dipping in turpentine orchard, 244 Dipterocarpaeeae, 218, 504 Dipterocarpus spec, 504 Dissertations on volatile oils, 37 Distillation, 18, 19 after fermentation, 30 , destructive, 18 , definition by Brunsehwig, 24 , definition of, in historical writ- ings, 22 , downward, 18, 35, 59 , fractional, 19, 44, 188 over burnt lime or chalk, 39 , history of, 51 , treatises on, 23, 30, 37 • under diminished pressure, 09 , upward, 18, 35 with acetic acid, 19 with acids and salts, 36, 40, 60 with alcohol, 19 with steam, 09, 85 716 Index. Distillation with water, IB, 19 Distillerie ambulante, 002 Distilling apparatus, liistory of, 51 Diterpene, 40, 127 Dittany oil, 001 Dog fennel oil, 007 Dorema animoniacuni, i570 Dostenol, 020 Double balsam fir, 251 Dragonic acid, 082 Drimys winteri, 302, 500 Drusenol, 498 Dryobalanops spec, 502 Dutch myrtle oil. 331 Eau de Carmelites, 010 de Cologne, 34, 010 Eberwurzol, 090 Eeuelle a piquer, 402 Edelscharfgarbenol, 075 Edeltanneiinadelol, 25[! Edeltannenzaphenijl, 259 Elaoptene, 41 Elaphriuni aloexylon, 492 Elder blossom oil, 003 Elecampane oil, 070 Elemi oil, 490 Elettaria cardanionium, 315 cardamomum, White et Maton. 315 Empleurum serrulatuni, 457, 458 Empyreumatic oils, 18, 24, 35 Enfleurage tl froid, 591 Erasine, 254 Erechthites hieraeifolia, 587 Ericaceae, 220, 584 Erigeron canadensis. 0(i8 oil. (i(iS Erytlno.vylaccae. 217, 453 Erythroxylon coca, 453 Esdragonol, 082 Esels-Fenchel, 508 Essence d'absynthe. 084 d'amandes ameres. 436 d'aneth, 578 d'angclique, 570 d'anis. 558 d'asarct. 340 Essense d'ase fetide, 574 d'aspic, 007 de badiane, 353 basilic, 059 baume de copahu, 445 Ijaume de tolu, 448 bergamotte, 473 betula, 331 bois' de cedre, 276 bois de Rhodes, 592 rose, 592 bois de santal des Indes Oc- cidentales, 480 bois guiac, 453 cajeput, 518 calamus, 301 camomille, 070 camomille romaine, 072 cananga. 302 canelle de Ceylon, 377 canelle de Chine, 382 cardamome. 315 carvi, 550 cascarille. 495 citron. 405 citronelle, 291 coclilearia. 407 coriandrc. 541 cubebe. 322 cumin. 544 cypres, 209 d'elerai, 490 d'erigeron. 008 d'estragon. 082 de fenouil. 503 fenouil d'oau. 568 feuilles de l>etel, 326 feuilles de bucco, 457 feuilles de cedre, 278 feuilles de celeri, 547 feuilles de jaborandi, 457 galanga. 312 gaultheria. 585 genievre. 270 geramium des Indes. 281 girofle. 512 graines d'ombrette. 501 d'hedeoma, 017 Index. 717 Essence d'lioublon, 336 d'houblon d'Espagne, G22 d'hysope, U18 d'iris concrete, 308 de kuro moji, 404 laurier, 402 laurier cerise, 442 lavande, 000 ledon, 584 licari, 402 limette, 477 linaloe, 492 liveche, 509 uiacis, 300 mandarines, 479 niarjolaine, 021 mastice, 490 -. niatico, 325 nielisse, 010 mcntlie crepue, 651 mentlie poivree, 030 moutarde, 409 muscade, 300 myrcia, 510 myrrhe, 486 myrte, 507 neroli, 480 neroli Portugal, 483 d'oliban, 489 d'orange bigarade, 473 d'orange Portugal, 471 de patchouli, 050 persil, 547 petit-grain, 484 piment, 509 poivre, 320 pouliot, 655 racine d'aunee, 670 romarin, 594 rose, 423 rue, 455 ^ santal, 338 sassafras. 395 sauge, 012 semen contra d'Amerique, 349 semences de eeleri, 545 serpelot, 628 Essence de ^erpentaire du Canada, 347 sombul, 576 styrax, 419 tanaisie, 679 terebenthine Americaine, 239 terebenthine Francaise, 247 thuj'a, 267 thyme, 023 tiges de girofle, 518 — ■ valeriane, 063 vetiver, 289 ylang-ylang, 362 zedoire, 311 Essences, pine needle, 258 Estagnons, 428 Ester number, 193 Esters, 174 Estragol, 501 Estragon oil, 682 Ethyl alcohol, 127 as adulterant, 200 camphor, 320 Eucalyptol, see cineol. Eucalyptus amygdalina, 524, 530, 539 baileyana, 532, 533 bridgesiana, 536 eamphora, 540 capitellata, 533, 534 citriodora, 530, 537, 538, cneorifolia, 525, 530 corymbosa, 532 crebra, 533 dealbata, 537 dawsoni, 540 dextropinea, 535 diversicolor, 539 dumosa, 530 eugenioides, 533, 534 fastigata, 533 fissilis, 539 globulus, 524, 526 goniocalyx, 525, 536, 539 gracilis, 539 haemastoma, 538 hemiphloia, 533 incrassata, 525 laevopinea, 535, 530 lehmanni, 539 718 Index. Eucalyptus leucoxylon, 525, 533 longifolia, 340 loxophlebu, 535 macioiiliynclia, 533 maculata, 53(j var. citriodoia, 537 nielliodora, 525 micioeorys, 533 obliqua, 533, 534 occidentalis, 540 odorata, 525, 530 Eucalyptus oils, 524 eineol containing, 526 citral containing, 538 citronellal containing, 536 with peppermint-like odor 538 with indefinite odor, 539 Eucalyptus oleosa, 530 pauciflora, 540 piperita, 524, 538 planchoniana, 537 polyantlienia, 525 populifera, 532 punctata, 534. 535 resinifera, 532 risdonia, 533 rostrata, 531 sideroxylon, 525, 533 smithii, 530 staigeriana, 538 stuartiana, 540 tereticornis, 540 tereticornis var. brachycoris, 534 tesselaris, 540 viminalis, 537 Eudesmol, 530, 541 Eugenia acris, 510 earyophyllata, 513 Eugenol, 180 assa}', 510 Eupatorium foenieulaceuni, 607 Euphorbiaceae, 218, 405 Euryangium sunibul, 570 Examination of oils, 184 Fabiana imbrieata, 602 Fatty oils as adulterants, 201 Faule Heinz, 02 Feldkiimmelul, 028 Feldthymianol, 628 Fenchelholzdl, 396 Fenchelol, 563 Fenchene, 112 Fenchone, 166 Fennel, Asia Minor, 568 Bitter, 507 Dog, 067 Indian, 507 oil, 503 Persian, 508 Koman, 5(i7 Kussian, 508 Sicilian, 508 Syrian, 508 wild, 567 water, 508 Fenouil, 563 d'eau, 568 Fermentation as preliminary to distil- lation, 36 Ferula asa foetida, 574 galbanidua, 575 opo[)onax, 48S rubricaulis, 575 schair, 575 somliul, 570, 607 Feuerkrautijl, 587 Feuilles de cedre, 278 Feverbush, 405 Feverfew, {)78 Fichtennadelijl, 226. 258, 260 from Picea excelsa, 260 Siberian, 205 Swedish. 202 Fidschi Sandelholziil. 345 Fiji sandelwood oil, 345 Finoccliio d'asino, 508 Fire weed, 587 Flealiane, (iOS Florentine llask, 70 Flores cassiae, 382, 390 Foelire, 2(i2 Foeniculuni capilhiceuni, 504 dulee, 566 panmorium, 567 Index. 719 JToeniculum piperitum, 568 sinense, 353 vulgaie, 564 Foenum cameloruiu, 299 Folia eedri, 278 rractional distillation, 44, 188 -Frankincense, 489 Fiirfurol, 157 Furnus aeediae., 62 -Fusanus spicatus, 345 •GageUil, 331 Gaiiae, bois, 453 •Galanga, 312 -Galangal oil, 312 Galbanum oil, 575 Galgantol, 312 Galipea eusparia, 459 officinalis, 459 Galipene, 460 Galipol, 459 ■Galley furnaces, 63 Garden cress. 40(i nasturtium, 452 'Garlic oil, hedge, 409 Garlic oil, 305 Gaultherase, 495 'Gaultheria fragrans, 589 fragrantissima, 589 leucocarpa, 590 procumbens, 332, 585 punctata, 589 ■Gaultherilene, 333 •Gaultherin, 333, 495, 584, 586 Gebrannte Waesser, 24 Weine, 24 Gemniage, 247 il morte, 247 'Gemme, 247 Genepi des Alpes, 587 Genepikraut, 587 Genievre, 270 Genista tridentata, 447 Geraniaceae, 217, 449 Geraniol, 131 Geranium des Indes, 281 ■ 'Geranium, East Indian, 281 indicum, 281 Geranium oil, 449 , Turkish, 281 Geranium, rose, 449 Getah rasamala, 421 Gingembre, 313 Gingergrass oil, 285 Ginger oil, 313 , wild, 347 Girolle, 512 Glechoma hederacea, 612 Glucotropaeolin, 453 Golden rod, 668 Gomenol, 522 Graines d'ambrette, 501 Grains of paradise oil, 318 Gramineae, 213, 280 Grana moschata, 501 paradisi, 318 Grandel, 248 Grape fruit, 480 Grey gum, 534, 535 ivy, 612 Grlinminzol, 629, 052 Guaiac wood oil, 453 Guaiene, 126 Guaiol, 148, 454 Guajaeholzol, 453 Guayana laurel oil, 394 linaloe oil, 394 Giiljag, 428 Gum ammoniac, 576 blue, 526 grey, 534, 535 slaty, 540 sweet, 420 York, 535 Gundermunnkrautijl, 612 Gurjun balsam oil, 503 as adulterant, 199 Ilanurmelidaccae, 182, 419 Hanfiil, 337 ITaselwurzijl, 346 Hasoronto, 346 Hedeoma pulegioides, 617 Hedge garlic, 409 liedyehium coronarium, 312 oil, 312 7-20 ln(Jex. lleleniii, UTU Heliehrysuiu oil^ (J70 stoeclias, (iTO Heliotropin, 157 Helm, 55, 58 Hemlock needle oil, 263 spiuce, 251 tannennadelijl, 2U3 Hemp oil, 337 > Henna oil, 507 Heraeleum giganteum, 581 sphondj'lium, 582 Herba inatricariae, 678 sehoenanthi, 299 squinanthi, 290 Hibiscus abelmosehus, 501 Ilinoki oil, 269 Hopfeiiol, 336 Hop oil, 336 Horse, mint, 015 radisb, 408 Houblon, 336 d'Espagne, 022 Hiibl's iodine method, 192 Huile aetheree, 227 blanclie de choix rectifiee, 236 fine rectifiee, 236 rectifiee, 236 volatile de cognac, 498 de li de vin, 498 Humulene, 126 Humulus lupulus, 336 Hundefenchelol, 067 Hungarian water, 20, 34 Hyawa gum, 492 Hydrocarbons, 112 Hydroeuminene, 545 Hydrocyanic acid, 182, 437, 443, 444, 447 assay, 441 , detection of, 440 Hydroquinone ethyl ether, 358 Hydroxy aeetophenone, 662 Hysope, 618 Hyssop oil, 618 Hyssopus otlicinalis, 018 Icica heptaphylla, 492 lllicium anisatum, 353 japonicum, 355 parvillorum, 090 religiosum, 355, 362 verum, 356, 090 Imperatoria ostruthium, 577 Indian hemp, 337 Indigofera galegoides, 447 Indigofera oil, 447 Indol, 592 Ingwerol, 313 Inula helenium, 070 Iodine addition metliod, 192 Iridaceae, 313, 307 Iregeuin, 310 Iridic acid, 310 Iris llorentina, 308 germanica, 308 pallida, 308 Irisol, 308 Iron bark, 533 Irone, 310 Isoborneol, 111 phloryl ester, 688 Isopol, 618 Iva oil, 675 Ivaol, 675 Jaborandibliitterol, 459 .Taborandi, false, 326 Jaborandi leaf oil, 459 Jasmal, 591 Jasmone, 592 Jasminium grandifioruni, 590 Jasmin oil, 590 Juglandaceae, 214, 331 .Tuglans regia, 331 Juncus odoratus. 299 Juniper, 270 berry oil, 270 from J. phoenicea, 273 from J. oxycedrus, 273 camphor, 148, 272 wood, oil of, 24. 272 Juniperus communis, 270 oxycedrus, 270, 273 phoenicea. 273 sabina. 273 virginiana, 276, 278 Index. 721 KadeoL 273 Kaemplieriaol, 312 Kaenipheria lotundaj 312 Kamelgiasijl, 299 Kamilleiiol, deutsolies, 070 romiseh, 072 KanokosO, 000 Kapuzinerki'essenol, 452 Kavmoliter Geist, 34^ 010 • Katzenininzijl, 012 Kaju ra^amala, 421 lakka, 421 Keibeliil, 541 Kesso, 000 Kesso root oil, GOO Kessowurzelol, 006 Kessyl acetate, 607 alcohol, 148, 067 Ketones, 158 Kiefer, 202 Kiefeinadelol, 202 PJnglish, 203 German, 202 Swedish, 202 KienOl, 226, 254 Finnish, 257 German, 255 Polish, 250 Russian, 250 Swedish, 257 Kiku oil, 082 Kir^chlorbeerijl, 442 Knoblauchol, 305 Komaki, 391 Kraiiseniinzol, 051 Kressenol, 400 Kretisch Dostenol. 622 Krumndiolzijl, 201 Kummelijl, 550 Kiiromoji oil, 404 Labiatae. 220, 594 Labrador tea oil, 584 Lactones, 174 Ladanum oil, 505 Lamljie, 428 Lana liatii. 291 oil. 296 Langpfefferol, 322 Lantana camara, 504 Lilrchennadelol, 266 Larch needle oil, 266 turpentine oil, 249 Larix cedrus, 279 decidua, 250, 200 europfea, 250 sibirica, 205 Larixolin, 234 Latschenkieferol, 201 Lauchhederichol, 400 Lauraceae, 215, 377, 493 Laurel berry oil, 403 leaf oil, 402 oil from Guayana, 394 , mountain, 404 Laurene, 403 Laurier, 402 cerise, 442 Laurinic aldehyde, 450 Laurinic acid. 403 Laurocerasin, 443, 444 Laurus benzoin, 405 eaniphora. 371 nobilis, 403 Lavande, 000 Lavendelol, 600 Lavender camphor, (i08 Lavender oil, 20, 000 Lavatera olbia, 057 Lavandula angustifolia, 000 dentata. Oil latifolia, 000, 607 officinalis, 000 pedunculata. 611 spica, 600. 607 stoechas, 607, Oil vera, 000, 004 \'ulgaris, 000 Lawsonia inermis. 507 Lebanon cedar oil. 279 Lebensbaum, 267 Ledene, 126 Ledone, 584 Ledum camphor, 148, 585 palustre, 584 Legfijhre, 261 722 Index. Leguiiiinosae, 'illi, 445 Lemon camphor, 408 Lemongrasiil, 285 Lemongi-as:S oil, 285 Lemon oil, 465 Lemonol, 132 Lepitlium eampestre, 406 latifolium, 400 ludel-ale, 400 sativum, 400 Levant worm seed, 683 Levisticum officinale, 509, 570 Lieareol, 128 Lieari, 492 Liebstoek friichte, 570 Liebstoek kraut, 570 Liebstoekijl, 509 Lie de vin, 053 Lignaloe, 492 Lignum aloes, 492 cedri, 270 floridum, 390 pavanum, 396 Rhodii, 592 santali. 338 xyloraarathrum, 390 I^igustieum levisticum, 569 Likari, 493 Liliaceae, 213, 304 Lima di spagna, 478 duleis, 478 Lime oil, 477 Limettbliitterol, 478 Limette, 477 Limettier ordinaire, 478 Limettol, 477 Limoeiro bravo, 309 domato, 369 Limonene, 113 Linaloe, 492 Linaloe oil, 492 , Guayana, 394 Linalool, 128 Linalue, 492 Linden blossoms, oil of, 501 Lindenbliitlienol, 501 Lindera sericea, 404 Lippia eitnodora, 593 Liquidambar altinga, 421 orientale, 419 styraciHuum, 420 Liveche, 509 Loblolly pine, 242 Loffelkrautol, 407 Longdeaved pine, 242 Long pepper, oil of, 322 Lophanthus anisatus, 061 Lophanthus oil, 001 Lorbeerbeerenol, 403 Lorbeerblatterol, 402 Lorbeerol, californisches, 404 Lovage, 509 Lycopus virginicus, 029 Lythraceae, 219, 507 iJacchina, 462 Mace oil, 360 Magnoliaceae, 215, 353 Majoranol, 621 Malakarunnay, 460 Male fern oil, 225 Malvaceae, 218, 494 ^lana pangiri, 291 oil, 296 ^landarinenoel, 479 Mandarin oil, 479 Mandelic acid nitrite, 440 Marjorlaine, 621 Marjoram, sweet, 621 Massoya aromatiea, 405 Massoy bark oil, 405 Massoyene, 405 Massoyrindenol, 405 Mastice, 496 Mastiche, 496 Mastix oil, 496 ilatico camphor, 148, 326 ilatico oil, 325 Matricaria chamomilla, 676 parthenium, 678 Maumene's sulphuric acid test, 192 Meerrettigtil, 408 ileisterwurzol, 577 Jlelaletica acimiinata, 523 eajeputi, 518 decussata, 523 Index. 723 Melaleuca ericifolia, 523 genistifolia, 523 leucadendion, 518 var. lancifolia, 523 linariifolia, 523 minor, 518 squarrosa, 523 uncinata, 523 viridillora, 518, 522 wilsonii, 524 Meliaeeae, 218, 494 Melissa officinalis, 610 Melisse, (ilO Melissenijl, (JlO Mentha aquatica, 630, 652, 654 ■ arvensis, 630, 654 var. piperascens, 629, 630 balsamica, 630 canadensis, 630, 654 var. glabrata, 032 erispa, 629, 630, 652 oils, (i29 palustris, 630 pulegium, 617, 655 rubra, 630 sarceniea, 630 silvestris, 629, 652 viridis, 629, 652 Menthe basiliquee, 649 crepue, 651 poivree, 630 Menthene, 122 Menthol, 145 assay, 651 Menthone, 171 assay, 051 Mespilodaphne pretiosa, 402 Metanethol, 561 Methacrylie acid, 673 Methyl alcohol, 128 Methyl chavicol, 179 Methyl heptenone, 158 i Methyl nonyl ketone, 450, 458, 479 Methyl number, 197 Methyl ortho cumaric aldehyde, 386 Meum athamanticum, 568 Michelia champaca, 353 longifolia, 353 Michelia uilagirica, 392 Mierotaena e^'mosa, 056 Mignonette flower oil, 418 root oil, 418 Milfoil, 675 Mineral oil as adulterant, 201 Mint, Canadian, 653 mountain, 601 pepper, 030 wild, 654 ilohrenkopf, 54, 58 ilohrencil, 583 Monarda didyma, 616 fistulosa, 615 punctata, 615 Alonatomie series of terpenes, 40 Monimiaoeae, 215, 368 Monotropa hypopitys, 584 Moraceae, 214, 336 Moschuskornerol, 501 Moschuswurzelol, 576 Mosla japonica, 660 Mosoilbluthenol, 365 MotiJ'a, 282 Mountain laurel oil, 404 mint oil, 601 Moutarde, 409 Muscade, 306 Muscatnussol, 366 Muskateller Salbei, 614 Mustard oils, 182 oil, black, 409 Avhite, 410 Mutterkrautol, 678 Myrcene, 511 Myrcia asplenifolia, 331 cerifera, 331 gale, 331 Myricaeeae, 214, 331 Myristica fragrans, 366 mosehata, 366 officinalis, 366 Myristicaeeae, 215, 306 Myristicin, 368 Myristicol, 367 :\[yristie acid, 310. 368 methyl ester, 310 Myrocarpus fastigiatus, 447 r24 Index. Myi'onate of potassium, 410 Mj'ioxylon peiuiferum, 449 Myrrh oil, 480 Myrrhenol, 480 Myrtaceae, 219, 507 Mj'rtenol, 507 Myrtle oil, 507 Dutch, 331 Myrtol, 508 Myrtus cheken, 508 communis, 507 Xapha, 480 Nardostachys grandiflora, 667 jatamansi, 576, 667 Nasturtium, garden, 452 officinale, 417 Xectandra eaparrapi, 394 puchury, 393 Negra mina, 369 Nelkencassie, 393 Xelkcnholz, 393 NelkeniSl, 512 XelkenrinUe, 393 Nelkensaure, 512 XelkenstieliJl. 518 Kelkenzimmtijl, 393 Xepeta cataria, 612 gleclioma, 612 Ncroli, 480 Neroli camphor, 482 Neroli oil, 480 Xeroli Portugal. 483 Xgui-camphor, 143, 669 fen. 143, 669 P ien, 669 Xiaonli oil, 522 Nigella damascena, 352 oil, 352 -ativa. 352 Xitriles, 182 Xitrogen-containing oils, 182 Norway spruce, 260 Xos mo.scado do Brasil, 401 X'^umher, acid, 193 ester, 193 iodine. ]!)2 nietliyl, 197 X'umber, saponification, 193 Xussfichte, 254 Xutmeg oil, 366 Xut pine, 254 Xux mosehata, 366 Ociraum basilicum, 659 var. pilosum, 657 Oeosotl, 420 Ocotea caudata. 394, 493 oil, 394 Oculi populi, 330 Oenanthe aquatica, 568 phellandrinm, 568 Oil-containing plants. 212 Oils, analysis of, 98 attempted syntliesis, 41 bituminous, 35 classification by Dumas, 42 constituents of, 97 containing nitrogen, 182 containing sulphur, 182 empyreumatic, 18, 35 laiown to Arnaldus Villanovus, Lullus, Sto. Amando and Sala- dinus of Aesculo, 20, 21 known up to 1730, 32 mentioned in Brunschwig's Destil- lirbucli. 24 Ryft"s Destillirbueh, 26 tlie Annotations of Cor- dus, 28 the Dispensatoriiun Nor- icum, 34 tlie Tliesaurus of Ges- ncv. 28 purificati(m of. 94 treatises on. 50 Olea aerea. 28 Oleaceae, 220. 590 Olcfinie camphors, 542 sesquiterpenes. 123 terpenes, 103 Oleum absynthii. 084 amygdalarum amararum, 437 andropogonis nuiricati, 289 auisi steHati. 353 anonae. 3(i2 Index. 725 Oleum anthemidis, 672 asari canadensi, 347 ■ europaei, 346 aurantii amari, 473 dulcis, 471 floium dulee, 483 balsami copaivae, 445 tohitani, 448 basiliei, 659 benedietinuni eompositum, 24 bergamottae, 473 betulae lentae, 331 buccu foliorum, 457 eadinuni, 273 calami, 301 canangae, 362 cardamomi, 315 casearillae, 495 ehamomillae, 676 ehamomillae eitratum, 677 ehamomillae romanae, 672 ehamomillae vulgai'is, 676 chenopodii anthelmintici, 349 cinnamomi eassiae, 382 Zeylaniei, 377 eitri, 465 eitronellae, 291 eochleariae, 407 cubebarum, 322 eupressi, 269 draeunculi, 682 elemi, 490 erigerontis, 668 florum aurantii, 480 foliorum betle, 326 eedri, 278 r jaborandi, 459 matieo, 325 patchouli, 656 galangae, 312 geranii indieum, 281 helenii, 670 humuli lupuli, 336 iridis. 308 juniperi. 270 kuromoji, 404 ligni cedri, 276 guajaci, 453 Oleum ligni santali, 338 sassafras, 396 limettae, 477 linaloes, 492 lauri foliorum, 402 laurinum, 403 lauro cerasi, 442 macidis, 366 mandarinae, 479 masticis, 496 ■ . matricariae, 676 Menthae, 630 crispae, 651 piperitae, 630 pulegii, 655 mirabile, 20 myrrhae, 486 nueis mosehati, 366 olibani, 489 palmarosae, 281 petit grain, 484 piperis, 320 polemii, 630 pvilegii, 030, 655 i-adicis helenii, 670 rosaeeum, 423 rosarum, 423 verum, 424 rosatum, 423 rutae, 455 sabinae, 273 santali ex India Occidentalis, 486 serpylli, 628 sinapis, 409 styracis, 419 tanaeeti, 679 terebinthinae americanum, 239 gallieum, 247 thujae, 267 thuris, 489 Valerianae, 663 vini, 36 wittnebianum, 519 zedoariae, 31 1 Olibene, 492 Omam, 557 Omum water, 557 Onion oil, 306 T2G Index. Oponal, 48