As it is shown, the maximum pre-war prices have not been reached again, in spite of the universal depreciation of the money. Although in November 1921 the price went down as far as 2/2 per lb.), it was believed that this was not the lowest yet, for there were considerable stocks and little demand. In 1921, 4000 cases of 662 lbs. each arrived in London, where abundant stocks existed already. The oil was imported partly in exchange for textiles.

3

It is further stated that formerly there was a good market for staranise oil, chiefly for liqueurs and confectionery. Nowadays the Russian demand is missing and France, Germany and the United States require but little. In the latter country, the decrease in the demand for staranise oil is ascribed to the prohibition of alcoholic drinks. The best consumers of the articles are now most likely Spain and South America, but it is expected that the French and English demand will increase again.

Oil of Tagetes anisata. The fresh herb of Tagetes anisata, Lillo, n. sp., a composita growing in the pampas of Argentina at an elevation of from 1000 to 3000 m., yielded on steam distillation, according to F. Zelada3) 0.7 to 0.8 per cent. of a green oil. The product resembled anise oil and had the following properties: b. p. 214 to 2180, solidification p. -6°, d150 0.9862, a -1°10′, n1.5432, ester v. after acetylation 23.4, sap. v. 3.1, iodine v. 158.5, alcohol as C16H180 0.852 per cent., ester as C16H17OCOCH, 1.082 per cent., total alcohol as C16H180 3.229 per cent., soluble in 5 vols. of 90 per cent. alcohol1).

Tarragon Root Oil. See Estragon root oil, p. 34 of this Report.

Thyme Oil. · The Spanish oils of thyme are of different composition and may be grouped in oils containing thymol, carvacrol, or citral. The same division could be used for the manifold species of Thymus occurring in Spain. According to the 'few existing authentical indications concerning the botanical origin of the Spanish thyme oils, there seems to be a certain conformity in the characteristics of the plants belonging to one and the same of the groups mentioned. According to Rubeck and E. H. Holmes 5), Thymus vulgaris, L., and Thymus Zygis, L., which are much alike and are both known in Spain by the name of tomillo salsero, being used as pot-herbs, certainly belong to the first group. Thymus hyemalis, Lange, according to Holmes the mother-plant of the so-called Spanish verbena oil, is closely allied to Thymus hirtus, Willd. (tomillo limonero); both kinds contain citral). The similarity appears to be less striking (the relative indications in books, etc. are very scanty) between Thymus Mastichina, L., (tomillo blanco) and Thymus cephalotus, L., the oils of which according to Dorronsoro?)

-

1) Chemist and Druggist 95 (1921), 631. 2) Com. Bericht (German) 1921, 46. 3) Parfum. moderne 14 (1921), 32. 4) There seem to be grave discrepancies between the acetylation and ester values and the amount of alcohol, etc. calculated. Besides, C16H180 seems to stand for C10H180. 5) Perfum. Record 11 (1920), 339. 7) Comp. Report April 1911, 111.

6) Cf. Bericht (German) 1921, 87.

contain about 60 per cent. of cineole. We do not know, however, what variety of Thymus plants contain the oils rich in carvacrol. Holmes may be right in saying that Thymus Piperella, L., and Thymus cæspiticius, Hoffm., the popular name of which (pebrella) indicates a sharp taste like pepper, belong to the carvacrol group. An oil distilled from the fresh herb of Thymus capitatus, Lk. (from Granada) contained according to our own investigation 6 per cent. of thymol and a liquid phenol, perhaps carvacrol1).

This is about all that has been recorded as to the exact botanical origin of the Spanish thyme oils. On the other hand it is known that more than 30 (Willkomm 2) states 39) different kinds of Thymus are spread over the Iberian peninsula. They partly grow in one and the same district, have great similarity and are perhaps not always differentiated by the gatherers. The thyme plants are gathered above all from the "tomillares" (tomillo thyme) which are so characteristic for Spain and, with exception of the Northatlantic zone of the peninsula, occur in the central table-land as well as in the coast provinces and the lowlands along the Ebro, in South Aragon, Catalonia, Valencia, lower Andalusia and Algarbia, covering enormous spaces of uncultivated land. These "tomillares" attain their largest dimensions in the table-land, along the Duero, on either side of the central mountain chain and in the East, South and SouthWest of New Castile. There are thyme, lavender, sage and rosemary heaths, named after the labiate that preponderates. C. Hartwich) gives a very good description of such a heath:-"On this waste ground of débris the plants grow isolated, though fairly close together, so that the naked soil can be seen everywhere in between. This is the reason why such stretches of land often appear absolutely bare from a distance. The dominating plants, as the name of the steppe indicates already, is a species of thyme (Thymus Zygis, L.). The plant forms round little shrubs, perhaps as large as a fist, sometimes, when a stem grows a little higher, miniature trees, like those we owe to the Japanese art of gardening. They have small, needle-shaped leaves, on which the golden-yellow oil glands can be seen through a magnifying glass, and are covered with tiny red flowers. A stem which I examined at home was nine years old." The Thymus species most frequently named and apparently also the most widely distributed in Spain are Thymus vulgaris, L., Thymus Zygis, L. and Thymus Mastichina, L. As E. M. Holmes 1) determined, Thymus Zygis differs from the otherwise similar common thyme, as follows: The bracts are larger than the ordinary leaves, the whirls of whitish flowerets from an uninterrupted spike and no axillary or terminal heads as with Thymus vulgaris. According to Willkomm5) the common thyme is to be found in Navarra, in the plain of Pamplona, along the Duero and the Iberian central mountain chain, in the Nord-West of Guadalajara and in the mountainous regions of Catalonia and Valencia, whereas Thymus Zygis occurs in the North of Old Castile, near Alar del Rey (Palencia) in the upland ol Murcia in New Castile, in the Vega of Granada, in the Sierra Nevada and in the uncultivated coast regions of the provinces of Cadiz and Huelva. - Thymus Mastichina grows on waste ground and by the side of paths and fields in Cantabria, in the slate mountains of Asturia and Leon, in the northern table-land (together with Thymus vulgaris), in the lavender heaths of New Castile along the central mountain chain (together with Thymus Zygis), on sandy soil between Almeria and the Bay of Gibraltar, on the dry calcareous hills round Granada, and in the "tomillares" of the coast zone of Cadiz and Huelva (together with Thymus Zygis). Of

-

1) Bericht October 1889, 56.

2) Engler, Die Vegetation der Erde. Grundzüge der Pflanzenverbreitung auf der iberischen Halbinsel. By R. Willkomm. 1896. 3) Spring holidays in Spain. Apotheker-Ztg. 21 (1906), 4) Loc. cit. 5) Loc. cit.

842.

the other species the following are mentioned:-Thymus hirtus, Willd., which thrives in Central and southern Spain, on the calcareous hills round Granada and in the lower regions of the Pinsapo Forest, Thymus hyemalis, Lange, in south-eastern Spain, Thymus cephalotus, L., in Valencia, in lower Asturia and, according to Dorronsoro1) in Almeria, Thymus cæspiticus, Brot., in Estremadura and Galicia, Thymus Piperella, L., in Valencia on rocky slopes, Thymus cerpylloides, Bory, (Samarilla) in the alps of the Sierra Nevada. To quite another species belongs the so-called Andalusian thyme (Tomillo andaluz tomillo carrasqueno) or Corydothymus, which according to Blas Lazaro1) is Corydothymus capitatus, Rchb. B. Dorronsoro 2) writes about it as follows: -“Various kinds of thyme are distilled in Spain, viz., the tomillo corriente (common thyme) = tomillo aceitunero (olive thyme) Thymus vulgaris, L., the tomillo risquero (thyme of the rocks) Thymus Zygis, L., the tomillo sanjuanero (St. John's thyme) = Thymus hyemalis, Lg., and the tomillo carrasqueno (holm-oak thyme) or tomillo andaluz (Andalusian thyme), which latter, however, is no real thyme, but Corydothymus capitatus, Rchb., belonging to an allied species."

=

=

In August 1915, we examined in our research laboratory a Spanish oil from Barcelona, on whose botanical origin, unfortunately, nothing definite could be ascertained. Since only very little positive is known as to the chemical composition of the Spanish oils, the results of the following investigation gave no clue concerning the botanical source of the oil. Owing to the war, the work had unfortunately to be discontinued and was terminated only before long, when the oil had been left standing for nearly six years (protected from direct light) after having been fractionated and freed from phenols by treatment with dilute caustic lye.

The original oil showed the following constants: d150 0.9297, ap +0° 35', soluble in 3.5 vols. and more of 70 per cent. alcohol; phenols 45 per cent., for the greater part thymol.

The most volatile fraction of the b. p. 130 to 132° smelled of amyl alcohol and gave the characteristic naphthylurethane, m. p. 51 to 52° obtained by us on a previous occasion. In the fractions of b. p. range 132 to 150° we suspected owing to their amylaceous smell the presence of amylcarbinols. Since they consisted doubtlessly of mixtures, contaminated possibly with small amounts of amylic or similar ketones, we refrained from further isolation and identification. We only by way of experiment, succeeded in isolating a naphthylurethane, m. p. 47 to 48°. We were unable to prove the existence of a ketone, nor the formation of such by oxidation with bichromate solution.

A small fraction, b. p. 145 to 150° (d150 0.8495, ap +3° 28′, П200 1.45052), yielded on benzoylation with the aid of pyridine a benzoate, b. p. 134 to 135° (6 mm.), which on saponification gave rise to an alcohol with the characteristic odour of By-hexenol. This alcohol had previously) been obtained by us in shape of its phenylacetate from the last runnings of Japanese peppermint oil. Although the oil showed the same boiling point (156) as the above-mentioned alcohol, we were unable to raise the melting point of the naphthylurethane beyond 58 to 60°, whereas the derivative of the pure alcohol from peppermint oil melts at 72°. In spite of this discrepancy we do not hesitate to accept the identity of the alcohol with 6,7-hexenol. A closer examination carried out with more material wil! in all probability confirm this identity and thus prove the existence of free 6,7-hexenol in Spanish thyme oil.

p. 134.

1) Cf. Bericht (German) 1921, 87. 2) Estudio quimico de esencias naturales españolas. Madrid 1919, 3) Report 1918, 39; Walbaum, Journ. f. prakt. Chem. II. 96 (1918), 245.

In the next fractions we found after repeated, careful fractionation a new terpene with a carrot-like odour and the following constants:

The values obtained on combustion pointed to a terpene C10H16:0.1822 g. substance gave 0.5879 g. CO2, 0.1958 g. H2O.

manner.

.

The nitrosochloride, purified by means of chloroform and methyl alcohol, shows a strong tendency to decompose and can therefore be prepared and purified only in small amounts. Decomposition starts at about 85° in a very sudden and violent The piperidide melts at 194 to 1950, the nitrolbenzylamine indistinctly from 105 to 1080; the anilide was not obtainable, neither a solid nitrosate. When dissolved glacial acetic acid and cooled down the terpene adds somewhat more than two atoms of bromine; the resulting bromide remains oily. Likewise, the hydrochloride obtained by saturating, in glacial acetic acid solution, the terpene with hydrogen chloride gas was liquid. On trying to hydrate the terpene by action of acetic and sulphuric acids resinification resulted. When oxidized by means of permanganate solution, with cooling by ice (according to the method for obtaining pinonic acid), the terpene gave rise to a neutral oxidation product soluble in water and chloroform, which did not distil without decomposing and was therefore not yet obtainable in the crystalline state. On further oxidation with neutral permanganate at 100° there was obtained, in addition to oxalic acid, m. p. about 100°, and acetic acid (Ag estimated in the silver salt 64.20 per cent.), an acid which decomposed on distillation in vacuo and which evidently was not a ketonic acid. Treatment with dimethyl sulphate yielded no ester. Details as to the chemical structure of the terpene are to be expected only after closer investigation. We wish to add that this oil offered no clue for the presence of a-pinene, in contradiction to another oil which years ago1) we found to contain that terpene. Considering the great variety in the botanical origin of the Spanish thyme oils this different behaviour is by no means surprising.

A very small amount of camphene is present in the Spanish oil. It was identified by treating the fractions boiling above 157° in the usual manner with acetic-sulphuric acid, when a trifle of isobornyl acetate (b. p. 82 to 88° at 6 mm.; sap. value 202) was isolated by fractionation. The free isoborneol obtained therefrom by saponification melted at 208 to 2120.

B-Pinene was likewise a constituent of the oil. After oxidising a fraction b. p. 165 to 1690 with alkaline permanganate a hydrocarbon with the following constants was regenerated: b. p. 163 to 167°, d200 0.8520, α +3° 45', Пp200 1.46609, mol, refr. found 44.02, calc. 43.5. On further oxidation with permanganate is yielded nopinic acid, m. p. 126 to 127°. The hydrocarbon occurs in minute quantity only.

A hydrocarbon fraction, b. p. 165 to 168° (d150 0.8567, ap +3°57', np200 1.47141) which on saturating with hydrogen chloride gas and after some standing had yielded

1) Report October 1894, 57.

terpinene dihydrochloride, m. p. 52°, was suspected to contain sabinene. However, on oxidation with alkaline permanganate solution, no sabinenic acid was obtainable. p-Cymene could be proved to be present only after many fruitless attempts, by oxidation of fractions b. p. 175 to 179° with strong permanganate solution, when a-hydroxyisopropylbenzoic acid, m. p. 153 to 154°, was the result. On boiling with strong hydrochloric acid the difficultly-soluble propenylbenzoic acid, m. p. 160 to 1610, was formed. The amount of cymene present is exceedingly small. As far back as 1856 Lallemand1) was able to prove the presence of p-cymene in a thyme oil. However, it must remain an open question whether in this case an oil of different botanical origin was under investigation or whether the p-cymene had been formed, by a secondary process, from terpinene, an important constituent of the oil.

y-Terpinene is the main constituent of the phenol-free oil and could be traced in all sub-fractions b. p. 176 to 1830. All of these fractions gave on saturation with hydrogen chloride gas in glacial acetic acid solution, an oily hydrochloride which either was precipitated by addition of water or was obtained on evaporation of the solvent in an open dish after some standing, and could be brought to solidification by strong cooling and additionally after inoculation. When crystallized from methyl alcohol the dihydrochloride melted at 51 to 520, and in mixture with the corresponding derivative of dipentene very considerable depression of the melting point was observed. From various of the afore-mentioned subfractions there was obtained, on oxidation with alkaline permanganate in the cold, the erythritol C10H2004 characteristic of y-terpinene; m. p. 236 to 237°. On boiling with dilute sulphuric acid in a current of steam a smell of phenols (thymol, carvacrol) was noticed. When several fractions (b. p. 175 to 1790; 176 to 178°; 177°) were brominated in absolute ethereal solution, after being chilled down to freezing mixture temperature, separation of a solid, slightly yellow bromide was repeatedly observed which, however, on suction or on spreading on cooled porous plates decomposed rapidly with liquefaction and evolution of hydrogen bromide. Since just these fractions yielded y-terpinene dihydrochloride in good amount it might have been the case of a bromide of y-terpinene. Possibly the investigators working on terpinene have hitherto overlooked the fact that y-terpinene, in absolute ethereal solution at reduced temperature forms a bromide which is unstable at ordinary temperature when exposed to the air. That a-terpinene was absent was concluded from the non-formation of the nitrosite; likewise we were unsuccessful in obtaining, by oxidation with alkaline permanganate, the dihydroxy dimethyladipic acid characteristic of a-terpinene which in many cases, besides y-terpinene, is a constituent of essential oils.

Of alcohols, the following were found to be present:- linalool, borneol, terpinenol-4, and geraniol.

The first-named alcohol was found in fractions of the b. p. 77 to 78° (6 to 7 mm.) and the sp. gr. d150 0.8975 to 0.8991 which were separated from fractions containing borneol by sharp fractionating. To judge from the odour, an oil of the b. p. 197 to 199.5° and the sp. gr. d150 0.8750 consisted of fairly pure linalool from which the phenylurethane, m. p. 65°, was obtained without difficulty on treatment with phenylisocyanate. Oxidation with bichromate mixture yielded citral.

1-Borneol separated off in the solid state from the fraction b. p. 86 to 1020 (8 mm.) when distilling in vacuo, and was identified by its odour, its m. p. 204°, and by the formation of camphor on treatment with bichromate mixture.

1) Jahresber. d. Chem. 9 (1856), 616; acc. to Annal. de Chim. Phys. (3) 49 (1857), 148.