Semi-annual Report on Essential Oils, Synthetic Perfumes, and Related Materials

Oil of Abies Pindrow. - Cones and young shoots of the Indian silver fir, Abies Pindrow (Royle) Spach1), yielded on steam distillation an oil, of which we received a sample some time ago. It was colourless, of agreeable balmy odour and showed the following constants: d180 0.8647, α-10°59′, np200 1.47328, acid v. 0.3, ester v. 6.5= 2.3 per cent. ester (bornyl acetate), soluble with slight turbidity in 3 volumes and more of 90 per cent. alcohol; soluble in 1 vol. and more of 95 per cent. alcohol.

The tree occurs in the lower Himalaya regions, at a height of between 2400 and 3000 metres.

Oil of Aburachan. By distillation of the leaves and twigs of Lindera præcox, Bl., a lauracea growing in Japan, Y. Shinosaki) obtained about 0.3 per cent. of a light brown coloured oil which had a somewhat strongly camphoraceous odeur and the following characters: d150 0.9094 to 0.9178; a—3°57' to -5°1′; ПD200 1.4850 to 1.4866; acid value, 0.69 to 0.92; sap. value, 45.76 to 48.69; sap. val. after acetylation, 90.48 to 98.62. The following substances were isolated3): - 2 per cent. of a-pinene, 14 per cent. of camphene, 8 per cent. of cineole, 10 per cent. of an aliphatic terpene (b. p. 40 to 41° at 2 mm., d150 0.8251, no 1.4840), borneol present in the oil partly free and partly as ester, geraniol (23 per cent. with borneol), 8 per cent. of caryophyllene, 21 per cent. of d-cadinene, 5 per cent. of a sesquiterpene alcohol C15H26O, and a tertiary alcohol (b. p. 140 to 142° at 4 mm.; d150 0.9740; α-5o, nьzo 1.5072). From the alkaline liquor after saponification of the original oil there were isolated: acetic acid, a decylenic acid C10H18O2 (b. p. 106 to 107° at 1.5 mm., d150 0.9339, np200 1.4552, acid value 328 to 334.9, iodine value 142.24, probably identical with citronellic acid) and a saturated weak acid of higher series and having a high boiling point.

Ajowan Oil. of this Report).

Y. Murayama found in this oil a new terpene, moslene (cf. p. 51

Almond Oil, bitter. - A bitter almond oil "genuine, free from chlorine", sent us for inspection, proved an "excellent" acquisition for the buyer, as it was a crude, strongly chlorinated benzaldehyde of a reddish-brown colour (due to iron), containing about 30 per cent. of nitrobenzene.

The defects of the product were revealed at once by its constants, as it was far too heavy (d150 1.1237), had too high a refraction (np200 1.54876) and did not dissolve in 50 per cent. alcohol; besides, it gave a strong chlorine reaction. It resulted on closer investigation that these irregularities were due to nitrobenzene, present in the proportion

1) According to Brandis, this is only a variety of Abies Webbiana, Lindley. Comp. A. Engler and K. Prantl, Die natürlichen Pflanzenfamilien vol. II, 1, page 60. 2) Journ. chem. Ind. Japan 24 (1921), 444. According to Journ. Soc. chem. Ind. 40 (1921), A. 674. 3) Details are missing in the abstract.

indicated above. After having isolated it, it could be identified by its odour and its other properties:- d150 1.2032, np200 1.55104, solidification point +3.6°.

Nitrobenzene being highly poisonous, as we have repeatedly pointed out in our Reports1), its use as an adulterant is inexcusable. We can only take it that the seller was too silly to understand the bearing of his action, otherwise he ought to have realized what ill effects the addition of nitrobenzene to a product often used in the household may have.

As E. Pinoff2) says, the presence of nitrobenzene in bitter almond oil can easily be proved in the following way:-10 cc. of a 40 per cent. formaldehyde solution and 20 cc. of concentrated ammonia are filled in a cylinder holding 100 cc. and which can be closed with a stopper of india-rubber. After having shaken the mixture carefully for some time, it must be allowed to stand for five minutes. Then it is shaken vigorously with 10 cc. of the bitter almond oil and again allowed to stand. The pure bitter almond forms an emulsion with the formaldehyde-ammonia, whereas the nitrobenzene deposits as a clear liquid. The nitrobenzene is then reduced with zinc and hydrochloric acid to aniline, which can be identified by one of the well-known reactions. We are of opinion that the usual method, according to which the benzaldehyde is bound to bisulphite, is simpler and more convenient (cf. Gildemeister and Hoffmann, The Volatile Oils, 2nd edition, vol. I, p. 585).

Oil of Amomis jamaicensis. The oil of Amomis jamaicensis (wild pimento), the constants of which we quoted in our Report of 1920, p. 6 after a communication in the Bulletin of the Imperial Institute, London, has been further investigated by O. D. Roberts3). After removing the free acids (0.2 per cent. acetic and caproic acids), an aldehyde (0.1 per cent.) and a phenol (0.1 per cent., not eugenol) the oil was hydrolysed with boiling alcoholic potassium hydroxide and the oil separating after addition of water and extracting with ether was submitted to fractional distillation at 14 mm. pressure, which gave the following fractions: 1. B. p. 75 to 80° (175 to 190° at ordinary pressure), 32 per cent. of the original oil; 2. b. p. 80 to 95° (190 to 2050, ord. pr.), 42 per cent.; 3. b. p. 95 to 110° (205 to 220°, ord. pr.), 4 per cent.; 4. b. p. 110 to 1250 (220 to 235° ord. pr.), 6 per cent.; residue 16 per cent. of the original oil. Fraction 1 contained 47 per cent. cineole 15 per cent. of the original oil (resorcinol method and iodole addition compound), a-phellandrene (nitrite, m. p. 112 to 113°), and dipentene (tetrabromide, m. p. 124°). The principal part of fraction 2 had the constants: b. p. 197 to 1980, 500.8693, α-3°39′, ПD200 1.4655 and was identical with l-linalool (oxidation to citral; a-citryl-3-naphthocinchoninic acid, m. p. 200o). In fraction 4 geraniol was proved to be present (diphenylurethane, m. p. 80 to 81°). The residue boiling above 235° was heated on the water bath under reduced pressure for some weeks with sodium. There was thus obtained by distillation under 15 mm. pressure a colourless oil, with a slight balsamic odour, b. p. 245 to 290° (uncorr.), do 0.9320, which was still slowly attacked by sodium.

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The author summarizes his investigation as follows:- The oil of Amomis jamaicensis contains about 17 per cent. of terpenes (a-phellandrene and dipentene), 15 per cent. of cineole, 38.3 per cent. of alcohols (chiefly -linalool with some geraniol), 1.5 per cent. of ester (linalyl acetate), each 0.1 per cent. of phenols and aldehydes, both undetermined, 0.2 per cent. of acetic and caproic acids, and 27.8 per cent. residue probably containing sesquiterpenes.

1) Cf. for instance Report 1918, 5. 2) Pharm. Zentralh. 62 (1921), 610.

(1921), T. 95.

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Oil of Andropogon Iwarancusa. — J. L. Simonsen1) investigated the oil of Andropogon Iwarancusa, Jones, a graminea occurring in the Himalayas and the outer hill zone from Kashmir to Assam and ascending to 8000 ft. and above, also in the plains from North West Himalaya to Bombay Presidency. The pale yellow oil, which had been obtained in a 1 per cent. yield from the grass, possessed a marked smell of peppermint and had the following constants: -d 0.9203, [α]D‰00 +51.68°, np300 1.481, acid v. 0.7, sap. v. 12.0, sap. v. after acet. 47.4, percentage of ketone, by absorption with neutral sodium sulphite solution, 77 per cent. On distilling and refractionating the oil under diminished pressure (200 mm.), the following fractions were obtained: 1) 115 to 130° (14.6 per cent.), 2) 130 to 174 (1.6 per cent.), 3) 174 to 185° (70 per cent.), 4) 185 to 205° (12 per cent.). The first fraction consisted essentially of a hydrocarbon, b. p. 101° (100 mm.), 163 to 164° (698 mm.), d 0.8565, [a]D300 +54.82°, npo 1.474, smelling pleasantly reminiscent of cymene. When dissolved in acetic anhydride and treated with a drop of sulphuric acid, a transient purple coloration appeared, which rapidly passed into a deep brown. When the hydrocarbon was treated with hydrogen chloride in ethereal solution, an oil resulted which was probably a monohydrochloride; with hydrogen bromide in acetic acid solution a viscous oil was obtained, which was evidently a dihydrobromide C10H18Bг2. The hydrogen iodide derivative was very unstable, and decomposed even when kept at 0°. Fraction 2) consisted apparently mainly of a mixture of d-41-p-menthenone-3 and the hydrocarbon. Fraction 3) (0.9321, [α]D‰00 +36.76°, П 1.481) consisted, by 98 per cent., of d-41-p-menthenone and was purified by solution in sodium sulphite solution and reprecipitation (and racemisation, comp. Read and Smith, p. 34 of this Report) by alkali, when it showed the following constants: - b. p. 180 to 181° (200 mm.), 230 to 231° (697 mm.), do 0.9307, [a]D800 +7.92°, np300 1.481. Fraction 4) still contained a considerable quantity of the ketone. The identity of the racemic ketone with dl-41-pmenthenone-3=piperitone (comp. p. 149 of this Report) is proved, according to Simonsen, by the formation of the benzylidene derivative (m. p. 61°) and the hydroxylamino-oxime (m. p. 170 to 171°), furthermore by oxidation of the ketone, by ferric chloride, to thymol and by the reduction to menthol. Besides, the author prepared: the a-semicarbazone (m. p. 225 to 227°), the B-semicarbazone (m. p. 174 to 176°), an optically active ß-semicarbazone (m. p. 193 to 1940), the oxime (m. p. 117 to 118°), and proved thus the identity of his ketone with the 41-menthenone-3 obtained by Wallach and others). The discrepancies observed in the constants as compared with the values found by former authors (a-semicarbazone, m. p. 224 to 226°, B-semicarbazone, m. p. 171 to 1720, oxime, m. p. 107 to 109°) are explained by Simonsen by assuming that the compounds obtained formerly had not been quite pure and free from isomerides.

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On oxidising the ketone with potassium permanganate solution, at 0°, 1, y-acetyla-isopropylbutyric acid was obtained; b. p. 195 to 200° (48 mm.).

Thus the oil of Andropogon Iwarancusa consists up to 80 per cent. of d-41-menthenone-3 and of a hydrocarbon of unknown constitution.

Angelica Oil. - Last autumn, it is true, the Thuringian plantations supplied abundant quantites of raw material, but the prices remained high, as there was a vivid demand, owing to the completely exhausted stocks of oil. Although we had secured considerable lots, our production was scarcely large enough to come up to the requirements from all quarters, so that we were almost sold out at the beginning of the present year. The prospects are not very favourable, as there are only few

1) Journ. chem. Soc. 119 (1921), 1644. 2) Comp. Reports October 1910, 99; 1916, 18.

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