Patent GB-190325695-A (GB)
Title: Manufacture of New Compounds, Derived from Citrylidene-acetic Acid, its Nitrile or its Ethers.
Inventor: VERLEY ALBERT
Filed: 1903-11-24
Granted: 1904-01-28
Abstract: 25,695. Verley, A. Nov. 27, A.D. 1902, [date applied for under Patents Act, A.D. 1901]. Cyclo-citrylidene acetic acid, its nitrile and ethers; tertiary alcohols and their acetals and esters.-Relates to the production of new compounds, suitable for use in perfumery, from citrylidene acetic acid, its nitrite, or its ethers. (1) These compounds are transformed into cyclic isomers, by strongly agitating for some hours with syrupy phosphoric acid, containing about 8 per cent. of sulphuric acid, at a temperature of about 60‹ C. The resulting product is treated with water, extracted with ether and distilled in vacuo. By this means cyclocitrylidene-acetonitrite may be obtained which has an odour of violets. The cyclo-citrylidene acetate of methyl is a colourless liquid having an odour of migno nette. The cyclo-citrylidene acetate of ethyl has an odour of violets. The other ethers of cyclo - citrylidene acetic acid are colourless liquids, their odour becoming gradually less as the series is ascended. The cyclo-citrylidene acetic acid, obtained by direct isomerization, or by saponification of its nitrile or ethers, is a thick syrup, which can be oxidized to yield the #-cyclo-citral described by Tiemann. When hydrogenated by sodium amalgam in an alkaline solution it probably gives the acid the ethylic ether of which has a raspberry odour. (2) The ethers of cyclo-citrylidene acetic acid serve as a raw material for producing a new tertiary alcohol which, with its ethers, possesses a strong fresh odour of violets, as follows. The ether is treated with Grignard's iodo-methylate of magnesium The alcohol is liberated by water. It may also be obtained by treating #-ionone with the iodo-methyllate of magnesium. To obtain the corresponding ethers, the sodium derivative in an ethereal solution is treated with an acid chloride; or the alcoholic mass instead of being decomposed by water may be treated with an anhydride or an acid chloride. The acetic, butyric, valeric, benzoic, &c. ethers can be thus prepared, as well as the mixed acetals. In the latter case, instead of acid chlorides, the alcoholic chloro-methylates derived from formic aldehyde are used. All these ethers and acetals possess a violet odour. (3) The same alcohol and its ethers can also be obtained from an ether of citrylidene-acetic acid by the action of iodomethylate of magnesium, whereby an aliphatic tertiary alcohol having the formula :- is obtained. The same alcohol may be obtained by the action of iodomethylate of magnesium on pseudoionone. It has a pronounced grass-like odour. By acting on it with dilute acids at the boiling point it is transformed into a cyclic isomer, the a-isomeride of the above cyclic tertiary alcohol, the odour being very like that of the #-derivative. This body is also produced by the action of MgI.CH3 on a-ionone. By replacing the iodomethylate of magnesium by its homologues, homologues of the a- and #-derivatives of the alcohol may be obtained ; for example, the iodoethylate produces an alcohol, C16H28O, which is a syrupy liquid, while the action of the iodoethylate on ionone produces an intermediate alcohol having a formula C15H26O. These all possess an odour of violets.