NL8005768A - Perfumes contg crotonoyl gps - pref 2-ethyl-3,6,6-trimethyl-1-crotonoyl-2-cyclohexene prepd lefactorily active substd cyclogeranoyl derivs - Google Patents

Abstract

New perfumes of formula (I) (where A is -CO-CH=CHMe and one of the 3 dotted lines is an additional bond), (I'), or their isomeric mixtures are used in perfumery, e.g. for scenting soaps, detergents, aerosols, cosmetics, bath salts and oils. (I) are prepd. e.g. by oxidizing an alcohol of formula (I; A is CHOCH-CH=CH-Me). Perfume notes of (I') are reminiscent of tobacco and eucalyptus seed, smoky and fruity. Substd. cyclogeranoyl derivs., used as intermediates in synthesis of (I'), and of formula (I where A is -COOR and R is 1-4C alkyl or aryl, esp. Ph) also have olfactory props., with a fruity, tobacco-like not, esp. reminiscent of eucalyptus seed, and can be used in perfumery.

Description

/ · VO 1123

New fragrances.

The invention relates to new fragrances.

These fragrances are the compounds of formula 1 (see the formula sheet), in which R represents alkyl or aryl, in particular phenyl, and in which one of the three dashed lines 5 is an additional bond.

The invention also relates to a process for the preparation of the new compounds 1, their use as fragrances and fragrance compositions, characterized by a content of a compound of formula 1.

The compounds 1 and their isomeric mixtures have special fragrance properties. These odoriferous properties resemble those of the compounds 1 of the mother application 750 ^ 571. Also worth mentioning here is the slightly fruity, tobacco-like nuance, in particular reminiscent of eucalyptus seed.

However, the esters 1 can also be used as starting materials for the preparation of the compounds 1 of the parent application 7501571.

The compounds 1 can therefore, because of their interesting olfactory properties, find use as fragrances, e.g. in perfumery for the preparation of perfume compositions, such as perfumes, or for the perfuming of all kinds of products, such as soaps, detergents, solid and liquid detergents, aerosols or other cosmetic products, such as ointments, facial milk, cream, lipstick, bath salts, bath oils etc.

Due to its very natural nuances, the isomer mixture 1 is particularly suitable for modifying known compositions, e.g. such of the type chypre. It is very well suited in combination with wood nuanese, e.g. of p-tert-butylcyclohexyl acetate, sandalwood oil, patchouli oil, cedryl acetate, methyl ionone.

The concentration of the mixture 1 according to the invention can vary within wide limits depending on the purpose of use, e.g. between about 1 wt.% (detergents) and about 15 wt.% (alcoholic solutions). In perfume bases or concentrates, the concentrations can of course also be higher.

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The esters 1 can be used for the same purposes as the compounds of formula 1 of the parent application 750 ^ 571 ·

The esters 1 can be prepared according to known methods for the preparation of cyclogeranoyl derivatives. The syntheses are illustrated in the reaction scheme depicted on the formula sheet, wherein R and the dashed lines have the meanings already mentioned.

The cyclization of the compound 3 can be carried out in ways known per se. Suitable cyclizing agents 10 are inorganic and organic protonic acids, such as sulfuric acid, phosphoric acid, methanesulfonic acid, formic acid, acetic acid and the like, or Lewis acids, such as BF 2 • SnCl 2, ZnCl 2, and the like. The acid used determines to some extent the isomer ratio of the compounds of formula 1. For example, e.g. formic acid with a 10 # 's content of concentrated sulfuric acid preferably the α-isomer, while phosphoric acid yields a mixture in which the o and /' isomers predominate.

The cyclization can be performed with or without a solvent. Suitable solvents are inert solvents such as mizzene, benzene, nitromethane, and the like. The temperature is not critical (room temperature or higher or lower temperatures).

The esters 3 are advantageously prepared from U, 7-dimethyl-6-octen-3-one (2). Thereby one can e.g. working according to Horner-Wittig [Wadsworth-Bnmons modification, J. Am. Chem. Soc. 83, 1733 (1961)]: In the presence of an alkali metal hydride or alkali metal alcoholate as the base, the ketone is reacted with carbalkoxy-methylenediethylphosphonate.

They work efficiently in an aprotic. solvent, such as benzene, toluene, dimethoxyethane, and the like. The reaction temperature is not critical. A temperature range of about 40 DEG-60 DEG C. is preferred, but it is also possible to work at lower or higher temperatures.

However, reaction of k, 7-dimethyl-6-octen-3-one with bromoacetic ester / Zn according to Reformatzky and water separation from the primary formed hydroxy ester are also possible. It is expedient to work in an inert solvent such as diethyl ether, benzene, toluene and the like. The water cleavage from the primary obtained hydroxyester 80080068 3 is preferably effected under the influence of PBr4 in pyridine [Shriner, Organic Beactions J_, 1 (1947)] ·

Esterification of the acid 5 is expediently effected by treating one of its acid salts, e.g. of an alkali metal salt, with an alkyl halide, such as ethyl iodide in alcohol (see, e.g., Eouben-Weyl, Organic Methods Chemistry VIII, 541, (1952)]. The reaction temperature is not critical, but the reaction is conveniently conducted at room temperature.

Finally, the acid 5 is accessible from the acid 1+ or 10 from the nitrile 6, optionally via the aldehyde 8. The cyclization of the acid 4 can be effected as stated above for the ester 3. carried out in a manner. The cyclic nitrile J can be prepared by methods known per se, e.g. alkaline saponification until the acid 5> The cyclic nitrile 7 can, however, also first be converted into the aldehyde 8, so e.g. can be reduced with diisobutylaluminum hydride [Milder et al, <7. Org. Chem. 24, 627 (1959)]. The reduction is expediently carried out in an inert solvent, such as hexane or toluene, and preferably at room temperature. The resulting aldehyde is then effectively oxidized to acid 5 with the aid of silver nitrate / caustic 20 [see, e.g. Walborsky et al., J. Am. Chem. Soc. 73, 2593 (1951)]. It is expedient to work in an alcohol / water mixture and at room temperature.

Example I

50 g (0.224 mol) of e, t-3-ethyl-4,7-dimethyl-2,6- were added to a solution of 450 ml of concentrated formic acid and 50 ml of concentrated sulfuric acid cooled to 5-10 ° C. octadienoic acid ethyl ester. After all had dripped on, the mixture was allowed to come to room temperature. It was further stirred at this temperature for 1 hour. The reaction mixture was poured onto ice and extracted three times with hexane. The combined hexane solutions were washed with water (once), NaHCO2 solution (twice) and again with water (three times), dried over sodium sulfate and evaporated. The crude product (49.1 g) was fractionally distilled. 37 g (72%) of pure 2-ethyl-3,6,6-dimethyl-2-cyclohexene-1-carboxylic acid ethyl ester were obtained with a boiling point of 63 - 64 ° C / 0.05 mmHg, n = 1, 4645.

The c, t-3-ethyl-4,7-8005768 u dimethyl-2,6-octadienoic acid ethyl ester used as starting material could be obtained as follows:

In a four-necked flask equipped with a mechanical stirrer, dropping funnel, reflux condenser and thermometer, a solution of 13.6 g (0.59 g atom) of sodium in 335 cm ethanol was placed. A solution of 77 g (0.5 mol) k, 7-dimethyl-6-octen-3-one and 1U5,6 g (0.65 mol) was added at 0-10 ° C within 1.5 hours. carbethoxymethylenediethethylphosphonate with 300 ml of toluene dropwise. The mixture was then heated at 0 DEG-5 DEG C. for 15 hours and at 60 DEG C. for 5 hours. The reaction mixture was poured onto ice water and extracted three times with hexane. The combined hexane solutions were washed three times with water, dried over sodium sulfate and evaporated.

The crude product (109 g) was distilled in a phactic manner. 76.2 g (67 #) of pure c, t-3-ethyl-7,7-octadienoic acid ethyl ester were obtained at 67-69 ° C / 0.05 mmHg; n ^ = 1, ^ 667.

Example II

3

A mixture of 81 cm 3 of concentrated formic acid and 9 cm 3 of concentrated sulfuric acid was cooled to 5-10 ° C and 10 g (39.7 ml) of 3-ethyl-U, 7-dimethyl-1-2 were carefully added at this temperature. 6-octadienoic acid-n-butyl ester. The mixture was allowed to reach room temperature and stirred at this temperature for about 1 hour. The reaction mixture was poured onto ice and extracted three times with hexane. The combined hexane solutions were washed with water (once), NaHCO2 solution (twice) and water (three times), dried over sodium sulfate and evaporated. The crude product (9.1 g) was fractionally distilled. 6.9 g (69%) of pure 2-ethyl-3,6,6-trimethyl-2-cyclohexene-1-carboxylic acid n-butyl ester with a boiling point of 73-7 ° C / 0.003 mmHg were obtained; 20 nD = 1.U663.

The 3-ethyl-7,7-dimethyl-2,6-octadienoic acid-n-butyl ester used as starting material was obtained by transesterification from the ethyl ester as follows:

In a nitrogen purged flask, a solution of 100 mg of sodium in 8 U cm of n-butanol was introduced and cooled to about 5 ° C. At this temperature, 20 g (0.09 mol) of 3-ethyl-U, 7-dimethyl-2,6-octadienoic acid ethyl ester were added. Then it was heated for 5 hours at 35 ° C and 3 hours at 100 ° C. To work up, the reaction mixture was acidified with a few drops of glacial acetic acid and then the bulk of the n-butanol was distilled off on a rotary evaporator. The residue was taken up in hexane and washed with NaHCO 2 solution (twice) and with water (three times), dried with sodium sulfate and evaporated. The crude product (19.3 g) was fractionally distilled.

16 U g of pure 3-ethyl-4,7-dimethyl-2,6-octadienoic acid-n-20-hutyl ester (73%) with a boiling point of 90-900 / 0.0¼ mmHg were obtained; n ^ -1.4677. Example III Floral composition

Parts 10 2-ethyl-3,6,6-trimethyl-2-cyclohexene-1-carboxylic acid ethyl ester 100 laurine 760 linalool 70 n-hexyl salicylate 30 15 cyclamenaldehyde 20 galbanum oil concentrated 20 1 000

The composition was found to be much more vivid and to gain diffusion by the addition of 2-ethyl-3,6,6-trimethyl-2-cyclohexene-1-carboxylic acid ethyl ester.

8005768

Claims (2)

1. Process for the preparation of new fragrances, characterized in that compounds of the formula I (see the formula sheet), in which Rc-C, -alkyl or aryl is represented and one of the three dashed lines is an additional bond, prepared in a manner known per se. 2. Process according to claim 1, characterized in that: a) an ester of formula 3 (see the formula sheet), in which R and the dashed lines have the previously mentioned meaning, or b) an acid of formula 5 (see the formula sheet) in which the dashed lines have the meanings already mentioned esterifies. 3. Process for perfuming products, characterized in that a compound of formula 1 (see the formula sheet), in which R represents C 1-6 alkyl or aryl and in which one of the three dashed lines is an additional bond, is used. k. Fragrance composition, characterized by a content of a compound of formula 1, wherein R represents C 1 -C 12 alkyl or aryl and wherein one of the three dashed lines is an additional bond. A process for the preparation of new fragrance compositions according to claim U, characterized in that a compound of the formula I is added to known perfume compositions or that such a compound is mixed with suitable natural or synthetic compounds as a component for fragrance compositions or mixtures. · * »8005768 i" V / COOR r ° Γ Η vs 2. N 'CQOH \ <^. COOH \ << ^ COOR li c 1 wf a X / :: X> CH0 I) - »j 6 7 8 8005768