MXPA00009025A - Perfumes comprising 4-isobutylcyclohexanols - Google Patents

Abstract

The invention concerns perfumes and perfumed products comprising 4-isobutylcyclohexanols according to formula (I), wherein R1 represents hydrogen or a methyl or ethyl group and R2 represents hydrogen or a methyl group. The invention also concerns compounds according to formula (I) wherein R1 represents a methyl or ethyl group and R2 represents hydrogen or a methyl group.

Description

PERFUMES THAT INCLUDE 4-ISOBUTILYCYCLOHEXANOLS Description of the invention The invention relates to the 4-isobutyl-cyclohexane-1-ols, to their use as fragrance materials and to perfumes and perfumed products comprising these alcohols. In the technique of perfumery there is a continuous interest in new fragrance materials, on the one hand caused by a continuous need for compounds with a new odoriferous character, and on the other hand caused by the fact that many of the widely known materials have entered under scrutiny lately due to certain undesirable properties. In this way, some well-known fragrance materials have been criticized due to their instability, potential in some applications. Some of these are well-known floral fragrances, such as a-hexilcin aldehyde, 2-methyl-3- (p-tert-butylphenyl) propanal, 2-methyl-3- (p-isopropylphenyl) propanal, 3- (p-ter -butylphenyl) propanal and hydroxy-citronellal.

Some alkyl-substituted cyclohexanols are widely known in perfumery. In this way, S. Arctander, Perfume and Flavor Chemicals mentions 4-isopropyl-, 4-tert-butyl-, 4-teramyl-, 4-heptyl- and 2-methyl-4-teramyl-cyclohexanol (monographs Nos. 2692, 165, 1531, and 1749). The odorous character of the five compounds is predominantly to woods with notes Canforáceas, to pine, vetiver, cedar and also frequently dry with odoriferous notes to tar or leather. 2-tert-butylcyclohexanol (monograph No. 432) is also described as a dry, camphor, and tarry wood odor. The 4-isoamylcyclohexanols, particularly those substituted with di-, tri- and tetramethyl are described in U.S. Patent 4,400,545 as fragrance materials with balsamic, wood, sweet, root, moisture, earthy and leather odors. The 4- (alkyl of 8 carbon atoms) cyclohexanols are described in European Patent EP 005 196 as possessing an odor that resembles 4-tert-butyl-cyclohexanol, but less strong. The most important compound is 4- (2,2,3,3-tetramethylbutyl) cyclohexanol.

In Japanese Patent JP 02131405 (Hasegawa Koryo Co., Ltd.) 2-, 3- and 4-alkylcycloalkanols and esters thereof are described as roach repellents. In the past it has been established that these compounds are only used as fragrances, but for alcohols this is not further substantiated other than by reference to the Arctander monographs cited above, and no indication of the odoriferous character is given in this patent application. . In the European patent EP 0 053 979 the alkyl substituted 3- (2-alkenyl) -cyclopentanols are widely described with a wide variety of floral, fruity and woodsy notes of smell, reminiscent of roses, muguet, bergamot, cucumber , hay, dry wood, cedar or vetiver. The specific compounds shown are all unsubstituted 3 (2-alkenyl) cyclopentanols and 1,2,2-trimethyl-3 (2-alkenyl) cyclopentanols. In the United States patent US No. 4,277,618 describes the "L-methyl-2-C4-cyclohexanols (C4 = sec-butyl or tert-butyl) as intermediates in the synthesis of the corresponding acetates Only the latter are said to be fragrance materials.

In US Pat. No. 3, T69,330, l-ethyl-2-C4-cyclohexanols (C4 = n-butyl, isobutyl, sec-butyl or tert-butyl) are described as fragrance materials with a woodsy odor. It has now been found that the 4-isobutylcyclohexanols of the following formula I are valuable fragrance materials with a strong muguet odor, contrary to the related 4-tert-butyl-, tert-a and isoamylcyclohexanols, all having a smell predominantly wood and leather.

Formula I In formula I, Ri represents hydrogen, or a methyl or ethyl group. Preferably Ri is hydrogen or methyl. R2 represents hydrogen or a methyl group. Preferably, R2 is hydrogen. In this way, the invention provides perfumes and perfumed products comprising the alcohols according to the formula I. In addition, the invention provides a process for imparting a note of odor to thrush to the perfumes and products to be perfumed. Finally, the invention provides novel fragrance materials according to formula I above, wherein Ri is a methyl or ethyl group, as well as 2-methyl-4-isobutylcyclohexan-1-ol. The alcohols according to the invention can be used as such in a wide range variety of products, or can be used as components of a perfume to contribute to its muguet odor. This smell does not necessarily need to be It is the strongest or predominant odor note in the perfume or in the final perfumed product, but rather clearly contributes to a note to muguet to the full smell of such perfume or scented product. For purposes of this invention, a perfume is defined as a mixture of fragrance materials, if desired mixed with or dissolved in a solvent Suitable or mixed with a solid substrate, which is used to impart a desired odor to the skin and / or any product for which a pleasant odor is indispensable or desirable. The alcohols according to the invention and the perfumes containing them are particularly suitable for use, for example, in fabric washing powders, washing liquids, fabric softeners and other textile care products; soaps, bath and shower gels, shampoos, hair conditioners and other personal cleansing products; cosmetic products such as creams, ointments, toilet waters, products for use before shaving or after shaving, lotions for the skin and other types of lotions, talcum powder, body deodorants and antiperspirants. Other fragrance materials known in the art which can be sold in combination with an alcohol according to the invention in a perfume are, for example, natural products such as extracts, essential oils, absolutes, resinoids, resins, concretes, etc. , but also synthetic materials such as hydrocarbons, alcohols, aldehydes, ketones, ethers, acids, ethers, acetals, ketals, nitriles, etc., including saturated and unsaturated compounds, aliphatic, carbocyclic and heterocyclic compounds. Such fragrance materials are mentioned, for example in S. Arctander, Perfume and Flavor Chemicals (Montclair, NJ, 1969), in S. Arctander, Perfume and Flavor Materials of Natural Origin (Elizabeth, NJ 1960) and in "Flavor and Fragrance. Materials - 1991", Allured Publishing Co. Wheaton, 111. USA. Examples of the fragrance materials that can be used in combination with an alcohol according to the invention are: geraniol, geranyl acetate, linalool, linalyl acetate, tetrahydrolinalol, citronellol, citronellyl acetate, dihydromyrcenol, dihydromyrcenyl acetate, tetrahydromyrcenol , terpineol, terpinyl acetate, nopol, nopyl acetate, 2-phenylethanol, 2-phenylethyl acetate, benzyl alcohol, benzyl acetate, benzyl salicylate, styrylallyl acetate, benzyl benzoate, allyl salicylate, dimethylbe-cylcarbinol , trichloromethephenylcarbinyl acetate, p-tert-butylcyclohexyl acetate, isononyl acetate, vetyveryl acetate, vetyverol, α-hexylcinnamaldehyde, 2-methyl-3- (p-tert-butylphenyl) propanal, 2-methyl-3- ( p-isopropylphenyl) propanal, 3- (p-tert-butyl phenyl) propanal, 2,4-dimethylcyclohex-3-enylcarboxaldehyde, tricyclodecenyl acetate, tricyclodecenyl propionate, 4- (4-hydroxy-4-ethylpentyl) - 3-cyclohexencarboxald ehido, 4- (4-methyl-3-penteni) -3-cyclohexencarboxaldehyde, 4-acetoxy-3-pentyl-tetrahydropyran, 3-carboxymethyl-2-pentylcyclopentane, 2-n-heptyl-cyclopentanone, 3-methyl-2-pentyl -2-cyclopentenone, n-decanal, n-dodecanal, 9-decenol-l, phenoxyethyl isobutyrate, phenyl-acetaldehyde dimethyl-acetal, phenylacetaldehyde diethyl acetal, geranyl-trilel, citronellyl-nitrile, cedryl acetate, 3- isocanfilcyclohexanol, methyl ether of cedrile, isolongifolanone, aubepin-nitrile, aubepin, heliotropin, coumarin, eugenol, vanillin, diphenyl oxide, hydroxycitronellal, ionones, methylionones, isomethylionones, irons, cis-3-hexenol and esters thereof, musks of Indan, tetralin musks, isochroman musks, macrocyclic ketones, macrolactone musks, ethylene brasilate.

The solvents which can be used for perfumes containing alcohols according to the invention are, for example: ethanol, isopropanol, diethylene glycol monoethyl ether, dipropylene glycol, diethyl phthalate, triethyl citrate, isopropyl myristate, etc. The compounds according to the invention can be prepared according to procedures known in the art, particularly starting from 4-isobutylphenol and following the procedure described for the corresponding 4-isoamyl-cyclohexanols in US Pat. No. 4,400,545. The alcohols according to the invention are generally obtained as mixtures of the cis and trans isomers (OH and isobutyl on the same or opposite sides of the ring, respectively), the cis / trans ratio being dependent on the synthesis procedure. In general, the odors of the isomers are different and the isomers can be separated by methods known in the art such as column chromatography, fractional distillation and gas chromatography. The isomers can be used separately as fragrance materials or mixtures of isomers obtained from synthetic processes can be used as such, depending on which particular odor character or odor trait mixture is preferred for a particular application. Also, the alcohols according to the invention exist in various stereoisomeric forms. These are obtained by synthetic procedures described above as racemic mixtures, which can be separated into various stereoisomers by methods known in the art, particularly by gas chromatography using chiral columns. Therefore, the invention provides the alcohols as cis / trans and stereoisomeric mixtures as well as the various cis and trans stereoisomers separately and includes the use of these separate isomers as fragrance materials. The amounts in which an alcohol according to the invention can be used in perfumes or in products to be perfumed can vary within wide limits and depend, among other things, on the nature of the product, on the nature of the amount of the other components of the perfume in which the compound is used and the desired olfactory effect. It is therefore only possible to specify broad limits, which, however, provide sufficient information for the person skilled in the art to be able to use the alcohols according to the invention for this specific purpose. In perfumes, an amount of 0.01% by weight or more of an alcohol according to the invention will generally have a clearly perceptible olfactory effect. Preferably, the amount is 0.1% by weight or greater, more preferably at least 1%. In general, it will be less than 80% by weight. The amount of alcohol according to the invention in a product will generally be at least 10 ppm by weight, preferably at least 100 ppm, more preferably at least 1000 ppm. However, in particular cases, levels of up to about 20% by weight may be used, depending on the product to be perfumed.

EXAMPLE 1 Preparation of 4-isobutylcyclohexan-1-ol (1) To the solid aluminum chloride (1.25 mol) in a 1-liter, three-necked round bottom flask, nitrobenzene (500 ml) was carefully added. An exotherm was felt during this addition. The resulting solution was cooled to 10 ° C using an ice bath. To this was added isobutyryl chloride (0.52 mol) and phenol (0.50 mol, in nitrobenzene) via separate addition funnels while assuring similar addition rates. A slight exotherm (10-20 ° C) was noted during the course of the addition. The reaction was stirred for an additional 5 hours at room temperature and then left overnight. The reaction mixture was carefully poured into 1 liter of saturated aqueous sodium hydroxide solution. More sodium hydroxide was added to bring the pH to 10. This alkaline solution was then extracted with diethyl ether (2 x 500 ml) and the organic fractions were discarded. The aqueous solution was acidified with sulfuric acid to pH 1 and then extracted with 2 portions of 500 ml of diethyl ether.

The organic fractions were combined and washed with three 500 ml portions of water, dried with anhydrous magnesium sulfate, and then evaporated in vacuo, to yield a viscous residue (the crude yield was 91% which was 96%). pure% by gas chromatography analysis). The residue was purified by distillation and / or recrystallization (from diethyl ether / pentane to yield colorless crystals of l- (4-hydroxyphenyl) -2-methyl-1-propanone. 13 C NMR (CDC13): 206.0, 161.7, 131.5, 128.4, 116.0, 35.3, 19.6, KM. XE (CDCl 3): 8.5 (1H), 8.0 (2H), 7.0 (2H), 3.6 (1H), 1.3 (6H). (2) To 60 ml of 2-butanol containing a 5% suspension of Rh / C catalyst (1 g) was added 17 g of 1- (4-hydroxyphenyl) -2-methyl-1-propanone produced in the (1) previous. The resulting suspension was placed under a total hydrogen pressure of 70 bar and heated to 70 ° C while being followed by gas chromatography. Once finished, the catalysts were removed by filtration through celite, and the solvent was evaporated in vacuo. The length of the reaction time can be varied to almost completely produce 4-isobutylcyclohexan-1-ol or a mixture thereof together with the corresponding ketone (4-isobutylcyclohexan-1-one). Any ketone contaminants were removed from the product mixture by treating the product mixture with an excess of lithium aluminum hydride in diethyl ether followed by standard work. The resulting crude alcohol was purified by distillation to give a colorless liquid of 4-isobutylcyclohexanol. 13 C NMR (CDCl 3): (2 isomers) 71.2, 67.2, 46.2, 45.4, 35.6, 34.1, 33.5, 32.2, 31.4, 27.2, 25.0, 24.7, 22.9, 22.8. X H NMR (CDCl 3): 3.9 (1H), 3.5 (1H), 1.9 (1H), 1.8 (1H), 1.7-0.9 (10H), 1.7 (6H).

Perfume composition A perfume composition of the floral type was prepared according to the following recipe: a-Terpineol 12 parts Absolute jasmine 50 '4 parts Heliotropin, 20% DPG 2 parts Traseolide * 1 part Balm from Peru 1 part 4-isobutylcyclohexan-l-ol 2 parts * Indaz musk marketed by Quest International, Ashford Kent, United Kingdom. The addition of the alcohol according to the invention increases the character of the thrush of the composition and decreases the vinegar notes of terpineol.

Claims (10)

1. A fragrance comprising "fragrance materials known in the art and at least one alcohol according to formula I: Formula I wherein Ri represents hydrogen or a methyl or ethyl group, and R 2 represents hydrogen or a methyl group.

2. A perfume according to claim 1, wherein Ri represents hydrogen or a methyl group.

3. A perfume according to claim 1 or 2, wherein R2 represents hydrogen.

4. A perfume according to claims 1-3, wherein the alcohol is present in an amount of at least 0.01% by weight.

5. A perfume composition according to claim 1, wherein the alcohol is chosen from 4-isobutylcyclohexan-1-ol and 2-methyl-4-isobutylcyclohexan-1-ol.

6. A process for imparting a note of muguet odor to products to be perfumed, comprising the step of incorporating a perfume in the product according to any of claims 1-5.

7. A process according to claim 6, wherein the product to be perfumed is chosen from: fabric washing powders, washing liquids, fabric softeners and other fabric care products; soaps, bath and shower gels, shampoos, hair conditioners and other personal cleansing products; cosmetic products such as creams, ointments, toilet waters, products for use before shaving or after shaving, lotions for the skin and other lotions, talcum powder, body deodorants and antiperspirants.

8. The 4-isobutylcyclohexanols according to formula I: Formula I wherein Ri represents a methyl or ethyl group and R 2 represents hydrogen or a methyl group.

9. The 4-isobutylcyclohexanols according to claim 8, wherein Ri is a methyl group.

10. 2-Methyl-4-isobutylcyclohexan-1-ol.