NL8302893A - PERFUME COMPOSITIONS AND PERFUMED PRODUCTS CONTAINING AT LEAST ONE OR MORE ESTERS OF 2-ETHYL-2-METHYL-BUTANIC ACID AS PERFUME RAW. - Google Patents

Description

SO 31952 fr * * 2 * * r Perfume compositions and perfumed products containing at least one or more esters of 2-ethyl-2-methyl-butanoic acid as perfume raw material.

The invention relates to perfume compositions containing at least one or more esters of 2-ethyl-2-methyl-butanoic acid as perfume raw material and to perfume compositions perfumed with these compounds or these compounds respectively.

There is a continuing interest in the preparation and use of synthetic fragrances because, unlike natural products, they can always be prepared in demand-matched quantity and uniform quality.

Esters of 2-ethyl-2-methyl-butanoic acid with the general formula% C% were now found.

C 1 / C 11 wherein R represents an alkyl, alkenyl, alkoxyalkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl or aralkyl group of up to 8 carbon atoms are valuable fragrances. They are capable of imparting to perfume compositions and products a variety of desirable notes, especially notes of the green, fruity, minty, woody, and floral type. The ethyl ester in particular is distinguished by a natural scent character. This ethyl ester is described in British Patent 1,004,286 and by J.R. Roland, J.D.C. Wilson and W.E. Hanford in J.Am. Chem. Soc. 72, 2122-24 (1950). However, there is no evidence in both publications of the utility of this compound as a perfume raw material. With regard to the upper limit of 8 carbon atoms, it is stated for the sake of completeness that the volatility and, therefore, the odor strength of esters of 2-ethyl-2-methyl-butanoic acid, in which R contains more than 8 carbon atoms, is insufficiently assessed.

The esters according to the invention are prepared according to known esterification methods, for example by reacting the corresponding alcohol with 2-ethyl-2-methyl-butanoic acid or a conventional derivative thereof such as the acid chloride.

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The esters according to the invention can be used successfully in perfume compositions, or as such can be used as a fragrance-imparting agent in a variety of products. By the term "perfume composition" is meant herein a mixture of fragrances and optional auxiliaries, optionally dissolved in a suitable solvent or mixed with a powdery substrate, which is used to impart a desired fragrance to the skin and / or all kinds of products . Examples of such products are: soaps, detergents, air fresheners, room sprays, pommanders, candles, cosmetics, such as creams, ointments, toilet waters, pre- and aftershave lotions, talcum powders, hair care products, body deodorants and anti-perspirants.

Fragrances and perfume mixtures which can be used in combination with the compounds according to the invention for the preparation of perfume compositions are for example: natural products such as essential oils, absolute, resinoids, resins, concretes, etc., but also synthetic fragrances such as hydrocarbons, alcohols, aldehydes, ketones, ethers, acids, esters, acetals, ketals, nitriles, etc., including saturated and supersaturated, aliphatic, carbocyclic, and heterocyclic compounds. Examples of fragrances that can be used in combination with the compounds of the invention are: geraniol, geranyl acetate, linalool, linalyl acetate, tetrahydrolinalole, citronellol, citronelly acetate, dihydromyrcenol, dihydromyrcenyl acetate, tetrahydromyrcenol, terpine 8 9 3 3 * «, terpinyl acetate, nopol, nopylaacetate, 2-phenylethanol, 2-phenylethyl acetate, benzyl alcohol, benzyl acetate, benzyl salicylate, styrallyl acetate, benzyl benzoate, amylsalicylate, trichloroethyl acetyl, trichlorethylethyl iso-5-nonylacetate, vetiveryl acetate, vetiverol, aXfa-hexyXkaneeXaldehyde, 2-methyl-3- (p-tert-butylphenyl) -propanal, 2-methyl-3- (p-isopropylphenyl) -propanal, 3- (p- tert-butylphenyl) -propanal, tricyclodecenyl acetate, tricyclodecenyipropionate, 4- (4-hydroxy-4-methylpentyL) -3-cyclohexene-carbaldebyde, 4- (4-methyl-3-pentenyl) -3-cyclohexene-carbaldehyde, 10 4- 3-pentyl-tetrahydropyran, 3-carboxymethyl-2-pin .tyl cyclo-peatane, 2-n-heptyl cyclopentanone, 3-methyl-2-pentyl-2-cyclop entenone, a-decanal, n-dodecanaX, 9-decenol-1-phenoxyethyl isobutyrate, phenyl acetaldehyde dimethyl acetaldehyde acetaldehyde diethyl acetal, geranyl nitrile, citronellyinitrile, cedryxacetate, 3-isokamphylcyclo-15 hexanoX, cedryl methyl ether, isolongifolanone, aubepine nitrile, aubepine, heliotropin, coumarin, eugenol, vanilliert, diphenyloxethyl, hydroxy-joonone and esters thereof, musk fragrances, tetral musk fragrances, are chromanmus kiss odors, macrocyclic ketones, macroxacton musk fragrances, ethylene brassyl aromatic, nitro musk fragrances.

Excipients and solvents which can be used in perfume compositions containing one or more compounds of the invention are, for example: ethanol, isopropanol, diethylene glycol monoethyl ether, diethylphthalafafc and so on.

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The amounts in which the compounds according to the invention can be used in perfume compositions or products to be perfumed can vary within wide limits and depend, inter alia, on the nature of the product in which the fragrance is used, on the nature and the amount of the other components in the perfume composition and of the fragrance effect that is intended. Therefore, it is only possible to indicate very global limits, however, with which the person skilled in the art is provided with sufficient information to be able to use the compounds according to the invention independently. In most cases, an amount of only 0.1% by weight in a perfume composition will already be sufficient to obtain a clearly perceptible odor effect. On the other hand, to achieve special fragrance effects, it is possible to use amounts of 20% by weight or even more in a composition. In products perfumed with the aid of perfume compositions, these concentrations are proportionately lower, depending on the amount of perfume composition used in the product.

The following examples serve only to illustrate the preparation and use of the compounds of the invention. However, the invention is not limited thereto.

2 ° Example I

Preparation of ethyl 2-ethyl-2-raethyl-butyrate.

To a mixture of 260 g (2 mol) of 2-ethyl-2-methyl-butanoic acid and 386 g (8 mol) of ethanol, 260 g of concentrated sulfuric acid are added over 15 minutes with good stirring. The temperature thereby rises to approx. 25 60 ° C. The mixture is then heated under reflux for a further 3 hours while stirring. After the mixture has cooled to room temperature, the layers are separated.

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The bottom layer is diluted with 200 ml of water and then extracted with cyclohexane. The cyclohexane layer is combined with the original top layer and washed neutral with soda solution. The cyclohexane solution is then evaporated and the residue distilled under reduced pressure. 258 g of the desired ethyl ester are obtained, bpt: 65 ° C / 0.3 kPa; n20 / D = 1.4110; NiR (100 HHz, 6 in ppra to TMS, solvent: CC14): 0.81 (6H, t, J = 7Hz); 1.06 (3H, s); 1.24 (3H, t, J = 7Hz); 1.0-1.9 (4H, m); 4.08 (2H, q, J = 7Hz).

The compound has a pleasantly fruity and woody fragrance with as-10 pects reminiscent of tagetes oil.

Example II

Preparation of 2 '-ethylhexyl- (2-ethyl-1 -2-methyl-1) -butyrate.

A mixture of 15.5 g (0.12 mol) 2-ethylhexanol, 13 g (0.1 nol) 2-ethyl-2-methyl-butanoic acid, 100 mg p-toluenesulfonic acid and 150 ml toluene is heated to reflux the water formed is distilled azeo-tropically. After the mixture has cooled to room temperature, it is neutral washed with soda solution. The toluene solution is then evaporated and the residue distilled under reduced pressure. 14.5 g of the desired ester are obtained, b.p .: 95 ° C / 0.3 kPa; n24 / D = 1.4320; NMR: 0.81 (6H, t, J = 7Hz); 1.05 (3H, s); 0.6-1.9 (19H, m); 3.90 (2H, d, J = 6Hz).

The compound has a pleasantly minty and slightly fruity fragrance.

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r · Example III

The esters below were prepared as described in Example II:

Allyl-2-ethyl-2-methyl-butyrate: 5pt .: 95 ° C / 0.3 kPa; NMR: 0.81 (6H, t, J = 7Hz), 1.08 (3H, s); 1.0-1.9 C4H, m); 4.49 (2H, d with fine structure, J = 7Hz); 5.0-5.4 (2H, m); 5.6-6.1 (1H, m).

Spicy green and floral fragrance, somewhat reminiscent of tagetes oil. Isobutyl-2-ethyl-2-methyl-butyrate: 10 kpt .: 90 ° C / 0.3 KPa; n20 / D = 1.4155; NMR: 0.8I (6H, t, J = 7Jz); 0.94 (6H, d, J = 7Hz); 1.06 (3H, s); 1.0-2.2 (5H, m); 3.78 (2H, d, J = 6Hz). Woody and minty fragrance with floral aspects.

Cyclohexyl-2-ethyl-2-methyl-butyrate: bp: 90 ° C / 0.3 kPa; n20 / D = 1.4462; NMR: 0.80 (6H, t, T = 7Hz); 1.04 (3H, s); 1.0-2.0 (14H, m); 4.65 (1H, m).

Fruity fragrance.

21-methoxyethyl- (2-ethyl-2-methyl) -butyrate: bp: 75 ° C / 0.3 kPa; JMR: 0.81 (6H, t, 7Hz); 1.06 (3H, s); 1.0-1.9 (4H, m); 3.30 (3H, s); 3.46 (2H, t, J = 5Hz); 4.12 (2H, t, J = 5Hz).

20 Green and slightly woody fragrance.

Benzyl-2-ethyl-2-methyl-butyrate: bp: 118 ° C / 0.3 kPa; n20 / D = 1.4890; NMP: 0.77 (6H, t, J = 7Jz); 1.07 (3H, s); 1.0-1.9 (4H, m); 5.00 (2H, s); 7.0-7.3 (5H, broad s).

Green and slightly floral fragrance.

83 0 2 0 9 3 * 7 2'-phenylethyl- (2-eth.yl-2-raeth.yl) -fautyrate: bp: 125 ° C / 0.3 kPa; n20 / D = 1.4830; NMR: 0.73 (6H, t, J = 7Hz); 1.01 (3H, s); 1.0-1.9 (4H, m); 2.86 (2H, t, J = 7Hz); 4.20 (2H, t, J = 7Kz); 6.9-7.3 (5H, broad s).

5 Floral and slightly fruity fragrance.

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Example IV

A pine-type perfume composition, very suitable for shampoos and shower and bubble bath preparations, was prepared according to the following recipe:

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5 345 parts by weight bornyl acetate 100 "2-butyl-4,4,6-trimethyl-1,3-dioxane 50" Siberian pine needle oil 30 "5-acetyl-3-isopropyl-1,2,6,6-tetramethyl-indan 1Ö 30 "benzyl acetate 30" orange oil 30 "linalyl acetate 20" olibanum-resinoid 20 "tridecanal 15 15" 4-tert-butylcyclohexyl acetate j 10 "coumarin 10" terpineol 10 "terpinyl acetate 10" lavandin oil 20 10 "n-decanal 7 104" Citrovert * 5 "dodecanal 5" styralyl acetate 5 "3-isokamphylcyclohexanol 25 3" α-ionone 2 "isoeugenol 30" ethyl-2-ethyl-2-methyl-butyrate 218 "dipropylene glycol 1000 parts by weight 8302893-Tr. Ο.

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Example V

A floral fantasy perfume composition was prepared according to the following recipe: 350 parts by weight of Muguet base * 5 200 "Lilas base * 175" * Jasmin base * 75 "Hyacinth base * 70" bois de rose oil 70 11 dihydromyrcenol 100 "ylang-ylang oil 40" tricyclodecenyl acetate 40 "2- (heptyl-3) -dioxolane 30" litsea cubeba oil 20 "dimethyl benzyl carbinyl acetate 15 10" eugenol 10 "5-acetyl-3-isopropyl-1, 1,2,6-tetramethylindan 3 "2,4-dimethyl-cyclohexene-3-carbaldehyde 20 2" isoeugenol 50 "ethyl-2-ethyl-2-methyl-butyrate 1200 parts by weight

The perfume composition thus prepared can be successfully used in air-dyeing compositions made according to British Patent Specification 1,544,221.

K Perfume bases, marketed by Naarden International N.V.

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Claims (5)

Perfume composition or perfumed product, characterized by a content of one or more esters of 2-ethyl-2-methyl-butanoic acid of the formula CLfL i2 5 CJH- - C-COOR 25 I CH3 in which R is an alkyl, alkenyl, alkoxyalkyl -, cycloalkyl, alkylcyclo-5 alkyl, cycloalkylalkyl or aralkyl group having up to 8 carbon atoms. Perfume composition or perfumed product according to claim 1, characterized by an ethyl ester content of 2-ethyl-2-methyl-butanoic acid. Perfume composition according to claim 1, characterized by a content of at least 0.1% of one or more of the esters of 2-ethyl-2-methyl-butanoic acid defined in claim 1. Use of a perfume composition according to one or more of claims 1 to 3 or of one or more esters of 2-ethyl-2-methyl-butanoic acid defined in claim 1 for perfuming products. 5. Esters of 2-ethyl-2-methyl-butanoic acid of the formula CJL | 2 5 COHc - C - COOR 25. ch3 wherein R is an alkyl, alkenyl, alkoxyalkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl or aralkyl group having up to 15 carbon atoms, it being understood that the ethyl ester of 2-ethyl-2-methyl-butanoic acid is excluded. 8302 39 3