NL8701489A - New unsatd. cyclohexene carbinol derivs. - used in perfumes and perfumed prods. - Google Patents

Abstract

New cyclohexene derivs. of formula (I) are claimed. R1 = H or Me; R2 = prop-2-en-1-yl; but-2-en-1-yl; but-3-en-2-yl; or 2-methyl-prop-2-en-1-yl.

Description

N.0. 34605

The invention relates to trimethylcyclohexenyl and tetra-methylcyclohexenyl-methyl-alkenyl-carbinols, to perfume compositions, and to perfume compositions and perfumed products containing one or more of these compounds as perfume raw material. containing one or more of these alcohols as perfume raw material, as well as with these compounds, respectively. these compounds contain perfume compositions perfumed objects and materials.

10 There is a continuing interest in the use of synthetic fragrances in perfume compositions and perfumed products, such as cosmetics, soaps, detergents, household products, etc. This interest is stimulated by insufficient quantity, variable quality and often high price of natural fragrances. 15 A natural raw material whose fragrance is highly appreciated in perfumery is patchouli oil. There is therefore a great need for synthetic fragrances whose smell, in character, strength and shelf life, corresponds as closely as possible to that of patchouli oil.

Published European patent application 199330 discloses that 20 1- (1,4,6-trimethylcyclohex-3-en-1-yl) -ethanol-1,1 (1,4,6-trimethylcyclohex-3-en- 1-yl) -methanol, 2- (1,4,6-trimethylcyclohex-3-en-1-yl) -propanol-2 and 2- (1,4,6-trimethylcyclohex-3-en-1- yl) -butanol-2 fragrances are with a strong odor, which has essential odor aspects of patchouli oil.

It has been found in practice that in the fragrance of these compounds the camphorous-woody fragrance aspects of patchouli are well represented, but that they fall short in the earth-like aspects. However, a much more serious shortcoming of these compounds is that their scent volatilizes quickly, so that they are mainly suitable for the top note of 30 perfume compositions. Patchouli oil, on the other hand, is known for its very long-lasting fragrance and is therefore specially used for the heart and the foundation of a composition.

Surprisingly, it has now been found that (3,4,5-trimethylcyclohexenyl) and (1,3,4,5-tetramethylcyclohexenyl) -methyl-alkenyl carbinols having the structure of the general formula

I ƒ OH

40ιΓτ R2 40 8701489 * 2 in which a hydrogen atom or a methyl group and R £ a prop-2-en-1-yl-, but-2-en-1-yl-, but-3-en-2-yl- or 2-methyl-prop-2-en-1-yl group, valuable fragrances are with a powerful and very strongly reminiscent of patchouli. The compounds according to the invention 5 differ from those of European patent application 199330 not only in that they have a much more complete patchouli character in which the earth-like aspects are also well represented, but in particular in that they have a much longer lasting odor. Preference is given here to compounds in which R1 represents a methyl group.

The compounds of the invention are new. They can be prepared according to methods known for such compounds. As a first step in the synthesis, a Diels-Alder reaction of 3-methyl-pent-3-en-2-one as dienophile with penta-1,3-dienes, resp. 2-methyl-penta-1,3-dienes as dienes, for example as described for the corresponding reaction with isoprene in the above-mentioned European patent application 199330. As described there, the reaction may or may not be under the influence of a Lewis acid as a catalyst.

Trimethylcyclohexenyl and resp. Tetramethylcyclohexenyl methyl ketones can be converted into the desired carbinols of the invention using an allyl, methallyl or but 2-enyl halide in a Grignard reaction. Thereby advantageous use can be made of the so-called Barbier-Grignard procedure, eg as described by M. Peter Dreyfuss in J. Org. Chem. 28, 25 (1963), pp. 3269-3272. The Grignard reaction with butenyl halide gives a mixture of carbinols, in which Rl and resp. is a but-2-and-1-yl and a but-3-and-2-yl group. The mixture can, if desired, be separated into the two components using conventional separation techniques, but this is not necessary for the use as a fragrance.

The Diels-Alder reaction maintains the stereochemistry of the dienophile in the reaction product. Thus, starting from trans-3-methyl-pent-3-en-2-one, a mixture of the two in the first step of the scheme below with resp. 1 and 11 indicated stereoisomeric ketones.

40 8701489 3 & j α λλ Λ- Λ * J - * I /., "· * Γ χγ

I II

/ ^ Xflal. + Mg

The subsequent Grignard reaction results in a mixture of stereoisomeric carbinols (shown in Scheme above for R - allyl). The ketone mixture can also be separated by conventional techniques into the two components, which can then be converted individually into the respective carbinols. However, this is also not necessary, since the carbinol mixture obtained from the ketone mixture is as such very suitable for use as a fragrance according to the invention.

By the term "perfume composition" is meant here 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, space sprays, pommanders, candles, cosmetics, such as creams, ointments, lotions, toilet waters, pre- and after-shave lotions, talcum powders, hair care products, body deodorants and antiperspirants.

S701 483 4

Fragrances and fragrance mixtures which can be used in combination with the compounds of the invention for the preparation of perfume compositions are, for example: natural products such as essential oils, absolute, resinoids, resins, concretes, etc., and synthetic fragrances such as hydrocarbons, alcohols, aldehydes, ketones, ethers, acids, esters, acetals, ketals, nitriles etc., including saturated and unsaturated compounds, aliphatic, carbocyclic and heterocyclic compounds. Examples of fragrances that can be used in combination with the compounds of the present invention are: geraniol, geranyl acetate, linalool, linaloyl acetate, tetrahydrolinalole, citronellol, citronelly acetate, dihydromyrcenol, dihydromyrcenyl acetate, tetrahydromyolphenol, terplacineol, terplacineol phenylethanol, 2-phenylethyl acetate, benzyl alcohol, benzyl acetate, benzyl salicylate, benzyl benzoate, styrally acetate, 15 amyl salicylate, dimethyl benzyl carbinol, trichloromethylphenylcarbinyl acetate, p-tert-butylcyclohexyl acetyl acetyl -amyl cinnamaldehyde, α-hexyl cinnamaldehyde, 2-methyl-3- (p-tert-butylphenyl) -propanol, 2-methyl-3- (p-isopropylphenyl) -propanal, 3- (p-tert-butylphenyl) -propanal, tricyclodecenyl acetate tri-20 cyclodecenylpropionate, 4- (4-hydroxy-4-methylpentyl) -3-cyclohexenecarb-aldehyde, 4- (4-methyl-3-pentyl) -3-cyclohexenecarbaldehyde, 4-acetoxy-3-pentyl-tetrahydropyran, 3-carboxymethyl-2-pent ylcyclopentane, 2-n-heptylcyclopentanone, 3-methyl-2-pentyl-2-cyclopentanone, n-decanal, n-dead canal, 9-decenol-1, phenoxyethyl isobutyrate, phenylacetaldehyde-dimethyl-acetal, phenylacetaldehyde-diethyl acetal geranyl nitrile, citronellyl nitrile, cedrylacetate, 3-isokamphylcyclohexanol, cedryl methyl ether, iso-longifolanone, aubepine nitrile, aubepine, helitropine, coumarin, eugenol, vanillin, diphenyloxy, hydroxycitronellonone, ionones , indan musk fragrances, tetralin musk fragrances, isochroman musk fragrances, macrocyclic ketones, macrolactone musk fragrances, ethylene brassyl aromatic aromatic nitromus fragrances.

Excipients and solvents that can be used in perfume compositions containing compounds of the invention are, for example: ethanol, isopropanol, diethylene glycol monoethyl ether, dipropylene glycol, diethyl phthalate, triethyl citrate, etc.

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 8701489. 5 multitude of the other components in the composition and of the odor 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, in order to achieve special fragrance effects, it is possible to apply amounts of 50% by weight or even 10 more in a perfume composition. In products perfumed with the help of perfume compositions, these concentrations are proportionately lower, depending on the amount of 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.

Example I

Preparation of 4-Acetyl-3,4,5-Trimethylcyclohexene.

A mixture of 142 g (1.45 mol) of trans-3-methyl-pent-3-en-2-one, 460 g (6.8 mol) of 1,3-pentadiene and 100 mg of hydroquinone was added for 20 heated under pressure at 190 ° C for hours. The desired mixture of stereoisomeric ketones was isolated from the reaction mixture by fractional distillation under reduced pressure. 36 g were obtained; bpt: 81-82 ° C / 1.1 25 kPa.

Example II

Preparation of 4-Acetyl-1,3,4,5-Tetramethylcyclohexene.

A mixture of 98 g (1 mol) trans-3-methylpent-3-en-2-one, 157 g 30 (1.9 mol) 2-methyl-1,3-pentadiene, 20 g toluene and 100 mg hydroquinone was heated under pressure to 200 ° C for 9 hours. The desired stereoisomeric ketones were isolated from the reaction mixture as a mixture of about 70% component 1 and 30% component 11 (see Scheme above) by fractional distillation under reduced pressure. 77.4 g were obtained; bpt: 69-76 ° C / 0.3 kPa. Both components could be separated by preparative gas chromatography (column: 2 m, 10% DEGS, temp: 130eC, see Figure 6).

Example 111 40 Preparation of 2- (3,4,5-trimethylcyclohexen-4-yl) -pent-4-en-2-ol.

8701 489 ♦ 6

Under a nitrogen atmosphere, 2.56 g of allyl chloride (33.6 mmol) was added to 8 g of magnesium shavings in 80 ml of dry tetrahydrofuran. The formation of the Grignard compound was started by adding an iodine crystal. A mixture of 28.0 g (168 mmol) of the acetyl-trimethylcyclohexene and 19.2 g (252 mmol) of allyl chloride, dissolved in 150 ml of dry tetrahydrofuran, was added dropwise over one hour to this under continuous stirring. . The temperature of the reaction mixture was kept at about 50 ° C. The reaction mixture was stirred for an additional hour and then poured into an excess of saturated 10 Nl / Cl solution. This mixture was extracted 3 times with ether and the collected organic layers were dried and evaporated. The residue was fractionated to give 23 g of the desired alcohol as a mixture of isomers; bpt: 93-94 ° C / 70 Pa; np = 1.5030; IMR spectrum: Fig. 1. The aroma of the mixture showed such a combination of woody, green-spicy, camphor and earthy notes that the overall impression was very reminiscent of patchouli.

Example IV

Preparation of 2- (1,3,4,5-tetramethylcyclohexen-4-yl) -pent-4-en-2-ol.

The above compound was prepared as indicated in Example III. The Grignard compound was formed from 3.7 g of allyl chloride and 14.9 g of magnesium shavings in 70 ml of tetrahydrofuran. A mixture of 75 g of acetyl-tetramethylcyclohexene obtained according to Example II and 40 g of allyl chloride in 240 ml of tetrahydrofuran was added dropwise thereto. After working up, 79.5 g of the desired alcohol are obtained as a mixture of isomers; bpt: 100-102 ° C / 0.14 kPa; nj ^ 1,5020; KMR spectrum: fig. 2.

The mixture had a very complete and very long lasting patchouli fragrance.

30

Example V

Preparation of 4-methyl-2- (1,3,4,5-tetramethylcyclohexen-4-yl) -pent-4-en-2-ol.

The above compound was prepared as indicated in Example 111. The Grignard compound was formed from 2.25 g of methallyl chloride and 12 g of magnesium shavings in 100 ml of tetrahydrofuran. A mixture of 45 g of acetyl-tetramethylcyclohexene obtained according to Example II and 33.7 g of methallyl chloride in 200 ml of tetrahydrofuran was added dropwise thereto. After working up, 41.3 g of the desired alcohol were obtained as a mixture of isomers; bpt: 104-105 ° C / 0.14 kPa; n £) 3 = 8701489 7 1.5011; MIR spectrum: fig.3. *

The mixture had a pleasant patchouli odor.

Example VI

Preparation of 3-methyl-2- (1,3,4,5-tetramethylcyclohexen-4-yl) -pent-4-en-2-ol (A) and 2- (1,3,4,5- tetramethylcyclohexen-4-yl) -hex-4-en-2-ol (B).

A mixture of the above compounds was prepared as indicated in Example 111. The Grignard compound was formed from 2.25 g of crotyl bromide and 10 g of magnesium shavings in 50 ml of tetrahydrofuran. A mixture of 30 g of acetyl-tetramethyl-cyclohexene obtained according to Example II and 45 g of crotyl bromide in 200 ml of tetrahydrofuran was added dropwise thereto. After working up, 23 g of an approx. 1: 1 mixture of compounds A and B were obtained, each again consisting of both stereoisomers; bpt: 105-115 eC / 0.14 kPa; n ^ * 1.5038. The mixture was separated into the two components A and B by preparative gas chromatography (column: 2m, 10% DEGS; temp: 165 ° C). JMR spectrum of A: Fig. 4; NMR spectrum of B: Fig. 5. Compounds A and B both had a pleasant patchouli odor and were found to differ very little in odor.

20

Example Vil

A perfume for soap was prepared according to the following recipe:

Dihydromyrcenol 150 parts by weight 2-Butyl-4,4,6-trimethyl-1,3-dioxane 150 parts by weight 25 α-Amyl cinnamaldehyde 100 parts by weight

Benzyl salicylate 80 parts by weight

Benzyl acetate 50 parts by weight

Acetyl-cedrene 50 parts of 2-Methyl-3- (p-tert-butylphenyl) -propanal 50 parts of 30 Petitgrain oil 50 parts of 5-Acetyl-3-isopropyl-1,2,6,6- tetramethylindan 40 parts by weight Citronellol 40 parts by weight

Citronelly Nitrile 30 parts by weight

Coumarin 20 parts by weight of Methyl nonyl acetaldehyde 20 parts by weight

Benzoin Resinoid Sumatra 15 parts by weight

Styrally acetate 10 parts by weight

Lavandin oil 10 parts by weight

Methyl 2,4-dihydroxy-3,6-dimethylbenzoate 5 parts by weight of 40 4-Methyl-2- (tetramethylcyclohexenyl) pentenol of 8701 a 89 a 8

Example V 30 parts

Total 900 parts of 10% solution in dipropylene glycol.

5

Example VIII

A perfume for an after-shave lotion was prepared according to the following recipe:

Benzyl acetate 100 parts by weight 10 Amyl salicylate 100 parts by weight

Bergamot oil 80 parts by weight

Lemon oil 70 parts by weight

Geranium oil Bourbon 70 parts by weight

Citronellol 50 parts by weight 15 5-Acetyl-3-isopropyl-1,2,6,6-tetramethylindan 35 parts by weight

Heliotropin 35 parts by weight

Linalool 30 parts by weight

Mousse-de-chêne-absolute Jougoslav 20 parts by weight

Lavender oil French 20 parts 20 Petitgrain oil 20 parts 11-Oxahexadecanolide 10 parts

Lime oil 10 parts 2-Methyl-3- (p-tert-butylphenyl) -propanal 10 parts

Coriander oil 10 parts by weight 25 3-l-samphylcyclohexanol 10 parts by weight 2,6-Dimethyl-heptanol-2 5 parts by weight

Pennyroyal oil 5 parts by weight

Eugenol 5 parts by weight a

Ethylvanillin 5 parts by weight 30 Tetramethylcyclohexenyl pentenol of Example IV 50 parts by weight

Total 750 parts of SFC 10% solution in dipropylene glycol.

Example IX

An after-shave lotion perfumed with the composition of Example III was prepared according to the following recipe: A) 0.3 parts by weight 1-menthol 40 0.5 parts by weight Uvinol D 50 1 8701489 9 30.2 parts by weight propylene glycol 535 parts by weight of ethanol B) 2.0 parts by weight of aluminum chlorohydrate alantoinate 5 2.0 parts by weight of lactic acid 400 parts by weight of distilled water C) 20 parts by weight of perfume (Example VIII)

O

10 parts cremophor RH 40 10

The components listed under A, B and C were mixed separately until mixtures A, B and C. Mixture B was then added to mixture A with good stirring. Then mixture C was added and the total was homogenized by stirring. Thus, a slightly astringent after-15 shave lotion obtained, the fragrance of which was characterized by a pleasant patchouii note · 20 ^ Trademark of BASF for 2.2 ', 4.41-tetrahydroxybenzophenone.

2

Trademark of BASF for a reaction product of hydrogenated castor oil and epoxyethane.

8701 488

Claims (5)

1. Cyclohexene derivatives of the formula OH 5 / _R wherein R 1 is a hydrogen atom or a methyl group and R 2 is a prop-2-en-1-yl, but-2-en-1-yl, but-3-en-2- yl or 2-methyl-prop-2-en-1-yl group. 2. Cyclohexene derivatives of the formula set forth in claim 1, wherein R 1 has a methyl group and R 1 has the meanings set out in claim 1. 3. Perfume composition or perfumed product, at least containing a cyclohexene derivative as fragrance, characterized in that at least one of the compounds defined in claim 1 is present as fragrance. Perfume composition or perfumed product according to claim 3, characterized in that at least one of the compounds defined in claim 2 is present as perfume. Perfume composition according to claim 3 or 4, characterized in that it contains 0.01-50% by weight of at least one of the compounds defined in claim 1. is *** 6701 483