NL8700469A - New 4,8-cyclo:dodeca:dien:ol derivs. - used as basic perfume components esp. to give long lasting patchouli fragrance - Google Patents

Abstract

New 4,8-cyclododecadienol derivs. (I) of formula a, b or c are claimed. X-Y = dimethyloctadienylene gp. of formula (IV), (V), (VI) or (VII); R = Me, Et or vinyl. More specifically R = Me. (I) are prepd. from trimethyl-1,5,9-cyclododecatriene (II) by known methods, e.g. epoxidation of (II) to give (III), and reaction of (III) with an organo-metal reagent.

Description

* 1 N.0. 34335%

Alcohols derived from trimethyl-1,5,9-cyclododecatriens, and perfume compositions and perfumed products containing one or more of these alcohols as perfume raw materials.

The invention relates to alcohols derived from trimethyl-1,5,5-cyclododecatrienes, to perfume compositions containing one or more of these alcohols as perfume raw materials, as well as to these compounds, respectively. compositions containing perfumed products containing these compounds.

10 There is a continuing interest in the use of synthetic fragrances in perfumes and perfumed products, such as cosmetics, soaps, detergents, household products, etc. This interest is stimulated by the insufficient quantity, the varying quality and the often high price of natural fragrances. The perfume of patchouli is highly appreciated in perfumery. There is therefore a great need for synthetic fragrances, which are able to impart a pleasant and natural patchouli note to perfumes and perfumed products.

Surprisingly, it has now been found that new 4,8-cyclododecadien-20-nol derivatives of the general formulas 1, 2 and 3 on the formula sheet, wherein the ring portion XY represents a dimethyl octadienylene group with one of the partial formulas A, B, C and D and R has the meaning of a methyl, ethyl or vinyl group, valuable fragrances are with powerful and long-lasting, strongly reminiscent of patchouli. Preferred are the compounds of the invention, wherein R represents a methyl group. The above defined compounds can be considered as derivatives of trimethyl, 5,9-cyclododecatrienes of the general formula 4, wherein X-Y has the meaning indicated above. The formula 4 resp. formulas A, B and C to construct formulas 4A, 4B and 4C all represent 1,5,10-trimethyl-1,5,9-cyclododecatrienes; based on formula 4 resp. to construct formula D formula 4D stands for 1,5,9-trimethyl-1,5,5-cyclododecatrien. The above compounds have various cis / trans and stereoisomers, all of which are included in the formulas shown.

A mixture of isomeric 1,5,9-triraethyl-4,8-cyclododecadienols is described in U.S. Pat. Nos. 3,845,078, 3,896,180 and 3,929,675 as a fragrance with a woody-amber odor. These compounds are obtained by epoxidation of 1,5,9-trimethyl-1,5,9-cyclododecatrien followed by reduction of the epoxide. The epoxide, the acid-derived rearrangement ketone, and the corresponding tetrahydro derivatives are also described as compounds having a powerful woody-amber odor.

U.S. Pat. No. 3,723,478 describes comparable trimethyl cyclododecanols, but only as intermediates in the preparation of the corresponding ketones. These ketones are said to be fragrances with a woody fragrance; of the abovementioned alcohols, however, there is no indication as to odor or usefulness as a fragrance. In view of the purpose of the invention described in said patent, this can only lead to the conclusion that these alcohols therefore have no fragrance value. 4.4.7.7- and 5.5.8.8-tetramethyl-cyclododecanol are known (Chem. Abstr. 68, 104437t and 69, 2307d), but also without any mention of odor or utility as a fragrance.

The compounds of the invention are new and can be prepared by methods known per se for such compounds, starting from trimethyl-1,5,9-cyclododecatrienes of formula 4. The preparation of these hydrocarbons is described in U.S. Pat. No. 3,723,478 and literature cited therein. However, they are also commercially available. In both cases they consist of mixtures of double bond isomers in which the double bonds can each individually have the cis or trans configuration. In addition, these mixtures may contain either both 1,5,9 and 1,5,10-trimethyl-cyclododecatriens, or only 1,5,9 or only 1,5,10-trimethyl isomers. The composition of the isomer mixtures depends on the method of preparation. Although it is in principle possible with modern separation methods to separate said mixtures into components wholly or mainly consisting of one or a few isomers, this is not economical and is not necessary for the use in the invention.

A suitable process for the preparation of the cyclododecadienes of the invention is shown in the reaction scheme shown on the formula sheet. The first step in this scheme is the epoxidation of the above trimethyl cyclododecatriens to form monoepoxides of formula 5, wherein X-Y again has the above meaning. This reaction can be carried out by methods known from the literature, eg as described in U.S. Pat. Nos. 3,723,478 and 3,929,675, in particular with peracids such as perbenzoic acid, m-chloro-perbenzoic acid or peracetic acid in conventional inert solvents, eg chlorinated hydrocarbons such as chloroform, carbon tetrachloride or dichloromethane. Since each of the three double bonds present can be epoxidized, a mixture of cis / trans and stereoisomers is formed from each 8700466 3-cyclododecatriene isomer. The epoxides formed from 1,5,9-trimethyl-cyclododecatrienes are all represented by formula 5D, the epoxides formed from 1,5,10-trimethyl-cyclododecatrienes by formulas 5A, B and C, depending on which double bond is epoxidized.

Mixtures of alcohols of formulas 1 and 2 are obtained by reacting epoxides thus prepared with a suitable organometallic reagent as described by H. Kropf in Houben-Weyl, Methods of Organic Chemistry, Alkohole II, Vol. VI / la / 2, page 928-1074 and 1238-1295.

Examples of such reagents are: methyl, ethyl or vinyl lithium and preferably methyl, ethyl or vinyl magnesium halides. On the other hand, the epoxides described above can be isomerized to the corresponding ketones (formula 6) under the influence of a mineral acid or a Lewis acid such as BFg etherate. The isomerization is preferably carried out in an inert organic solvent, for example an ether such as diethyl ether or dioxane. These and the like reactions are described in U.S. Pat. No. 3,723,478. Said ketones can also be obtained directly from the trimethylcyclododecatrienes by oxidation with peracids as described in U.S. Pat. No. 3,929,675. By reacting these ketones with methyl, ethyl or vinyl metal compounds as described by H. Kropf in Houben-Weyl, see above, especially p. 928-1074, the alcohols of formula 3 are then obtained. In this case too, use is preferably made of Grig-nard reagents.

The above Grignard reactions are carried out in a conventional manner, for example as described in M.S. Kharasch and Q. Rein-muth, "Grignard Reactions of Non-metallic Substances", Prentice Hall,

New York, 1954.

The isomer blend mixture obtained according to the above-described preparation methods can, if desired, be separated by modern separation methods into components consisting wholly or mainly of only one or a limited number of isomers. As has already been stated for the starting compounds, such a separation is not necessary for the use of the compounds according to the invention as fragrance.

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, 40 air fresheners, space sprays, pommanders, candles, cosmetics, such as

87 0 0 4 £ Q

* 4 Ή creams, ointments, lotions, toilet waters, pre- and after-shave lotions, talcum powders, hair care products, body deodorants and antiperspirants.

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, 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, dihydromyrcenylacetol, terinylacetol, terpoline acetol 2-phenylethanol, 2-phenyl ether acetate, benzylalko. hollow, benzyl acetate, benzyl salicylate, benzyl benzoate, sty rally acetate, amyl salicylate, dimethyl benzyl carbinol, trichloromethylphenylcarbinyl acetate, p-tert-butylcyclohexyldehyde -dehyde -dexyldeyl-amethanol, vetiverol, ( methyl 3 (p-tert-butylphenyl) -propanol, 2-methyl-3- (p-isopropylphenyl) -propanal, 3- (p-tert-butylphenyl) -propanal, tricyclodecenyl acetate, tri-cyclodecenylpropionate, 4- ( 4-hydroxy-4-methylpentyl) -3-cyclohexene-carbaldehyde, 4- (4-methyl-3-pentenyl) -3-cyclohexene-carbaldehyde, 4-acetoxy-3-pentyl-tetrahydropyran, 3-carboxymethyl-2-pentylcyclopes-25 tane, 2-n-heptylcyclopentanone, 3-methyl-2-pentyl-2-cyclopentanone, n-decanal, n-dodecanal, 9-decenol-1, phenoxyethyl isobutyrate, phenylacetaldehyde-dimethyl acetal, phenylacetaldehyde-diethyl acetal, geranyl citronellyl nitrile, cedryl acetate, 3-isokamphylcyclohexanol, cedryl methyl ether, isolongifolanone, aubepine nitrile, aubepine, helitro-30 pine, coumarin, eugenol, vanillin, diphenyloxide, hydroxycitronellal, ionones, methyl ionones, isomethyl ionones, irons, cis-3-hexenol and esters thereof, indan musk fragrances, macrocyclic ketones, macro-lactone musk fragrances, ethylene brassyl aromatics and nitrous musk 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, etc.

The amounts in which the compounds according to the invention can be used in perfume compositions or products to be perfumed can vary widely within 8700463 * 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 intended fragrance effect. Therefore, it is only possible to indicate very global limits, however, with which sufficient information is provided for the skilled person 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 fragrance effect.

On the other hand, to achieve special odor effects, it is possible to use amounts of 50% 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 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

A) Preparation of trimethyl-5,9-cyclododecadiene epoxide (formula 5A, B, C)

To 204 g of a mixture consisting of about 90% 1,5,10-trimethyl and 10% 1,5,9-trimethyl-1,5,9-cyclododecatrien dissolved in 500 ml methylene chloride, 164 g anhydrous sodium acetate added. The mixture was cooled to 0 ° C and kept at this temperature, while 200 g of 40% peracetic acid was added over 90 minutes with continuous stirring. The reaction mixture was stirred at this temperature for an additional 1 hour.

The reaction mixture was then washed with 500 ml of water and the layers were separated. The organic layer was first washed with 600 ml of a 5% aqueous solution of ferrous ammonium sulfate and then with a saturated sodium bicarbonate solution. The organic layer was dried, the solvent evaporated and the residue distilled under reduced pressure. The desired epoxide was obtained in a yield of 174 g (80%); kpt. 117-120 ° C / 0.2 kPa, njjl = 35 1.5070.

The gas chromatogram of the obtained epoxide is shown in Fig. 1; it was obtained on a 50 m capillary column, stationary phase: OVAT-11, temp. 220 ° C, isothermal.

The NMR spectrum of the epoxide is shown in Figure 2j frequency: 100 MHz, solvent: CCl 2 internal standard: tetramethylsilane.

870 0 ':'? 6 B) Preparation of trimethyl-4,8-cyclododecadienone (formula 6A, B, C)

To a solution of 66 g of the epoxide thus prepared in 400 ml of dry ether was added in 45 min with continuous stirring, 20 ml of BF3 etherate, the temperature being kept between 20 ° and 30 ° C by cooling. The mixture was then stirred for an additional two hours at room temperature, after which the reaction mixture was poured into 400 ml of saturated soda solution. The organic layer was separated, washed again with saturated soda solution and dried. The ether was evaporated and the residue distilled under reduced pressure. The desired ketone was obtained in a yield of 33 g (50%); bpt: 115-120 ° C / 0.2 kPa, ngl = 1.5057.

The gas chromatogram of the ketone is shown in Figure 3 and the NMR spectrum in Figure 4. The experimental data are as set forth under (A).

15

Example II

Preparation of tetramethyl-4,8-cyelododecadienol (formula 3A, B, C, R = CH3) A solution of methyl magnesium iodide was prepared in the usual manner by dropping 16.2 g of methyl iodide into 2.4 g of magnesium-20 curls in 100 ml dry ether and this reaction mixture is stirred for another 30 minutes under reflux. After the solution had cooled to room temperature, a solution of 19.8 g of the ketone prepared according to Example IB in 20 ml of dry ether was added with continuous stirring over 15 minutes, after which the reaction mixture was stirred for another 2 hours under reflux. The cooled reaction mixture was then poured into a mixture of 30 g ammonium chloride, 200 ml water and 100 g ice. The organic layer was separated, washed with saturated soda solution and dried. The ether was evaporated and the residue distilled on a short-way distillation apparatus at a bottom temperature of 85-90 ° C / 7 Pa. 30.0 g (80%) of the desired alcohol are obtained; n§0 ** 1.5220.

Example III

Preparation of tetramethyl-4,8-cyclododecadienol mixture (formulas IA, B, C and 2A, B, C, R = CH3).

By using the preparation method described in Example II

on the epoxide prepared according to Example 1A instead of the ketone, a 1: 1 mixture of the above secondary and tertiary alcohols was obtained; bp: 84-87 ° C / 7 Pa, n ^ = 1.5228.

The gas chromatogram of the alcohol mixture is shown in Fig. 40 and the NMR spectrum in Fig. 6; the experimental data are as reported in Example I 87 0 0 4 6 8 t 7.

Example IV

Preparation of 1-ethyl-trimethyl-4,8-cyclododecadienol (formula 3A, B, C, R = C2H5).

The above alcohol was prepared as described in Example II, starting from 13.1 g ethyl bromide instead of 16.2 g methyl iodide and from the same amount of ketone obtained according to Example IB. After distillation of the crude reaction product on a short-way distillation apparatus (bottom temperature 85-90 ° C / 7 Pa), 18.0 g (80%) of the desired alcohol was obtained; njj ^ = 1.5054. The gas chromatogram of this alcohol is shown in Figure 7 and the NMR spectrum in Figure 8; the experimental data are as reported under Example I.

Example V

Preparation of 1-vinyl-trimethyl-4,8-cyclododecadienol (formula 3A, B, C, R = C2H3).

A solution of vinyl magnesium bromide was prepared in the usual manner by dripping 19.3 g of vinyl bromide into 3.4 g of magnesium shavings in 200 ml of dry tetrahydrofuran and stirring this reaction mixture for another 20 min under reflux. After the solution had cooled to room temperature, a solution of 11 g of the ketone prepared according to Example IB in 20 ml of dry tetrahydrofuran was added with continuous stirring for 10 minutes, after which the reaction mixture was stirred for another hour under reflux.

The cooled reaction mixture was then poured into a mixture of 50 g ammonium chloride, 300 ml water and 100 g ice. The organic layer was separated and the aqueous layer extracted 1 more time with 100 ml of ether. The organic layers were combined, washed with saturated soda solution and dried. The solvents were evaporated and the residue distilled at 7 Pa on a short-way distillation apparatus at a bottom temperature of 85-90 ° C. 9.9 g (80%) of the desired alcohol are obtained; n§0 = 1,5201

The gas chromatogram of this alcohol is shown in Figure 9 and the NMR spectrum in Figure 10; the experimental data are as reported under Example I.

Example VI

Preparation of tetramethyl-4,8-cyclododecadienol mixture (formulas 1D and 2D, R = CH3).

Starting from 1,5,9-trimethyl-1,5,9-cyclododecatrienes, the € 7 0 0 / - 5 9 · δ »* epoxide (formula 5D) was prepared as described in Example 1A. BP: 117-120 ° C / 0.2 kPa; ng ° = 1.5070

The gas chromatogram of this epoxide is shown in Figure 11 and the NMR spectrum in Figure 12; the experimental data are as reported in Example I.

The epoxide was treated with methyl magnesium iodide as described in Example II. A 1: 1 mixture of the secondary and tertiary alcohol was obtained in 80% yield based on the epoxide; bp: 85-87 ° C / 7 Pa, ng ° = 1.5235.

The gas chromatogram of the obtained alcohol mixture is shown in Fig. 13 and the NMR spectrum in Fig. 14; the experimental data are as reported in Example I.

Example VII

A perfume for shampoo was prepared according to the following recipe: Bergamot oil, reconstitute 100 parts by weight C 1 -amyl cinnamaldehyde 100 parts by weight muguet base 100 parts by weight benzyl acetate 70 parts by weight 5-acetyl-3-isopropyl-1, 1,2,6-tetramethylindan 50 parts by weight 20-methyl methylone 50 parts by weight methyl dihydrojasmonate 50 parts by weight lemon oil reconstituted 40 parts benzyl salicylate 35 parts rose oil Bulgarian reconstituted 30 parts 25 undecanal * 20 parts by weight coumarin 15 parts by weight benzoin-siam resinoid 15 parts by weight isoeugenyl acetate 15 parts by weight 11-oxahexadecanolide 10 parts by weight 30 2-methyl undecanal * 10 parts by weight dodecanal * 10 parts by weight costus oil reconstituted 10 parts by weight parts of mousse de chêne absolute 5 parts of methyl ethylol 5 parts of 35 iris oil 5 parts of undecalactone * 5 parts of cyclododecadienol mixture obtained according to Example III 50 parts of total 800 parts of 40 * as 10% solution in dipropylene glycol.

8700469

In the above recipe, instead of the cyclododecadienolen mixture obtained according to Example III, the cyclododecadienol obtained according to Example II could also be successfully used.

9

Example VIII

An aftershave lotion perfume was prepared according to the following recipe:

Bergamot oil reconstitute 100 parts of lemon oil reconstitute 100 parts of 10 flf-hexyl-cinnamaldehyde 100 parts of methyl 2-hexyl-3-oxocyclopentanecarboxylate 100 parts of labdanum absolute 80 parts of linalyl acetate 55 parts of linalool 50 parts 15-acetyl-3-isopropyl-1,1,6-tetramethylindan 30 parts rosemary oil Spanish 30 parts coumarin 20 parts mousse de chêne absolute 20 parts olibanum resinoid 20 parts of 20 3-isocampyl-cyclohexanol 20 parts of acetyl-cedrene 20 parts of 11-oxahexadecanolide 10 parts of 2-methyl-3- (p-tert-butylphenyl) -propanal 10 parts of armoise oil 10 parts of 25 fir balsam 10 parts of eugenol 5 parts of basil oil 3 parts of galbanum oil 3 parts of ethyl vanillin 2 parts of 30 allyl-3-methylbutoxyacetate 2 parts of cyclododecadienol mixture obtained according to Example 6 50 parts by weight total 800 parts by weight In the above recipe, instead of the cyclododecadienolen mixture obtained according to Example 6, the cyclododecadienol obtained successfully can be used according to Example IV. .

40 6700469 * 10

Example IX

An aftershave lotion perfumed with the composition of Example VIII was prepared according to the following recipe: A) 0.3 parts by weight of 1-menthol 5 parts by weight of Uvinol D 50 ^ 30.2 parts by weight of propylene glycol 535 parts by weight. parts of ethanol B) 2.0 parts of aluminum chlorohydrate allantoinate 10 2.0 parts of lactic acid 400 parts of distilled water C) 20 parts of perfume (Example VIII) 10 parts of cremophor RH 40 ^ 15

The components listed under A, B and C were mixed separately until blends A, B and C. Blend B was then added to mixture A with good stirring. Then mixture C was added and the total homogenized by stirring. Thus, a slightly astringent after-20 shave lotion was obtained, the fragrance of which was characterized by a pleasant patchouli note.

25 1 Trademark of BASF for 2,2 ', 4,4'-tetrahydroxybenzophenone 30 2 Trademark of BASF for a reaction product of hydrogenated castor oil and epoxyethane 8700463

Claims (6)

1. 4.8 "Cyclododecadienol derivatives of formulas 1, 2 and 3 on the formula sheet, in which the ring portion X - Y represents a dimethyloctadienylene group of the formula A, B, C or D and R represents a methyl, ethyl- or vinyl group. 2. 4,8-Cyclododecadienol derivatives of formulas 1, 2 and 3, wherein the ring portion X - Y has the meanings set out in claim 1 and R represents a methyl group. Use of the 4,8-cyclododecadienol derivatives defined in claim 1 or 2 as perfume raw material. Use of the 4,8-cyclo-dodecadienol derivatives defined in claim 1 or 2 for imparting a patchouli note to perfume compositions and products to be perfumed. Perfume compositions and perfumed products, characterized by a content of one or more of the 4,8-cyclododecadienol derivatives defined in claim 1 or 2. Perfume compositions according to claim 5, characterized by a content of at least 0.1% by weight of one or more of the 4,8-cyclododecadienol derivatives defined in claim 1 or 2. *** fc 7 0 ö 4 6 9