Methylcyclododecatri-2,5,9-en-1-ols, a process for their preparation, and their use

Abstract

The invention relates to new methylcyclododecatri-2,5,9-en-1-oles of formula ##STR1## in which one of the dashed lines represents a double bond and the other a single bond, and the endocyclic double bonds may be cis- and trans-configured,a process for their preparation and their use as scents.

Description

The invention relates to new methylcyclododecatri-2,5,9-en-1-ols, a process for their preparation, and their use as scents.

U.S. Pat. No. 3,723,478 disclosed the saturated alcohol 2,6,9-trimethyl-cyclododecan-1-ol as an intermediate for the preparation of the saturated ketone 2,6,9-trimethyl-cyclododecan-1-one; however, no reference was made to the sensory properties of the alcohol. U.S. Pat. No. 3,845,078 states that the mixture of the geometrical isomers of 1,5,9-trimethylcyclododeca-4,8-dien-1-ol has a tenacious, woody vetiver fragrance.

Surprisingly, it has now been found that methylcyclodedecatri-2,5,9-en-1-oles of the formula ##STR2## in which one of the dashed lines represents a double bond and the other a single bond, and the endocyclic double bonds may be cis- and trans-configured,

in contrast to the known 2,6,9-trimethylcyclododecane derivatives, have a fine woody note suggestive of ambergris, musk and sandalwood and thus has extremely valuable scent properties which are desired in perfumery.

The invention therefore relates to methylcyclododecatri-2,5,9-en-1-oles of the formula I.

The compounds of the formula I according to the invention are 2,6,9-trimethyl-cyclododecatri-2,5,9-en-1-ol and its isomer 2-methylene-6,9-dimethylcyclododeca-2,5,9-en-1-ol.

The two compounds of the formula I are obtained by monoepoxidizing 1,5,10-trimethyl-cyclododeca-1,5,9-triene, a commercially available compound, in a fashion which is known per se using a peracid, and heating the monoepoxide obtained, 1,6,9-trimethyl-1,2-epoxycyclododeca-5,9-diene, in the presence of aluminium isopropylate. By heating the epoxidation product in the presence of aluminium isopropylate, an opening of the epoxy ring by isomerisation is achieved which proceeds virtually in one direction.

The invention therefore relates to a process for the preparation of the compounds of the formula I, characterized in that, 1,5,10-trimethylcyclododeca-1,5,9-triene is monoepoxidized in a fashion which is known per se, and the 1,6,9-trimethyl-1,2-epxoy-cyclododeca-5,9-diene obtained is isomerized by heating in the presence of aluminium isopropylate with opening of the epoxy group.

The epoxidization of the starting triene is carried out by the conventional processes which are described in the literature, for example in U.S. Pat. No. 3,723,478, using peracids such as perbenzoic acid, monoperphthalic acid, or preferably, peracetic acid in inert solvents such as chloroform, methylene chloride, benzene or, preferably, toluene. The small amounts of diepoxide which are produced at an approximately 10% excess of the peracid, relative to the cyclic triene, can easily be removed by distillation.

The isomerization of the monoepoxide can be carried out in the presence of inert solvents, for example toluene; however, the isomerization is preferably carried out without solvent. The aluminium isopropylate is used in an amount of 0.5 to 5 mol %, preferably 1 to 3 mol %, relative to the monoepoxide. The reaction is carried out at temperatures from 120.degree. to 180.degree. C., preferably 140.degree. to 160.degree. C., and preferably at, for example, a reduced pressure of 3 mbar to 7 mbar.

The invention furthermore relates to the use of the compounds of the formula I according to the invention as scents. They are used in combination with other scents which are known per se, as described, for example, in Arctander, Perfume and Flavor Chemicals, Montclair, N.J. (USA), 1969, and etherial oils, as described in Arctander, Perfume and Flavor Materials of natural Origin, Elisabeth, N.J. (USA), 1960. They give these fragrance compositions a subtle, long-lasting woody fragrance with well-rounded and fixing properties. In general, they are used in an amount of 1 to 80% by weight, preferably 3 to 25% by weight, relative to the fragrance composition.

The fragrance compositions produced using the compounds of the formula I according to the invention are highly suitable for perfuming finished products in the aerosol, washing agent and industrial chemistry sector, but in particular in the fine perfumery and cosmetics sector. The fragrance compositions and perfumed products are produced in a conventional fashion, for example by mixing the components.

EXAMPLE 1

1,938 g (10.2 mol) of peracetic acid (40% strength) are added over 2 hours with stirring to a mixture of 1,836 g (9 mol) of 1,5,10-trimethyl-cyclododeca-1,5,9-triene, 171 g (1.62 mol) of soda and 2,700 g of toluene at 10.degree. to 20.degree. C. The reaction mixture is stirred for 3 hours at 10.degree. to 20.degree. C. and subsequently diluted with 1,500 g of water. The organic phase is separated off, washed until neutral and freed from excess peroxide by adding iron(II) ammonium sulphate. The solvent is then removed and the residue is distilled. The yield is 1,444 g (=72.9% of theory) of 1,6,9-trimethyl-1,2-epoxy-cyclododeca-5,9-diene, boiling point: 101.degree. C./1 mbar.

1,444 g (6.55 mol) of the monepoxide thus obtained are heated to 140.degree. to 145.degree. C. after addition of 25 g (0.12 mol) of aluminium isopropylate, a vacuum of 5 mbar simultaneously being produced. After heating for 3 hours at the reflux temperature, the reaction mixture is subjected first to coarse distillation and then to fine distillation. 1,209 g (83.7% of theory) of the isomeric mixture of 2,6,9-trimethyl-cyclododecatri-2,5,9-en-1-ol and 2-methylene-6,9-dimethyl-cyclododecane-2,5,9-trien-1-ol, boiling point: 111.degree. C./0.4 mbar, are obtained.

EXAMPLE 2

A perfume oil having a female note is produced by mixing the following components:

______________________________________Alpha-iso-methylionone 100Phenylethyl alcohol 70Hexenyl salicylate 50Benzyl salicylate 40Cyclopentadecanolide 25Jasmine base 50Rose base, de Mai type 40Styrolyl acetate 20Menthyl acetate 80Acetanisole 5Dimethylbenzylcarbinyl acetate 40Methyl octinoate, 10% strength indipropylene glycol 5Alpha-hexylcinnamaldehyde 604-(4-Hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde 40Isoeugenol methyl ether 80Musk ketone 152-Tert.-butylcyclohexyl acetate 30Allylamyl glycolate 3Alpha-damascone 2Nonadienal, 1% strength in diethyl phthalate 6Ylang-ylang oil 40Undec-8-en-1-al 22,6,10-Trimethyl-2,5,9-cyclododecatrien-1-ol + isomer 120Dipropylene gly 77 1,000______________________________________

EXAMPLE 3

A perfume oil having a male note is produced by mixing the following components:

______________________________________Bergamot oil, African synthetic 100Oil of rosemary 20Lime oil, West-Indian distilled 20Basil oil 10Mugwort oil 10Pine-needle oil 20Allyl cyclohexylpropionate 4Prenyl acetate 1Hydroxycitronellal 50Alpha-hexylcinnamaldehyde 404-(4-Hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde 30Dihydromyrcenol 40Marjolia base 50Oak moss, abs. Moroccan, 50% defatted 30Patchouli oil, decolorized 2201,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-.gamma.-2-benzopyran,50% strength in diethyl phthalate 100Methyl orcincarboxylate 102,6,10-Trimethyl-2,5,9-cyclododecatrien-1-ol+ isomer 160Dipropylene glycol 85 1,000______________________________________

Claims

1. A methylcyclododecatri-2,5,9-en-1-ol of the formula ##STR3## in which one of the dashed lines is a double bond and the other is a single bond.

2. A process for the preparation of methylcyclododecatri-2,5,9-en-1-oles of the formula ##STR4## wherein one of the dashed lines is a double bond and the other is a single bond,

which process comprises:

(a) monoepoxydising 1,5,10-trimethyl-cyclododeca-tri-1,5,9-ene with a peracid and

(b) isomerising the monoepoxide obtained, 1,6,9-trimethyl-1,2-epoxycyclododeca-5,9-diene, by heating in the presence of aluminum ispropylate.

3. A fragrance composition comprising an effective amount of a methylcyclododecatri-2,5,9-en-1-ol according to claim 1.