DE1817950C3 - The use of trans-l, 7,7-trimethyl-bicyclo (4,4,0) -decanone as a fragrance - Google Patents

Description

and is from J. Chem. Soc. 1967, p. 1878.

The compound mentioned has particularly interesting and valuable odor properties and is therefore usable as a fragrance in the perfume industry. The fragrance can in particular be used for production of diluted or concentrated perfumes and for perfuming products such as soaps, detergents and Detergents, cosmetic products, waxes and general products that result from sales-related Reasons normally perfumed should be used. The connection develops you intense noble wood-like smell with an amber-like scent note.

The proportions in which the compound mentioned to achieve the desired odor effects can be used vary within fairly wide limits and depend on the Nature of the products to which the new fragrance is added. In the manufacture of Perfumes are, for example, in amounts of 0.5 to 10% of the fragrances, based on the total weight of the perfume, achieved interesting results. If the compound is used together with other fragrances Perfuming of products is used, it can for example in amounts of 0.001 to 0.5%, based based on the weight of the product to be perfumed. In other cases, for example with the production of concentrates, which are diluted with solvents or with other fragrances before use be mixed, or serve as so-called perfume bases, the concentration of said compound can be higher than 10%, e.g. up to 15% or even higher.

The quantity ranges listed above do not represent absolute values, but are only intended as

understand exemplary information. Depending on the particular olfactory effects that you want to achieve, other concentrations can of course be used.

The trans-1,7,7-trimethyl-bicyclo (4,4,0) -decanone can be obtained by 1,7,7-trimethyl-bicyclo (4,4,0) decanol- (3) oxidized. The oxidation can by known methods, for example by means of silver carbonate in the presence of diatomaceous earth, or

by means of oxidation products of transition metals, e.g. B. Chromium and copper (see for example »Organic Chemistry "by D. J. Cram and G. S. Hammond [1959], pp. 432-436, McGraw-Hill, New York). The oxidation can also be carried out by means of a Ketones can be carried out in the presence of an aluminum alcoholate according to the Oppenauer method. When Ketones are, for example, acetone, cyclohexanone, diethyl ketone, methyl ethyl ketone and methyl hexyl ketone, while as alcoholates, for example, aluminum butoxide, aluminum isobutoxide or aluminum isopropoxide can be used. The oxidation is preferably carried out either with CK> 3 or with methyl ethyl ketone carried out in the presence of aluminum isopropoxide.

The oxidation product obtained by oxidation of the carbinol consists of a mixture of the cis- and trans isomers of 1,7,7-trimethyl bicyclo (4,4,0) decanone- (3). Crystallization of this mixture gives the solid cis isomer in pure form.

The liquid trans isomer can be obtained from the mother liquors obtained in the fractional crystallization be isolated, e.g. B. by distillation or by preparative gas chromatography.

The carbinol of formula I used to prepare the trans compound (see the following Reaction scheme) can be obtained, for example, by saponification of the esters of the formula II. the Saponification can be carried out by known methods, for example by means of alkalis, e.g. B. KOH, NaOH and LiOH, in Presence of aqueous alcohols, e.g. B. methanol or amyl alcohol can be carried out.

The 6,10-dimethyl-undeeatriene- (1,5,9) of the formula III used to prepare the ester II can by reacting a geranyl halide IV, e.g. B. the chloride or bromide, with an allyl halide V, z. B. the chloride or bromide, under the usual Grignard reaction conditions can be obtained. In the following reaction scheme, X stands for halogen and R for one straight or branched, saturated, aliphatic hydrocarbon radical with 1 to 6 carbon atoms or a straight or branched, unsaturated aliphatic hydrocarbon radical with 2 to 6 Carbon atoms.

CH ₂ X

Mineral acid

->

+ R-COOH

(V) CH ₂ -X

Saponification

-

Esterification

(II) O-CO-R

according to the invention

used

connection

oxidation

cis isomer

example

By mixing the substances listed below, a fragrance composition was obtained from the "Chypre" type made:

35

40

45

Components Parts by weight Undecanal, 10% *) 10 Dodecanal, 10% *) 20th Synthetic rose oil 60 Synthetic jasmine oil 120 Hydroxycitronellal 30th Isojasmone 5 y-methylionone 90 Styrax, 50% *) 60 Cinnamyl alcohol 15th Bergamot 45 Celery oil, 10% *) 70 Citral, 10% *) 30th Patchouli 100 Santal, oriental 20th Vetyver bourbon 40 Cedryl acetate 15th Oak moss, absolute, 50% *) 40 Myrrh oil 20th Labdanum Cistus, absolute, 10% *) 20th Degreased, natural civet, lOO / oig *) 20th Ketone musk 60 Coumarin 30th Ethylvanillin 15th Jasmine, absolutely 10 Bulgarian rose oil 5 Total 950 *) In diethyl phthalate.

55

60

To this mixture 50 g of trans-1,7,7-trimethyl-65 bicyclo (4,4,0) decanone (3) were added. One received on in this way a fragrance composition that had a pleasing, amber-like and woody scent note.

Preparation of the trans-1,7,7-trimethylbicyclo (4,4,0) decanone

a) 6,10-dimethyl-undeca triene- (1,5,9)

84 g (3.5 mol) of defatted magnesium turnings were suspended in 100 ml of absolute ether. The magnesium was activated with an iodine crystal. Within 3 hours, first 300 g (1.75 mol) of geranyl chloride and then a solution of 268 g (3.5 mol) of allyl chloride in 800 ml of ether were added dropwise. The reaction mixture was heated to boiling for 4 hours, then cooled and _{poured into a solution of 200 g of NH 4} Cl in 1 liter of ice water. The solution was extracted with ether. After concentration, the extracts yielded 384 g of crude 6,10-dimethyl-undecatriene- (1.5,9), which was further processed without prior purification.

b) 1,7,7-trimethyl-bicyclo (4,4,0) decanol- (3)

The 384 g of triene obtained in accordance with paragraph a) were added dropwise to a mixture of 2.7 kg of 98% strength formic acid, 270 g of concentrated sulfuric acid and 1000 ml of dioxane ^{over a period of about 1 1/2 hours at 50 °.} The reaction mixture was stirred at 60 ° for 3 hours, then cooled and then poured onto ice. After extraction with ether, the extracts were neutralized with 10% aqueous sodium bicarbonate and washed neutral with water. The extract was dried and concentrated in the usual way. The residue (430 g) was treated with 140 {. Potassium hydroxide, 140 ml of water and 1500 ml of methanol are mixed and the mixture is stirred at reflux temperature for 4 hours. After removing the methanol under reduced pressure, the residue was extracted with ether. The extract was neutralized, washed and dried in the usual manner. Concentration of the extract and concentration of the residue (350 g) in vacuo gave 1,7,7-trimethyl-bicyclo (4,4,0) decanol- (3) (bp. 114-125 ° / 0.001 torr, m.p. 53 -54 °).

c) Oxidation of 1,7,7-trimethylbicyclo (4,4,0) decanol- (3)

A solution of 0.53 mol of CrOj in 200 ml of water was dripped into a solution of 105 g (0.53 mol) of the carbinol prepared in accordance with paragraph b) in 800 ml of glacial acetic acid over a period of about 2 hours at 40-45 ". The mixture was heated for 4 hours at 70 °, then cooled and extracted with ether, the extract was treated and concentrated in the usual manner, giving 95 g of a crude mixture of cis- and trans-1,7,7-tri · methyl-bicyc! o (4,4,0) decanone- (3) in a weight ratio of about ι: 1. Recrystallizing the crude product twice in hexane gave 46.5 g of pure cis isomer with a melting point of 46-47 °. IR spectrum ( liquid phase): 965, 1215, 1450, 1705, 2940 cm '; NMR spectrum (CCI ₄ ): 0.86 (6H ₁ s), 0.96 (3H ₁ s), 1.43 (8H, m) , 1.95 (2H), 2.23 (2H, m) ppm (o).

The mother liquors obtained during the crystallization were concentrated. The residue, consisting largely of the trans isomer, was purified by preparative gas chromatography in a conventional polyethylene glycol column of 2.5 m at 150 ° with a helium flow of 40 ml per minute. The product obtained had the following NMR spectrum (CCI ₄ ) to: 0.87 (6H, s), 1.13 (3H ₁ s) ₁ 1.5 (8H, m) ₁ 2.2 (4H ₁ m) ppm (o).

Claims (1)

Claim: The use of trans-1,7,7-trimethyl-bicyclo (4,4,0) -decanone as a fragrance. The present invention relates to the use of trans-1,7,7-trimethyl-bicyclo- (4,4,0) -decanone as a fragrance for the manufacture of perfumes and perfumed products. The compound used in the present invention has the formula