DE1811289B2 - ice-1,7,7-trimethyl-bicyclo square bracket to 4,4,0 square bracket to decanone- (3), process for its production and its use as a fragrance - Google Patents

Description

The present invention relates to cisl, 7,7-trimethyl-bicyclo [4,4,0] -decanone- (3), a method for producing the same and its use as a fragrance according to the preceding claims.

The new compound has the formula

The new compound has interesting and valuable odor properties and can therefore be used as a Fragrance can be used in the perfume industry. The new fragrance can in particular be used for production of diluted or concentrated perfumes and 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 new compound develops an intense, precious wood-like odor with an amber-like scent note.

The proportions in which the new compound is used to achieve the desired olfactory effects vary considerably further limits and are based on the nature of the products, which the new fragrance is added. In the manufacture of perfumes, for example, amounts of 0.5 to 10% Fragrance, based on the total weight of the perfume, achieved interesting results. When the new Compound used together with other fragrances to perfume products, it can, for example, be in an amount of 0.001 to 0.5%, based on the weight of the to be perfumed Product. In other cases, for example in the production of concentrates, which are diluted with solvents or mixed with other fragrances before use or which serve as so-called perfume bases, the concentration of the named compound can be higher than 10%, z. B. to 15% or even higher.

The quantity ranges listed above do not represent absolute values, but are merely exemplary To understand information. Depending on the particular olfactory effects that you want to achieve other concentrations are of course used

_IS ^We D ^d i ^{n The} process for the preparation of the new compound is characterized in that 1 7,7-Tnmethyl-bicyclo [4,4,0] -decanol- (3) is oxidized in a manner known per se and the cis- Isomer of 1,7,7-Tnmethyl-bicyclo [4,4,0] -decanons- (3) by fractionated

Crystallization of the oxidation product isolated.

The oxidation can for example by means of silver carbonate in the presence of diatomaceous earth or ri.ttels Oxidation products of transition metals, e.g. B Chromium and copper (see, for example, »Organic

"Chemistry" by D. J. C r a m and G. S. H a m m ο η d Π9591 S 4 ^ 2 to 436, McGraw-Hill, New York), be performed. The oxidation can also be carried out using a ketone in the presence of an aluminum alcoholate according to the Oppenauer method

jo be carried out. For example, s.ch is suitable as ketones Acetone. Cyclohexanone, diethyl ketone, methyl ethyl ketone and methyl hexyl ketone, while as Alcoholates, for example aluminum butylate. Aluminum isobutylate or aluminum isopropylate

can be turned. The oxidation is preferably carried out either with CrO ₃ or with methyl ethyl ketone in the presence of aluminum isopropoxide.

^gC 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-Γ4 40 01-decanone- (3). Crystallization of this mixture gives the solid cis isomer in pure form. The trans connection is well known. It is produced in a different way without the cis compound being formed in this procedure (Journal of the Chemical Society. Jg. 1967. pp. 1876 to 1878. However, the use of the trans compound as a fragrance is not known.

The carbinol of the formula used as the starting product in the process according to the invention (see that following equation) 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. KOH, NaOH and LiOH in the presence of aqueous alcohols, e.g. B. Methanol or amyl alcohol.

The 6,10-dimethyl-undecatriene- ( 1,5,9) of the formula III can by

Implementation of a geranyl halide IV, e.g. B. of chloride or bromide, with an allyl halide V, e.g. the chloride or bromide, can be obtained under conventional Grignard reaction conditions. The establishment of the new connection is through

the following reaction scheme is shown, in which X denotes halogen and A that of the new cis-connection represents corresponding trans-connection.

CH, X

(V)

CH ₂ X

Mg

(IV)

(III)

Mineral acid
+ R - COOH

Saponification

Esterification

Ο —CO —R

(ID

(D

a) o.lO-Dimethyl-undecatrien-iUS ^)

oxidation

(A)

In the following exemplary embodiments, the temperatures are given in degrees Celsius.

example 1

A solution of 0.53 mol of CrO ₃ in 200 ml of water was converted into a solution of 105 g (0.53 mol) of 1,7,7-trimethylbicyclo [4,4,0] within about 2 hours at 40 to 45 ° -decanol- (3) (see below for preparation) added dropwise to 800 ml of glacial acetic acid. The mixture was heated at 70 ° for 4 hours, then cooled and extracted with ether. The extract was treated and concentrated in the usual manner. 95 g of a crude mixture of cis- and translJJ-trimethyl-bicyclol / M ^ -decanone-P) in a weight ratio of about 1: 1 were obtained. By recrystallizing the crude product twice in hexane, 46.5 g of pure cis isomer with a melting point of 46 ° to 47 ° were obtained. IR spectrum (liquid phase): 965, 1215, 1450, 1705, 2940 cm "¹; NMR spectrum (CCl ₄ ): 0.86 (6 H, s), 0.96 (3 H, s), 1 , 43 (8H, m), 1.95 (2H), 2.23 (2H, m) ppm {/>).

The production of the starting material was carried out as follows:

O
CH ₃

(compound according to the invention)

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-dimethylundecatriene- (1,5,9), which was further processed without prior purification.

40

60

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 were 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 was added dropwise.

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

The paragraph a) 384 g obtained were triene 'within front · ■ "■ -s 1 I ₂ hours at 50 ° was added dropwise a Genmu; of 2.7 kg 98% formic acid, 270 g concise! .oner sulfuric acid and 1000 ml of dioxane added. 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 manner. The residue (430 g) was mixed with 140 g of potassium hydroxide, 140 ml of water and 1500 ml of methanol and stirred for 4 hours at reflux temperature. After removing the methanol under reduced pressure, the residue was extracted with ether. The extract was neutralized, washed and dried in the usual manner. By concentrating the extract and concentrating the residue (350 g) in vacuo, 1,7,7-trimethylbicyclo [4,4,0] -decanol- (3) (bp. 114-125 ° / 0.001 torr, melting point 53 to 54 °).

Example 2

A mixture of 19.6 g of 1,7,7-trimethyl-bicyclo- [4,4,0] -decanol- (3) prepared according to paragraph b) of Example 1, 72 g of methyl ethyl ketone, 50 ml of toluene, 10.5 g of aluminum isopropoxide and 2 g of aluminum chloride was heated to boiling for 6 hours. After cooling, the reaction mixture became stirred together with 200 ml of 10% sulfuric acid and then extracted with toluene. The extract was made treated and distilled in the usual way. 8.2 g of i, 7,7-trimethyl bicyclo [4,4,0] -decanone- (3) were obtained of bp 85 to 90 ° / 0.001 Torr, from which the cis compound was obtained as described above.

Example 3

246 g of 1,7,7-trimethyl-bicyclo [4,4,0] -decanol- (3) (preparation see below) were dissolved in 2.5 kg of pure acetone . 642 g of "Jonesschem oxidizing agent" (prepared according to J. Chem. Soc. 39, 1946) were added dropwise to the solution with cooling at such a rate that the temperature of the reaction mixture remained between 23 and 25 °. The reaction mixture was left to stand for 2 hours and then stirred together with 1.5 liters of water and 500 ml of petroleum ether (boiling range 80 to 100 °). The mixture was left to stand overnight and then extracted twice with petroleum ether. Customary treatment of the combined extracts gave 220 g of crude ketone. By distilling this crude product, 107.6 g of the mixture of the cis and trans isomers of 1,7.7-trimethyl-bicyclo- [4,4.0] -decanone- (3), bp 77 to 85 '0.015 to 0.025 Torr, which was separated as described in Example 1, was obtained.

The starting material was obtained as follows:

a) 6,10-dimethyl-undecatriene- (1,5,9)

51 g (2.1 mol) of magnesium turnings were suspended in 1700 ml of ether and activated with an iodine crystal. A solution of 153 g (2.0 mol) of allyl chloride in 200 m ' Ether was added dropwise at such a rate that the reaction mixture during the dropping was kept at reflux temperature. The mixture was then left for another 2 hours heated under reflux and then at reflux temperature with a solution of 210 g (1.05MoI) technical, 82% geranyl chloride in 200 ml of ether added dropwise. The reaction mixture was stirred for a further 2 hours at room temperature, then cooled to 10 ° and slowly with 20% acidified with aqueous acetic acid. The mixture was extracted with ether, whereupon the extracts with 10% aqueous sodium hydroxide, washed with water and dried in the usual manner and were narrowed. 217 g of crude product were obtained in the form of a pale yellow liquid, the content of which of 6,10-dimethyl-undecatriene- (l, 5.9) was about 80% according to gas chromatographic analysis. That The raw product was processed further without prior purification.

b) l, 7,7-trimethyl-bicyclo [4,4,0] -decanol- (3)

500 g of 6,10-dimethylundecatriene ( 1,5,9) were concentrated at 30 to 35 ° in a mixture of 1 kg of acetic acid and 165 g Sulfuric acid added dropwise. The reaction was strongly exothermic and lasted about 4 hours. That The reaction mixture was stirred for a further 3 hours at 40, whereupon, with vigorous stirring, from 3 to 51 Ice water was added. The mixture was washed twice with petroleum ether (boiling range 80 to 100) extracted. The extracts were neutralized with 10% aqueous sodium hydroxide and with water

washed. The remaining moisture was by azeotropic distillation of the extract with the Solvent removed. Further concentration gave 562 g of crude product, which together with 1124g amyl alcohol and 199g (3.54 mol) potassium

, ₅ hydroxide was refluxed for 4 _1/2 hours. After cooling, the reaction mixture was stirred with 101% of water and then the alcoholic layer was separated off. By treating the latter as usual and distilling the residue

246 g of 1,7,7-trimethyl-bicyclo- [4,4.0] -dccanoM3) with a boiling point of 95 to: 2770.025 to 0.08 Torr were obtained.

Usage example

By mixing the substances listed below, a fragrance composition became more flowery. "Chypre" -like type made:

Components

Gcuidits-I ei Ie

(£ 1

Decanal, 10% *)

Undecanal, 10% *)

Dodecanal, 10% *)

Synthetic lily of the valley

Synthetic rose oil

Synthetic jasmine oil

Synthetic carnation

Bergamot

Ylang

Tarragon, 10% *)

Oak moss, absolute, 50% *)

Benzoin tears, 10% *)

Degreased natural civet, 10% *)

j'-methylionone

Patchouli

Santal, oriental

Coumarin

Ambrite musk

Ketone musk

Orange blossom, absolutely 10% *)

Jasmine, absolutely

Rose, absolutely

Undecalactone, 10% *)

Vanillin, 10% *)

Total

*) In diethyl phlhalal.

45

10

150

150

90

60

90

45

30th

20th

10

15th

60

30 25 10 50 15 10 20 10 _5

990

10 g of cis-l, 7,7-trimethylbicyclo [4,4,0] -decanone- (3) added In this way, a fragrance composition with a pleasing amber-like and woody fragrance note was obtained.

Claims (3)

Patent claims: 1. cis-l, 7,7-trimethyl-bicyclo [4,4,0] -decanone- (3). 2. Process for the production of the ketone according to Claim 1, characterized in that one lJJ-trimethyl-bicyclo ^ AOD-decanol-ß) in an is oxidized in a known manner and from it the cis-isomer of l, 7,7-trimethyl-bi9ydo [4,4,0] -decanons- (3) isolated by fractional crystallization of the oxidation product. 3. Use of the compound according to claim 1 as a fragrance.