SU1213021A1 - 5-methylgeranylchloride as semiproduct for synthesis of fragrant substances - Google Patents

Abstract

5-Metsch1 geranyl chloride formula G as an intermediate for the synthesis of fragrant substances. (L u y o d o y

Description

one

The invention relates to a new chemical compound, specifically to 5-methylheranyl chloride o6p;

   1 x / h

A geranyl chloride is known, from which citral can be synthesized. This is a fragrant and intermediate product for the production of other blowing agents, as well as biologically active substances, including juvenoids of altozar and altoside.

The purpose of the invention is to find a new intermediate for the synthesis of new fragrances: 5-methylcytral and 5-methyllinalol.

The 5-methyl geranyl chloride of formula 1 is obtained from hydrochlorides, methyl penadienes and isoprene in the presence of, for example, tin tetrachloride, zinc chloride, etc. as a catalyst. The latter is added to the mixture of the starting materials in an organic solvent (for example, dichloroethane, white spirit, etc.) or without it. At the end of the reaction, the catalyst is removed from the reaction mixture as a complex with an amine (for example, urea) or in a solution of a heterogeneous solvent where the catalyst is dissolved (for example, water, a solution of salts in water, glycol, etc.). After distillation, unreacted starting materials are reused in the process.

The target product 5-methyl gerani-chloride is separated from the mixture in two types. As a complex salt, tertiary a MiiHOB (for example, dimethylanic, hexamethylene tetramine, etc.) is used in further syntheses, for example, by a known method in the Sommle reaction. A 5-methyl citrale is obtained, having a pleasant citrus smell with a lemon tint. In the case of obtaining the chloride fraction, its saponification, a mixture of alcohols containing up to 63% of 5-methyl lynopool is obtained, also fragrant. th substance, possessing the smell of herbs with a terpene tint.

Example 1. To a mixture of 59.3 g of methyl pentadiene hydrochlorides and 34 isoprene, a 2% solution of tetrachloride tin in a solution of white spirit is added with stirring. During the reaction, the temperature of the mixture

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rises from 20 to 55 ° C. The mixture is then cooled and 10 ml of a concentrated calcium chloride aqueous solution are added. The mixture is stirred, settled and the aqueous solution is separated. Unreacted components are distilled off from the reaction mixture to obtain 34.4 g of product (telomer), which contains 53.2%

10 5-metshirshash1 chloride.

Cj chloride fractions are distilled off from telomere (81% of telomere and 5 methylmeranyl chloride is obtained from the latter in the form of the dime 5 complex of tylphenyl-5-methylheranyl ammonium chloride complex. 9.3 g of C fraction of chlorides (containing 65% of 5-methylhexane 1-chloride) , 5.4 g of dimethylaniline and 5.4 g of methanol are stirred and left to stand for a day, then 25 ml of 50% methanol and 30 mp of petroleum ether are added, mixed, settled and the layers separated. the solution is washed twice with petroleum ether, then methanol is distilled off under moderate vacuum Toluene is added to the residue and the azeotrope is distilled from the mixture under moderate vacuum.

30 residues distilled residues of toluene. The mixture is heated to 120 ° C and the dimethylaniline and 5-methylheranyl chloride formed during pyrolysis are distilled under vacuum. Last washed

35 with a 10% acetic acid aqueous solution to remove dnmethyl-aniline impurity, then an aqueous solution of calcium chloride and dried over sodium sulfate.

40 Get 3.2 g of 5-methyl 1: chloride: b.p. (2 mm Hg) hj 1.4742; dT 0.064; purity 99.0% (PKH).

Mol. Of mass: determined 186.7, 45 are numerically 186.7.

Determined,%: C 70,7; H 10.2; C1 18.9.

Calculated,%: C, 70.75; H 10.26; 50 CF 18.99.

Yield 52.9%. The structure of the substance is confirmed by NMR-spectrum data, Example2. To a mixture of 10.8 g

d

hydrochlorides of methyl pentadiene and 55 11.2 g of isoprene; 0.02 g of zinc chloride was added with stirring. Reaction temperature. At the end of the reaction, 4 mp of 51213021 are added to the mixture.

count, mix, settle, and separate the glycol solution. The unreacted components are distilled off and 15.6 g (70.9%) of the reaction product (telomer) containing 48.0% of 5-methyl geranyl chloride (PKH) is obtained. The latter is washed in 5 methyl linalool.

Example 3 To a mixture of 3.3 kg of technical hydrochloride methylpantadiene (85.1% hydrochlorides, 14.9% of light hydrocarbons) and 3.7 kg of isoprene, 2.2% of tin tetrachloride in dichloroethane was added with stirring. During the reaction, the temperature rises from 15 to 33 ° C. At the end of the reaction, the mixture is cooled to 0.5 kg of urea, stirred and filtered through cotton wool. Of

Editor N.Egorova

Compiled by V. Zhidkov Tehred M. Kuzma

723/35 Circulation 379Subscription

VNIISH State Committee of the USSR

for inventions and discoveries 113035, Moscow, Zh-35, Raushsk nab., 4/5

Branch ShSh Patent, Uzhgorod, Proektna St., 4

unreacted components were distilled off into the reaction mixture. The remainder, 4.4 kg (70.8%) of telomer, containing 45.3% of 5-methyl geranyl chloride (GLC), was isolated from the mixture as a complex salt of hexamethylene tetramine. From the latter, 5 methylcytral is synthesized.

Thus, the -5-methyl citral obtained from the new intermediate product has a perfume rating of 4.2 (organoleptic assessment according to the tiball system) has a pleasant citrus smell with a lemon tint, moreover, its smell is more resistant than, for example, citral - known fragrant substance.

Proofor N. Ordeyi

Claims (1)

5-Methylheralin formula as an intermediate for the synthesis of fragrant substances.