CS267946B1 - The method of producing geraniol and nerol by linalool isomerism is catalytic - Google Patents

Abstract

The solution relates to a method for producing synthetic terpene aromatic substances geraniol and nerol by catalytic isomerization of linalool in the presence of orthovanadic acid esters in an amount of 0.1 to 1% by weight as a catalyst and organic solvents and/or silicon tetrachloride in an amount of 0.2 to 2.3% by weight as a promoter. The isomerization is carried out in the liquid phase at temperatures of 130 °C to 170 °C. A conversion of 00a up to 30% and a selectivity of 00a up to 90% are achieved. The use is expected in the perfume and cosmetic industry.

Description

en 267 9 ^ 6 B1 1

The invention relates to a process for the production of geranol and nerol by a catalytic isomerisolium olool such that the composition of the catalyst systems is composed of 0.1 to 1.0% by weight of orthovanadic acid. and organo-chlorosilanes and / or silicon tetrachloride in an amount of 0.2 to 2.3% by weight. as a promoter at temperatures of 130 to 170 ° C.

Allyl rearrangement as an isomerization reakola of a tertiary unsaturated olefin of the Josystomatic is investigated by a number of research institutions. In the last desiccant, the allyl rearrangements for isomerization of lloloolol are used, the products indicated, the isomerisole are the torpedo fragrances geraniol and norol. Isomorizáoia llnaloolu Jo reak-oia equilibrium and undergo equation; Γ3 CH 3 - (j = CH-CH 2 -CH 2 -C-CH 1 = CH 2 CH 2 -CNCH-C 1 -C 4 -C 11 CH 2 -OH,

OH CH "linalool geraniol (norol) wherein the direction of the reactivity depends on the reaction subunit. Isomerism of llnalool (3,7-dimethyl-1,6-octadien-3-ol) produces two isomers, namely geraniol (3,7-dimethyl-2,6-octadiene-1-ol), trans-isomer with the conformational designation E, and nerol (3,7-dimethyl-2,6-octadiene-1-ol), the cis isomer with the conformational designation Z, in a ratio of about 3: 2 to each other. Metal catalysts V, V to VII are known as catalysts for reacting reactants. of the Mendelian Periodic Element Set.

Known procedures for breaking isomerisol-allylol to geraniol (nerol) employing acid catalysts such as phosphoric acid, sulfuric acid, florldromic acid and the like have not been found to result in the formation of a large amount of unreacted products and the resulting selectivity of the isomerization reaction. According to U.S. Pat. No. 2,307,468, the isomerization of unsaturated alcohols utilizes the transient alcohols V to VH. groupsMendelejovej periodiokej sústavek. These are esters of vanadic, molybdic, tungstic, perhemic, alcohol, methanol, ethanol, n- and iso-propanol, seo. buanols, and so on. A disadvantage of some of these compounds is that esters of lower alcohols, e.g., triisobutylortovanadate, are sensitive to the presence of water and already hydrolyze in contact with air humidity, (NF Orlov, MG Voronkov, Izv. Akad. Nauks USSR, Od, Chlm. 1957,933) . According to the patent NSR 21 16 698, the new wolf frame compounds designated by the general formula (WO (OR) (OR 1) (OR 1) (OR 1) / n L, where R 1, R 2, R 4, R 6, are used as allylic acid catalysts. eu of a hydrocarbon group or a group of the formula R @ 1, R @ 2 and R @ 5, respectively. are also hydrocarbon groups; L is one or more pyridine, dicyclohexylamine, trioycyclohexylphosphine, and isomeric reactants with 00a 90% selectivity. According to U.S. Pat. No. 4,254,291, proesallyl rearrangement using certain acid-forming metals, e.g., B, Sn, Zr, utilizes an allyl alcohol ester which, in the presence of vanadium catalyst, skews from the tertiary alcoholate to the primary and secondary alcohols. secondary alcoholate, The isoesters of acid-forming metals with isomerized alcohol are hydrolyzed with methanol or dilute liquor. The resulting boronic, olefinic or quartzated esters of the methanol (e.g., triazotylborate) or alcohol-free salts of the above acids impart to the by-products of said process. The French Patent 1819 ** 6 discloses the epic epoch of the production of primary or secondary alcohols by the isomerization of J-ethylene alcohols in the presence of metal overheating compounds V to VII. of the Mendelian period, a system of elements at 50-250 ° C in the liquid phase. As isomerization catalysts, ammonium metavanadate or tero-orthoaddic acid esters are used. butyl alcohol, tero. amyl alcohol, oyklehexanol, tetrahydrolinalool and the like, dosed in an amount of up to 4% by weight, calculated on the morated alcohol. A conversion of 17.3% to 34.2% with a selectivity in the range of 22.2 to 89.9% is achieved. The isomerization processes utilize conventional cell isomerization catalysts, predominantly the orthovanadic acid esters dispensed in a relatively large amount, many of which already hydrolyze in contact with the moisture and thereby lose their effectiveness. Up to a conversion of 00a to 20-20% with very different selectivity. The Wolf frame catalysts disclosed in NSR-pat, 21 16 698 require complicated and costly preparation. U.S. Pat. No. 4,254,291 utilizes conventional isomerization catalysts (esters of ortho-adadicadic acid), in addition, it consumes boric acid, tin or zirconium, which esters with methane or alkali salts represent waste products of isomeric reactors.

Disadvantages of the aforementioned processes are the preparation of geraniol and nerol by the liquid-lysooliocyanous lysine thiocyanate in the presence of orthovanadic acid esters in an amount of 0.1 to 1.0% by weight as a catalyst at 130-170 ° C according to the invention. the isomerization reaction promoters are trimethylsilysiline and / or diphenyldiohalosilane and / or silicon tetrachloride in an amount of 0.2 to 2.3. The advantages of the process according to the invention are that the isomerism is carried out in the presence of a minimal amount of orthovanadic acid esters in the isomerization reaction. by combining it with the promoters of organosiloxanes and / or silicon tetrachloride, the achievement of a reaction equilibrium of the isomerism is achieved, with a 20 to 3% conversion selectivity of up to 90. The isomerization is carried out in a liquid phase without a solvent, or in the presence of a solvent, using a hydrocarbon solvent such as xylene or a solvent and a high boiling point, e.g. polyethylene glycol 300 (PEG-300: polyethyl glycol · having an average molecular weight of ω 300). The advantage of using an edible dissolving agent is that the crude isomerization product is subjected to a vacuum distillation to a molecular or film evaporator, the isomerization products and the flood alcohol are separated from a catalyst and a catalyst which can be re-used together with a relatively isomerization reaction. Isomerization reactions It is advisable to perform in an inert atmosphere, e.g., the presence of air in the atmosphere deteriorates the selectivity of the catalysts. The isomerism pressure does not affect, but when the lower boiling point solvent is used, it is necessary to perform the reaction at a waiting time to reach the desired reaction temperature. The isomerization reaction is carried out in the temperature range of 130 to 170 ° C, while the reaction temperature is increased by the temperature, but also by the formation of byproducts, that is, by the selectivity of the reaction. Low temperatures improve the selectivity, but greatly increase the time to reach the reaction equilibrium. Reaction progress is monitored by statographers.

The following examples illustrate the invention and its advantages: Example 1

40 g of linalool, 100 g of xylene, 0.4 g of triethanolaminortovanadate and 0.4 g of trimethylohlorosilane are charged into a 25 ml glass three-necked flask equipped with a stirrer, a low-temperature heater, an azeotropic attachment and electrical heating. With constant agitation, the mixture is heated and maintained at 142 ° C. After a few hours of the isomerization reaction, the chromatograph determines the geraniol and nerol content of 28.9 $> · CS 267 946 B1 3 Example 2

154 S of linalool, 40 g of toluene, 0.75 8 of triethanolaminortovanadiene and 1.5 S of diphenyldlchlorosilane are placed in a 1 liter sloping autoclave, heated, aloe-tipped, and under a inert atmosphere of N2, the sarcogenic mixture is maintained at 16 ° C. C, After one hour of isomerization reaction in the reaction mixture, the chromatographies were determined to be 56.5% linalool, 9% nerol and 12.9 geraniol, 43.5% conversion.

52.2% selectivity

Comparing Example 2

154 g of linalool, 40 g of toluene and 0.75 g of triethanolaminortovanadiene are added to a 1 L glass autoclave as in Example 2. As described in Example 2, 154 g of linalool, 40 g of toluene and 0.75 g of triethanolaminortovanadiene are charged. While stirring and under an inert atmosphere of N 2, the reaction mixture is maintained at 16 ° C. The Styrooh watchmaker isomerization reaction was measured in a reaction mixture of 74.1% linalool, 2.4% nerol and 3.6% geraniol.

25.9% Conversion

Selectivity 23.2% Preparation of the catalyst (1) 30 g of vanadium oxide, 3 g of residual linalool distillate, 200 g of toluene are placed in a 1 l sloping autoclave equipped with a stirrer and an azootropic extension. The mixture is maintained under stirring at an inert atmosphere of 15 ° C and a pressure of 1 bar.

The catalyst formed after Styrooh hours was removed, filtered off and dried, yielding 33.3% of catalyst. Example 3

Place 400 g of linalool, 100 g of polyethylene glycol 3θ3.8 of the catalyst prepared according to (1) and 1 g of diphenyldiohalosilane in a 1 liter glass autoclave as in Example 2. \ t While stirring and in an inert atmosphere, the reaction mixture was maintained at 164 ° C. 74.3% Hnal opium, 8.8% nerol and 13.3% geraniol were assayed by chromatography for the reaction mixture in the reaction mixture.

25.7% Conversion

Selectivity 85.9% Example 4

In a 1 l sloping autoclave as in Example 2, 200 g of linalool, 538 of the desilane residue obtained in Example 3 are added after distilling off linalool, nerol and geraniol and 0.5 g of diphenyldohalosilane. While stirring and under an inert atmosphere of N 2, the reaction mixture was maintained at 164 ° C. After 3 hours of reaction, 71.4% linalool, 7.4% nerol and 11.6 geraniol were determined in the reaction mixture.

28.6% Conversion

Selectivity 66.4% Example 5

250 g of linalool, 312 g of xylene, 0.675 B of triethanolaminortic acid and 3.81 g of diphenyldioloreaniline are charged into a 1 l autoclave of a 17377 grade stirrer, heating and azeotrope attachment. While stirring and in an inert atmosphere, the reaction mixture is maintained at 150 ° C, after 4 hours of reaction in the reaction mixture.

Claims (1)

Process for the production of geraniol and nerol by catalytic isomerization of linalool in the liquid phase in the presence of orthovanadic acid esters in an amount of 0.1 to 1.0 wt.% As catalyst at temperatures of 130 to 170 ° C, characterized in or diphenyldioharsilane and / or silicon tetrachloride in an amount of 0.2 to 2.3% by weight,.