CS235228B1 - Processes for producing (3Z, 5E) and (3Z, 5Z) -6,10-dimethylindeca-3,5,9-trien-2-one, or mixtures thereof with other isomers of 6,10-diinethylene-3,5,9- 2-triene-days - Google Patents

Abstract

The purpose of the invention is to produce (3Z, 5E) and (3Z, 5Z) --6-10-dimethylundeca-3,5,9-trien-2-one or their mixture with other isomers 6,10-dimethylundecatrien-2-one in a simple, technically easy to perform method. The stated purpose is achieved by mixing the organic or inorganic acid 3,7-dimethyl-6-octen-1-yn-3-ol and technical 2-methoxypropene in a molar ratio of 0.5. ΙO-3 to 2.1. ΙO'3 : 1 : 2 to 2.2 and heating the reaction mixture at a temperature of 20 to 120 ° C for 2 to 20 hours in an unstirred closed tank. The field of application is the pharmaceutical industry, specifically the production of vitamin A and E intermediates.

Description

23S228

The present invention relates to a process for the preparation of (3Z, 5E) and (3, Z, 5E) -6,10-dimethylindeca-3,5,9-trien-2-ones of formula I and II or mixtures thereof with other isomers 6, Of 10-dimethylindene catrien-2-one chemical formulas III, IV and V, as an economically advantageous feedstock for the synthesis of beta-ionone and other compounds useful in the production of vitamin A and E.

Him

HC 'OII

HC

SCH

II

C x R CH- θ 'C Ης Λ'

HC

II C.

CH

II

CH CH, I. (3Z, 5E) -isomer C h3 II. (3Z, 5Z) -isomer CH *

HC

CH

II CH.

HC

HC

II c • c% o

CH / CH 2 CH 2

I 2CH

IIC

A R Ch. III. (3E, 5Z) -isomer old designation "cis" IV. (3E, 5E) -Isomeric old designation "trans" V. allene isomer wherein R is a chemical moiety of formula CH 3 - C = CH — CH 2 —CH 2 -

The prior art processes for the production of (3Z, 5E) and (3Z, 5Z) -6,10-dimethyluoro-3,5,9-trien-2-ones have theoretical or little practical significance (e.g. De Simone and Gradeff, Ger. Offen 2404). 913), since the production of 6,10-dimethylundecatrien-2-one is used for the production of particularly beta-ionone, and its isomers (3E, 5Z) and (3E, 5E) of the formulas III are exclusive. and IV. in the older literature referred to as cis and trans pseudocononers. However, these are available by more practical methods.

Older, more important methods of preparing a mixture of isomers (3E, 5Z) and (3E, 5E) -6,10-dimethylindeca-3,5,9-trien-2-one are based on obtaining the pure isomers required by condensation of citral or a mixture of enelacetate and citral diacetate with acetone, for example Saucy G Merbet R. Helv. Chim. Acta 42: 1145 (1959), or for the preparation of a pure isomer of formula V which is smoothly isomerized to the desired pure isomers (3E, 5Z) and (3E, 5E) with alkali as reported by SaucyG. Chim. Acta 50, 1158 (1967).

According to the last cited procedure, 1 mole of 3,7-dimethyl-6-octen-1-yn-3-ol (dehydrolinalol) and 2 mole of 2-methoxy-propene under acidic catalysis of 150 mg of p-toluenesulfonic acid in a hydrocarbon medium, for example 300 ml ligroin at 1 MP and by heating at 92 ° C for 17 hours, an analytical yield of 95% of theory is 6,10-dimethyl-4,5,9-undecatrien-2-one, which is isolated by traces of potassium hydroxide in 150%. ml of methanol at 0 to 10 ° C practically quantitative pseudojonon of chemical formulas III. aIV. The process for the preparation of these substances is described in a variant without the use of a pressure in the amount of organic solvent in the case of otherwise modified molar ratios of reactants with the same effect as the pressure process. In the case of industrial availability of 2-methoxypropene, the procedure of the Saucy, Merbet author stage may be considered to be the most advantageous of all the older procedures. The difficulties only exist in industrial applications where a pressure or non-pressurized pathway does not lead to a unified production of kettoallene of the chemical formula V and subsequent to the

Claims (1)

6 235228 5 dojone in isomers of formula IIIa IV. but to a mixture of these isomers with the isomeric chemical formula I and II. Unsuitable isomers of the formulas I and II under the conditions described in the literature reach an average of 10% of theory on dehydrolinalol, which is a great advantage in the use of such a mixture of beta-ionone production, therefore the yield of beta-ionone decreases from that of other semi-source sources such as pseudojonon citral to 20% of theory, where the necessary purification operations are economically unrealistic, the clarity of the synthesis pathway, as well as the disadvantages of the process, is the use of an inert solvent, high pressure and technically demanding maintenance of the low-boiling 3-methoxypropene (b in 34 ° C) reaction system in a pressure-free process. It has been found that the abovementioned drawbacks of the prior art can be eliminated by the simplest, technically feasible method of the invention, which makes it possible to prepare a mixture of any 6,10-dimethylundecatrien-2-one isomers using 2-methoxypropene from dehydrolenol. without solvents in high-yield unmixed tanks, which is an economically advantageous raw material base for the production of Ions. The novel raw material base is related to the existence of an effective industrial method of its treatment to the necessary mixtures of the compounds of formulas III and IV, which are the subject of another of our invention AO No. 27,638. and II without other isomers of formula III, IV and V. By the process of the invention, by reaction of 3,7-dimethyl-6-octen-1-yn-3-ol with 2-methoxypropene under acid catalysis, for example, t-toluenesulfonic acid, at a pressure of 0.0 to 0.2 MPa for 2 to 20 hours at 30 to 120 ° C, characterized in that the technical 2-methoxypropene is used in an amount of 2 to 2.2 equivalents and the reaction is carried out in an unmixed, sealed tank without any solvent to give (3Z, 5Ej and (3Z, 5Zj-6,10-dimethylindeca-3,5,9-trien-2-one or mixtures thereof with (3E, 5Z), [3E, 5E) -6-10-dimethyl-undecatriene-3,5,9-trien-2-one and 6,10-dimethyl-4,5,9-trien-2-one, as the econe the preferred raw material basic industrial production of Ions. Examples 1 to 3 illustrate the method according to the invention, but are not limited thereto. EXAMPLE 1 0.1 g of p-toluenesulfonic acid dissolved in 76 g of 3,7-dimethyl-6-octen-1-yn-3-ol with 110 ml of technical 2-methoxypropene is added to an unmixed tank. The tank contents are sealed and heated to 40 ° C. There is no overpressure in Manometertan. After heating for 2 hours, the tank was cooled, the catalyst was neutralized by the addition of 0.5 ml of triethylamine and the light solids were distilled off. The residue is distilled under a pressure of 67.2 Pa at 85 to 95 ° C to give 96 g of a mixture of 27% 3,7-dimethyl-6-octen-1-yn-3-ol, 8.9% (3Z, 5E) and (3Z, 5Z) -6,10-dimethylindeca-3,5,9-trien-2-one and 10.2, respectively. 14.5% (3E, 5Z, and (3E, 5E) -6,10-dimethylundeca-3,5,9-trien-2-one, respectively. Example 2). as described in Example 1, the reaction mixture is heated for 4 hours at 60 ° C, at a pressure of 0.02 MPa, the catalyst is neutralized by the addition of triethylamine, the light particles are distilled off and the residue is distilled under pressure 67.2 Paper temperature 90-95 ° C 24.78 g of desilate with 94.15% of [3Z, 5EJ and (3Z, 5Z) -6,10-dimethylindeca-3,5,9-triene are obtained] EXAMPLE 3 0.5 g of p-toluenesulfonic acid dissolved in 380 g of dehydrolinalol with 382 g of technical 2-methoxypropene are added to an unmixed tank, and the contents of the closed tank are heated at 100 DEG C. the catalyst is saneutralized and the light particles are distilled off to give a 490 g mixture containing 41.61% (3Z, 5Ej and (3Z, 5Z) isomers of pseudojonone 18.25 (3E, 5Z). 5E) and (3E, 5Zj isomers of pseudojonon and 32.22% 6.1 O-dimethyl-4,5,9-undecatrien-2-one, wherein the recoverable material yield for the production of <3 -onon is 94% of theory with respect to dehydrolinalol. SUBSTITUTE Production method (3Z, 5Ej and (3Z, 5Z) -6,10-dimethyluoro-3,5,9-trien-2-one, or mixtures thereof with other 6,10-dimethylindene-3,5 isomers, 9-trienone under acidic organic or inorganic acid catalysis such as p-toluenesulfonic acid, by reacting 3,7-dimethyl-6-octen-1-yn-3-ol with methoxypropene, at EXTRACTION at a temperature of 30 to 120 ° C, at atmospheric pressure to an excess pressure of 0.2 MPa, for a period of 2 to 20 hours, characterized in that the corresponding acid and 3,7-dimethyl-6-octene are added 1-in-3-ol and subsequent 2-methoxypropene in a molar ratio of 0.5.10-3 to 2.1.10-3: 1: 2 to 2.2.