SU1088284A1 - Method of producing butanoate of 3,7-dimethyl-2,6-octadiene-1-ol - Google Patents

Abstract

METHOD OF OBTAINING BUTANOAT 3;, 7-DSHETHYL-E-2,6-OCTADIEN-1-OLA Pushttmp Jaashtsh-Tyych Shya. BIBLIYTGPD: the processing of technical mixture. -1-chloro-3,7-dimethyl-E-1-chloro-7-vimethyl-Z-and 1-chloro-2,7 dimethyl-E-2,6 octadiene. K-dimethylaniline followed by extraction with the obtained the quaternary ammonium salt with water, salting out potash, heating the selected salt with an alkali metal salt of butyric acid and isolating the tse-: left product by distillation, which is due to the fact that, in order to increase the purity of the target product, processing the mixture H, N-dimeshganilin lead to the degree converted .. NIN 1-chloro-3,7-dimethyl-E-2,6-octadiene, equal to 50-80% ,. „

Description

The invention relates to the improvement of the method of producing butanoate-3, 7-dimethyl-E-2,6-octadien-1-ol, which is used as a sex attractant for insect pests, for example, for male seed beetle and steppe beetles (Agriofces .spututor. L, and Agriotes gurgistanug Fald). - - -

Izvesa-en method of obtaining complex

esters by reacting halogen derivatives of hydrocarbons with alkali metal salts of organic

ACID

However, this method results in individual bHbix end-products with e, readings using individuals ;. dual source derivatives.

The closest; The inventive method is a method for producing oily esters

I. .

acids, namely, butanoate 3,7-dimethyl-E-2, 6-octadien-1-ol by processing a technical mixture of 1-hp6ro-3,7-dimethyl-E-1-chloro-3,7-dimethyl-g-

00 00 NJ and 1-chloro-2.7 dimethyl-E-2,6-octadig. ;: enes .H, L-dimethylaniline until almost complete conversion of 1-chloro-3,700 dimethyl-E-2,6-octadiene to quaternary ammonium salt followed. extracting the obtained salt with water, salting out the potash, heating it with; an alkali metal salt of butyric acid and the allocation of the desired product: that by distillation,

I The disadvantage of the method is that the purity of the target product is 89% and the presence of 3,7-dimethyl-E- and 2,7-dime butanoate impurities. Tyl-E-2, 6-oct-tadien-1-ol, which are inhibitors of sexual communication, in the amount of 4 and 7%, respectively. It does not allow it to be used as a sexual attractant for insect pests. The aim of the invention is to increase the purity of the target product. The goal is achieved by the method of producing 3,7-dimethyl-E-2,6-octadien-Iola bu-, tanoate by treating a technical mixture of 1-chloro-3,7, -dimethyl-E- (1) 1-chloro-3,7 dimethyl- g- (11) and 1-chloro-2,7-dimethyl- -2,6-octadiene (III) H K-dimethylaniline to the extent of conversion of 1-chloro-3, 7-dimethyl-E-2,6-octadiene, equal to 50-80%, followed by extraction of the obtained quaternary ammonium salt with water, salting out the potash, heating the selected salt with an alkali metal salt of butyric acid and isolating the target product by distillation. A distinctive feature of the method is the processing The technical mixture containing isomeric chlorine derivatives N, N-dimethylaniline to the extent of conversion of 1-chloro-3,7-dimethyl-E-2., 6-octadiene equal to 50-80%. The process is carried out as follows. The mixture of isomeric halogen derivatives is treated at 20 C M, N-dimethylans1IN. The monitoring of the degree of conversion is periodically determined by the determination of ionic chlorine in the reaction mixture. Under these conditions, the impurity, sordine, is used. Neither (II) and (111), as less reactive, react only to insignificant degrees. Next, the formed quaternary ammonium salt is extracted from the reaction mixture with water, the aqueous solution is washed with petroleum; ether and saturate with potash, toluene is added to the leached salt, distilled off at 50 ° C and in a vacuum (50-100 mm Hg, water remains as an azeotrope with toluol. Satrom to the salt solution in toluene is added butanoate sodium and heated for 4 h at. After treating the reaction mass, the product is rectified in vacuum, Schroe process thus allows to obtain a product with a purity of 98-99%, which is necessary for using it as a sex attractant, Example 1, 200 g (1.16 mol) of a mixture of isomeric halogen derivatives (get during hydrochlorination of linalool) containing 50% I and 20% II, / treated at 80 g (0.66 mol) of N N-dimethyl-aniline. Every day 844 ki in the reaction mixture, the content of ionic chlorine is determined (titration with silver nitrate) and the amount of chlorine contained in the form of HC1 (titration with NaOH). Based on these data, the content of the quaternary ammonium salt formed in the reaction mixture is calculated. After conversion of 80% I (5-6 days) to the ammonium salt, the latter is extracted with water. The aqueous solution is washed with petroleum ether, then saturated with potash, toluene is poured into the separated ammonium salt, the remaining water is distilled at 50 ° C / 50-10p mm, the mixture is heated for 4 hours at 56 g (0.51 mol) of sodium butanoate. After reactivation of the crude product on a column with an efficiency of 10 To t, at 4 mm Hg, one hundred g out 70 g (yield 67% per reacted I) of the product, t, bale, G20-12N, 1.4610, 0.901, the content of butanoate is 3,7-dimethyl-E 2,6-octadien-1-ol-98, 3% (determined using GLC), Literature data: t, kip, 151153 ° C / 18 mm. 142-143 ° C (13 mm); - 0.9008 (3), Example 2, 200 g (1.16 mol) of a mixture of isomeric halogen derivatives (obtained by heat measuring isoprene with its hydrochlorides) containing 60% 1.4% II, 7% III, treated with 80 g (0 , 66 mol) N, H-dimethylans1. After conversion of 50% to quaternary ammonium salt, the latter is extracted with water and converted into the ester. as in example 1, treatment of 40 g (0.37 mol) of sodium butanoate. Obtain 52 g of the target product, yield 70%. on I, the content of butanoate 3,7-dimethyl-E-2, 6-rctadien-1-ol is 99%, the compound constant is t, kip, 120-121 C / 4 mm, p 1.4610, d4 ° 0 , 90i “Prize, 200 g (1.16 mol) of a mixture of isomeric terpene halogen derivatives obtained by telomerization of isoprene with its hydrochlorides, containing 60% 1-chloro-3, 7-dimethyl-2, 6-kt a diene (I), is treated 80 g (0.66 mol) K, H-dimethylaniline After the 65% compound I is converted to the quaternary ammonium salt, the latter is removed with water. The aqueous solution is washed with petroleum ether, then saturated with potash, K exuded by quaternary ammonium. toluene (100 ml) is added. At a vacuum of 100-50 mm and temperature, the residual moisture of the azeotrope with toluene is distilled. To the rest of the flask, 48 g (0.436 mol) of sodium butanoate is added to a solution of the quaternary ammonium salt in toluene and heated for 4 hours at. After cooling, it is washed with water, then with 5% HC1 and again with water until neutral wash water. After rectification of the obtained crude product in vacuum (4 mm), on a column with an efficiency of 10 tons, t, a fraction with t, kip, 120-121 s (4 mm) was isolated in a quantity of 69 g - 66% yield (i ) i p 20 1.4610, d - 0.901, the content of 3,7-dimethyl-E-2,6-octadien-1-ol butanoate is 98.6% .. 4 P. m and me 4 (comparative) . 200 g (1.16 mol) of a mixture of isomeric hylogen derivatives containing 60% 1.4% and 7% are treated with 133 g (1 jl mol) N, H-dimethylaniline and left to stand for 20 days. B Quaternary ammonium salt 99.2% is converted. Then, as in Example I, the salt is treated with 70 g (0.635 mol) of sodium butanoate and 99 g of the desired product is recovered, vj /, 73%, T. CSH1. 120-121 C / 4, nj i, 1.4621, 0.904, containing 89% buganate, 3,7-dimethyl-E-2,6-octadien-1-opa, 4% butanoate 3,7-dimethyl-2 , 6-octadiv-1-ol and 7% 2,7-dimethyl-E-2,6-octadien-1-ol butanoate. As shown by biological tests, a product with such a degree of purity does not attract male click beetles, and. therefore, it cannot be used as a bottom attractant.

Claims (2)

METHOD FOR PRODUCING BUTANOATE 3., 7-DIMETY L-E-2,6-OCTADIEN-1-OLA pu-