SU1361140A1 - Method of obtaining divinyl ether of thiodiglycol - Google Patents

Abstract

This invention relates to acyclic mercaptans, in particular to the preparation of thiodiglycol divinyl ester (EEG), which can be used in various organic syntheses. In order to increase the VEG yield and simplify the process, the interaction of vinyl 2-chloro ether (VChE) with Na sulphide is carried out at a molar ratio of 1: 0.5-1 and 20- 90 ° C. The process is carried out in the presence of catamine AB or triethylenbenzylammonium chloride (as a quaternary ammonium salt) in an amount of 2–5 mol.% Of taken VHCE. The process time is reduced to 3 hours against 10 hours with a VEG yield of 71–99% versus 43% by the well-known method 1 C. p. . l-lyo (L with:: A :) 05

Description

one

136

The invention relates to the improvement of the method for the preparation of the divinyl ester thiodiglycol of the formula

Cll CEOCR CE SC R CE OCH

(one)

which can be used in various organic syntheses.

The purpose of the invention is to increase the yield of the target product and simplify the process, which is achieved by reacting vinyl-2-chloroethyl ether with sodium sulfide with a molar ratio of initial reagents of 1: 0.5, 1, and a temperature of 20 ° C to 90 ° C in the presence of a quaternary ammonium salt, preferably catamine, N (CH,) CH CgH5lCl or triethylbenzylammonium chloride, in an amount of 2-5 mol% of taken vinyl 2-chloroethyl ether

Example 1 about Into the reaction flask are placed 36.0 g (0.15 mol) of sodium sulfide, 21.3 g (0.2 mol) of vinyl-2-chloroethyl ether, 4.2 g (3.0 mol.%) Of catamine AB and stir vigorously with stirring for 3 hours. 10 ml of water are added to dissolve the resulting sodium chloride, the organic layer is separated and subjected to distillation. 1.8 g of vinyl-2-chloroethyl ether and 15.7 g (90.2% of theories) of divinyl ether thiodiglycol. The output of 98.7% in entered into the reaction of vinyl-2-chloroethyl ether, so kip. 90 ° C (3 mm pToSTs), 1, 4900,

Found,%: C 55.20 55.21; H8.16; 8.20; S 18.37, 18.30,

 ,

.Calculated,%; C 55.14, H 8.10, S 18.40.

IR spectrum, 820, 970, 1200, 1320, 1615, 3050 (characteristic absorption bands of the vinyloxy group) and PMR spectrum (SCC, 5 ppm):

 s

; With With

/ n.

,

6.38 d, d (N,), 4.10 d "d. (Nd), 3.90 d, d (On), JrpoHc 1 Hz, J, e 7.5 Hz, Jrew 3.0 Hz, 3.78 t, (OCH), 2.73 t (SCH ,,), J 7.0

02

Pr and measures 2, 10.6 g (0.1 mol) of vinyl-2-chloroethyl ether, 18.0 g (0.075 mol) of sodium sulfide, 3.5 g (5 mol%) of a 50% aqueous solution of catamine AB is heated at 60 ° C for 5 hours to obtain 0.4 vinyl 2-chloroethyl ether and 7.9 g (90.8% of theory) of the desired product. The output of 94.3% on entered into the reaction of vinyl-2-chloroethyl ether,

Pr and measure 3.5.3 g (0.05 mol) of vin1-2-chloroethyl ester, 12.0 g (0.05 mol) of sodium sulfide, 0.57 g (5 mol%) of triethylbenzylammonium chloride are heated at 90 From 5 hours, 0.9 g of vinyl-2-chloroethyl ether and 3.4 g (78.2% of theory) of the product are obtained. The output of 94.2% on the entered vinyl-2-chloroethyl ether,

EXAMPLE 4, 5.3 g (0.05 mol) of vinyl 2-chloroethyl ether 9.0 g (0.037 mol) of sodium sulfide, 0.57 g (5 mol%) of triethylbenzylammonium chloride is heated at 60 ° C for 3 h, 0.5 g of vinyl-2-chloroethyl ether and 3.4 g (78.27, from theory) of the product “Output 87.2% of the incoming vinyl-2-chlorine ethyl ester , Example 5 „21.3 g (0.2 mol)

vinyl 2-chloroethyl ether, 36.0 g (0.15 mol) of sodium sulfide, 3.0 g (2 mol%) of a 50% aqueous solution of sodium cadmin AB are heated at 2 h, yielding 4.2 vinyl-2- chloroethyl ether and 13.5 g (77.6% of theory) of the product The yield of 96.4% on the entered vinyl-2-chloroethyl ether

Example 6, 21.3 g (0.2 mol) of vinyl 2-chloroethyl ether, 24.0 g (0.1 mol) of sodium sulfide, 4.2 g (3 mol%) of catamine AB are heated at 60 C for 2 hours , 4.8 g of vinyl-2-chloroethyl ether and 12.7 g (73.0% of theory) of the product are obtained. The yield is 94.1% for the vinyl-2-chloroethyl ether that has entered.

Example 7: 10.65 g (0.1 mol) of vinyl 2-chloroethyl ether, 18.0 g (0.075 mol) of sodium sulide, 0.7 g (1 mol%) of a 50% aqueous solution of catamine AB is heated at 60 C for 5 h, to obtain rf 5.0 g of vinyl 2-chloroethyl ether and 4.0 g (46.0% of theory) of the product. Output of 87.0% on the entered vinyl-2-chloroethyl ether,

EXAMPLE 8 5.3 g (0.05 mol) of vinyl 2-chloroethyl ether, 12.0 g (0.05 mol) of sodium sulfide, 0.57 g

.313

(5 mol%) of triethylbenzylammonium chloride is stirred at 20 ° C for 6 h, 3.6 g of vin1-2-chloroethyl ether and 1.2 g (28.0% of theory) of the product are obtained. The output of 71.4% came in vinyl-2-chlorine ethyl ether,

EXAMPLE 10.65 g (0.1 mol) of vinyl 2-chloroethyl ether, 24.0 g (0.1 mol) of sodium sulfide, 0.23 g (1 mol%) of triethylbenzylammonium chloride are heated at 90 ° C for 4 h, 1.2 g of vinyl 2-chloroethyl ether and 2.8 g (32.3% of theory) of the product are obtained. The output of 36.3% on the entered vinyl-2-chloro ether 10y about

Thus, the proposed method is simple to perform, technologically advanced (the use of methanol is eliminated and the process time is reduced to 3 hours against 10 hours) and allows to obtain divinyl ether thiodiglycol with a yield of 71-99 against 43% by the known method

40 Formula

the invention

1, Method for preparing thiodiglycol divinnate ester of formula

CHj CHOCH.CH2SCH2CHj OCH CHg

the interaction of vinyl 2-chloroethyl ether with sodium sulfide, characterized in that, in order to increase the yield of the target product and simplify the process, the latter is carried out at a molar ratio of initial reagents equal to 1: 0.5, 1, 1, respectively, and a temperature of 20 ° C to 90 ° C in the presence of a quaternary ammonium salt in an amount of 2, 0, 5 mol,% of the taken up higher 2-chloroethyl ether, 2, Method According to 1, about tl and h and y and with the use of katamin AB or triethylbenzylammonium chloride as the quaternary ammonium salt.

Claims (2)

Claim 1. A method of producing a thiodiglycol divinyl ester of the formula sn ₂ = choch ₄ ch _z sch ₂ ch ₂ och = CH _{2 by the} interaction of vinyl-2-chloro-ether ether with sodium sulfide, characterized in that, in order to increase the yield of the target product and simplify the process, the latter is carried out at a molar ratio of the starting reagents being 1: 0.5 ... 1, respectively, and a temperature of 20 "to 90 C in the presence of a quaternary ammonium salt in an amount of 2. _0, 5 mol% of taken vynil-2-chloroethyl ester , 2, The method according to π, 1, with the fact that catamine AB or triethylbenzylammonium chloride are used as a quaternary ammonium salt.