SU1384574A1 - Method of producing 2-oxy-3-chloropropylalkyl sulfides - Google Patents

Abstract

The invention relates to sulphides, in particular to the preparation of 2-ox-3-hlrr-propyl-alkyl sulphides (CH) of the formula RSCHiCH (OH), where. R is alkyl with 2-8 carbon atoms, which are used as intermediates in organic synthesis. The purpose of the invention is to increase the yield of cholesterol and simplify the process. The preparation of cholesterol is carried out by the interaction of the corresponding alkyl mercaptans with epichlorohydrin in the presence of sodium hydroxide in a solvent at a molar ratio of 1: 1-1.1: 0.1-1 and (-10) - (+20) C. The solvent is water or brine or their mixture with hexane or benzene. Yield up to 95%. The method ensures the safety of production as a whole, the process can be implemented in a single reactor with repeated use of sodium hydroxide. I (O

Description

00 00 4: SP

This invention relates to an improved process for the preparation of 2-hydroxy-3-chloropropyl-alkyl sulfides of the formula

RSCH2CHCH2C1, OH

(I)

ten

where R is alkyl with 2-8 carbon atoms, which are used as intermediates in various organic syntheses.

The purpose of the invention is to increase the yield of the target products and simplify the process, which is achieved by using in the process of the interaction of alkyl mercaptans with epichlorohydrin as the base of sodium hydroxide, as a solvent - water or

water-salt solution or a mixture thereof, v .. o

.jn sodium and 1 MP of water) at 5 ° С and perexane or benzene and conducting

15

11 g. Measure 3. To 5.1 g (0.056 M) epichloride idrin, with stirring, the mixture obtained and 4.5 g (0.05 M) of butylmercaptan, 2 tons (0.05 M) of sodium hydroxide are added dropwise. and 8 ml of water so that the temperature does not exceed 0-5 ° C, the cooling is removed and the temperature rises spontaneously to (min). The organic layer was separated, dried over MgSQ, and 8.60 g of 2-hydroxy-3-chloropropylbutyl sulfide was obtained, b.p. 7b-72 ° C / / 0.1 mmHg, p 1.4967. Yield 94% ..

Example 4. To a mixture of 5.1 g (0.056 M) of epichlorohydrin and an aqueous solution of sodium hydroxide (prepared from 0.2 g (0.005 M) of hydroxide

stirring and add 4.5 g (0.05 M) of butylmercaptan so that the temperature does not exceed the precipitation and the temperature rises spontaneously to 20 ° C (0.5 h). The organic layer was separated, dried over MgSO4, and 8.5 g of 2-hydroxy-3-chloro-propyl butyl sulfide was obtained. Yield 93%. I Example 5. To a solution of 10.2 g

process at a molar ratio. alkyl mercaptan epichlorohydrin-sodium hydroxide 1: 1-1.1: 0.1-1 and temperature (-10) - (+20) 0.

The invention is illustrated by the following examples.

Example 1. For a mixture of 6.2 g (0.1 M) of ethyl mercaptan and 1.2 g (0,) of sodium hydroxide in a saturated saline solution (obtained by dissolving 3.7 g of sodium chloride in 10.8 MP of water) at -10 ° C and stirring, 9.25 g (0.1 M) of epichlorohydrin is added so that the temperature

, v .. о „

11 g. Measure 3. To a mixture of 4.5 g (0.05 M) butyl mercaptan, 2 tons (0.05 M) of sodium hydroxide and 5 tons (5 g (0.05 M) of butyl mercaptan) was added dropwise with stirring to 5.1 g (0.056 M) 8 ml of water, so that the temperature does not exceed 0-5 ° C, the cooling is removed and the temperature rises spontaneously to (min). The organic layer was separated, dried over MgSQ, and 8.60 g of 2-hydroxy-3-chloropropylbutyl sulfide was obtained, b.p. 7b-72 ° C / / 0.1 mmHg, p 1.4967. Yield 94% ..

Example4. To a mixture of 5.1 g (0.056 M) epichlorohydrin and an aqueous solution of sodium hydroxide (prepared from 0.2 g (0.005 M) hydroxide

stirring and add 4.5 g (0.05 M) of butyl mercaptan so that the temperature does not exceed the precipitation and the temperature spontaneously rises to 20 ° C (0.5 h). The organic layer was separated, dried over MgSO4, and 8.5 g of 2-hydroxy-3-chloropropylbutyl sulfide was obtained. Yield 93%. I Example 5. To a solution of 10.2 g

(0.11 M) of epichlorohydrin in 30 ml of hexane at 5 ° C and with stirring are added a mixture obtained from 9 g (0.1 M) of butylmercaptan, 4 g (0.1 M) of sodium hydroxide and 16 ml of water, so that

did not exceed, the mixture was allowed to withstand 35, the temperature did not exceed 5-7 ° C and, at this temperature, 40 min. After the completion of the reaction, the organic layer was separated, dried over MgSO4 and 13.9 g of 2-hydroxy-3-chloro-1-ethyl sulfide with , kip. 110 ° C / 15 mmHg, 1.5050. Yield 90%.

Pr immer2, To a mixture of 6.2 g, (0.1 M) ethyl mercaptan, 15 ml of hexane and 0.4 g (0.01 g) of sodium hydroxide in a saturated aqueous salt solution (obtained by dissolving 1.23 g of sodium chloride in 3.6 ml of water) at 0 ° C and stirring, add 9.25 g (O, 1 M) of epichlorohydrin so that the temperature does not exceed 1P ° C, the mixture is kept at this temperature for 20 minutes, the cooling is removed and the temperature rises spontaneously To a further 20 ° C and further 0.5 hours. After completion of the reaction, the organic layer is separated, dried over MgSO / / and 14.2 g of 2-hydroxy-3-chloropropyl ethyl sulphide are obtained. Vyshod 92%.

water was reacted as described in Example 4. After removal of the solvent, 17.3 g of 2-hydroxy-3-chloropropylbutyl sulfide are obtained. Yield 95%.

PRI me R. 6. To a solution of 10.2 g (0.11 M) of epichlorohydrin in 40 ml of benzene at 5 ° C and stirring is added a solution of the thiolt, obtained from 9 g (0.1 M) of butylmercaptan, 4 g

(0.1 M) sodium hydroxide and 16 ml of water so that the temperature does not exceed 5-7 ° C and the reaction is carried out as described in Example 2. After removing the solvent, 16.8 g of 2-hydroxy-3-chloropropyl butyl sulfide are obtained. .Outlet 92%.

Example 7. To a mixture of 10.2 g (O, 11 M) of epichlorohydrin and an aqueous solution of sodium hydroxide (prepared from 1.6 g (0.04 g) of sodium hydroxide and 6.5 ml of water) while stirring 14.6 g (0.1 M) octyl mercaptan is added so that the temperature does not exceed 10-15 0. Cooling

removed and the temperature spontaneously rises to 20 ° C, kept at this temperature for 0.5 hours. After completion of the reaction, the organic layer is separated, dried over MgSO4 and 21.5 g of 2-hydroxy-3-chloroproxy1 octyl sulfide are obtained. bp 122-123 ° C / 0.1 mm

 Hg, 4862. Yield 90%.

Thus, the proposed method leads to an increase in the yield of the target product from 75 to 95%, which makes it easy to control the process, which increases the safety of production as a whole. The great advantage of the proposed method is the possibility of implementing waste-free technology and the repeated use of sodium hydroxide. The whole process can be implemented in a single reactor. The method does not require significant technological studies, allows to significantly reduce material costs and explosion and fire safety of the process.

Claims (1)

Invention Formula The method of obtaining 2-hydroxy-3-chloropro pilalkyl sulfides of the general formula RSCH2CHCH2C1, he where R is C-Cg-alkyl 5 by reacting the corresponding alkyl mercaptans with epichlorohydrin in the presence of a base in a solvent, characterized in that, in order to increase the yield of the target product and simplify the process, sodium or hydroxide is used as the base water-salt solution or their mixture with hexane or benzene and the process is carried out at a molar ratio of alkyl mercaptan-epichlorohydrin-sodium hydroxide 1: 1-1.1: 0.1-1 and temperature (-10) - (+20) ° WITH,