SU717029A1 - Method of preparing di-(beta-alkylthioethyl)-oxides - Google Patents

Description

one

The invention relates to the field of chemistry of organosulphuric compounds, namely to an improved method for the preparation of DI (alkylthio ethyl) - oxides of the general formula

(RSCHjCiy O (1),

where R is alkyl containing from 2 to 5 carbon atoms.

These compounds can be used as intermediates for the synthesis of physiologically active substances.

A known method for producing di- (-alkylthiosl) oxides by alkylation of DI- (p-mercaptoethyl) - oxide in the presence of alkali metal alkoxides or by reacting DI- (α-chloroethyl) - oxides with mercapts in the presence of alkaline reagents 1

A disadvantage of the known method is associated with the relative inaccessibility of the initial intermediates.

The aim of the invention is to simplify the process for the preparation of di- (-ad. Alkylthioethyl) oxides.

The goal is achieved by the method of obtaining di- (p-alkylthioethyl) - oxides of general formula I using derivatives (-meas

captoethanol), which is distinguished by the fact that the corresponding tri- or di-ft-alkyl mercaptoethyl phosphorous acid ester is used as a derivative (-mercaptoethanol, which is subjected to hydrolysis at a temperature of 100-1. In summary, the process is expressed as:

2 (RSCH5, CHj, 0), jP + SHftO - -.3 (PSCH, CH) O + 2H3P05;

(RSCHa CH O) ,. PH + HaO- - () О + ..r

The process is carried out by heating the mixture of reagents at 100-150 ° C, followed by boiling the reaction mixture with an organic solvent, forming an azeotropic -cMecj with water.

Target products are obtained with a good yield and in a suit. distillation under reduced pressure. The structure of the obtained compounds was confirmed by the methods of PMR and mass spectrometry

KIM

Claims (3)

Alkylthioethylfrsfes required for the implementation of the above method can be obtained by transesterification of the corresponding lower alkylphosphites with alkylthioethanols. The latter, in turn, receive; high VB code condensing ethylene oxide with mercaptans. h Example Di- (ethylthioethyl) oxide. To 10.4 g (0.03 mol) of tri- (y-these thioethyl) phosphite, 0.8 g (0.045-mol) of water is added with stirring and a temperature of 20-25 ° C and the mixture is heated for 1 h to After cooling to 120 ° C, 30 ml of toluene is added to the reaction mass and the mixture is boiled in a device with a Dean-Stark nozzle for 5 hours. The reaction mass is washed with water to a neutral medium, dried aeotropically, the solvent is distilled off and the residue with a yield of 85%, 7.4 g of substance S are obtained from a colorless bidet with a moving liquid; Pr 1,5010; about, 0049; CRC: found 56.98, calculated 57.50; t .. kip. 88-90 / 2 mm. Found,%: C 49.36; And 9.27; 5 32.54; ZCgH OS Calculated,%: С.49,44; H 5.34; .532.99. PRI m 2. Di- (α-butylthi-ethyl) - oxide. A mixture of 3 g (0.01 mol) of di - (- butyl thioethyl) phosphite and 0.2 g (0.01 mol: water is heated with stirring for 40 minutes to. Then 20 m of toluene are added to the reaction mass and the mixture is boiled in a device with a Dina-Starka nozzle for 5 hours, the phosphorous acid formed is washed with water, the organic layer is dried azeotropically, the solvent is removed in vacuo and the substance is obtained with a yield of 2.2 g (-88%); D l, 49QO; d 0.9612; MR,: found- but 75.33, calculated 76.18; so-called bp 120-1240 / 2-3 mm.,%: From 57.27; H 10 , 64; S 25,15. ------.----- - - - .--; ..if-.ii4: s --v - d - Wi v; sQWy: Srt - Calculated,%: C 57.55; H, 10.46; -S25.60. 3. Di- (p-amylthioethyl) - oxide. A. A mixture of 4.75 g (0.01 mol) of tri- (p-amylthioethyl) phosphite and 0.27 g of 71702 i 9 4 - L (0.015 mol) of water is heated with stirring for an hour, then add 15 ml of toluene and boiled in a device with a Dean-Stark nozzle for 5 hours. The reaction mass is washed with water, dried, the solvent is removed and the substance is obtained in the residue in 3.7 g (89%) yield; ng 1.4865; , 9452; M «C: found 84.74, calculated 85.42; bp 143-145 ° / 3 mm. Let's go, but,% C 59,76; H 11.58; 5 22.70:, Calculated,%: C 60.37; H 10.86; S 23.02. . B. A mixture of 0.015 mol of di - (- amylthioethyl) phosphite and 0.015 mol of water is heated with stirring until. temperature for 40 minutes. Add 20 ml of toluene and boil. V. instrument with a Dean-Stark nozzle for 6 hours. The reaction mass is washed with water, dried, the solvent is yielded, and the residue is obtained in a yield of 3.9 g (94%); n |) ° l, 4858; d 0.9431; bp 146-148 / 3-4 mm. Found,%: C 60.34; H 11.01; S 22.84. The invention The method of producing di- (5-alkylthioethyl) -oxides of the general formula (RSCH2CHg) 2.6 (I), where H is alkyl containing from 2 to 5 carbon atoms, using derivatives of-mercaptoethanol, from l and h and in order to simplify the process, the corresponding tri- or di-yi-alkyl mercapto-ethyl phosphorous acid ester is used as a derivative of -mercaptoethanol, which is subjected to hydrolysis at a temperature of 100-1SO C. Sources of information taken into account in examination 1 Patent of France f 2101234, cl. C 07 C 149/46, published 1976 (prototype).