SU1643534A1 - Process for obtaining 1-alkylthio-1, 2-bis (alkylseleno)-2- chloroethenes - Google Patents

Abstract

The invention relates to sulfur-containing substances, in particular the preparation of 1-alkylthio-1,2-bis (alkyl seleno) chloroethenes of the total RSC (SeRj) C (Cl) -SeRj, where a) R is ethyl, R butyl, b) R is ethyl, RI is methyl, c) R isopropyl, R is methyl, d) R is isopropyl, RI is butyl, which can be used in fine organic synthesis of active substances. The goal is to create a new method of obtaining these new substances. The synthesis is carried out by the reaction of the compounds of the general f-ly R-S-C CC1 with the corresponding dialkyl di-selenide in diethyl ether at boiling. Yield,%, b.p., s (mmHg), gross-la: a) 79.5, 165-l66 (2), C42a, ClSSe4; b) 84.5, 133-136 (4), SvN S188eg; c) 87, 130-131 (3), С, НсЭС158ед; j g) 87, 166 (3), Cl3Hts.ClSSe4;

Description

The invention relates to the chemistry of organic compounds of selenium, specifically to a new method for the preparation of previously unknown 1- (alkylthio) -1,2-bis (alkylseleno) -2-chloroethenes of the formula

RSC (SeR) C (Cl) SeR, „

where R is C4Hff and C4H, j (I) or R is CeHfH R, is CH "(II), or R-iso-C3H7 and (Ill) i or R is iso-C3H7 and R4-C (TV) Which can find various practical applications, in particular, as fine organic synthesis reagents, starting materials for the production of biologically active substances for medical and agricultural purposes.

The purpose of the invention is to develop a new method of obtaining new 1- (alkylthio) -1,2, -bis- (alkyl seleno) -2-chloroethenes.

This goal is achieved by the reaction of alkylthiochloroacetylenes with di-, butyl-, dimethyldi-selenides in diethyl ether at boiling {(30-36 C) for 3-4 hours.

The yield of products (I-IV) 79-87%. Alkylthiochloroacetylene and dialkyldidelenide are reacted at an equimolar ratio. When the reaction temperature decreases to 10-15 and 20 ° C (examples | 5 and 6), the reaction rate and the yield of the desired product decrease. Control over the completeness of the reaction was carried out by the method of PKH. Increase temperature

l

oh oh

A reaction above the boiling point of the solvent (ether) is impossible. Replacing the ether with methylene chloride leads to a decrease in the reaction rate, which even in 18.5 hours took place only by 70%, and correspondingly to a decrease in the yield of the target product to 55% (Example 7).

The synthesized compounds are light yellow liquids with a specific odor, soluble in most organic solvents. .

The proposed method for the preparation of 1- (organylthio) -1,2-bis- (organic-gelled) -2-chloroethenes is effective and simple to use, does not require expensive equipment, catalysts, pressure, significant energy expenditures for its implementation. Compounds used as starting materials are readily available.

Example 1. 1-Ethylthio-1,2-bis- - (butylseleno) -2-chloroethylene (I).

2.54 g of ethylthiochloroacetylene and 5.73 g of dibutyldielenide are dissolved in 50 ml of dry diethyl ether. The resulting solution was boiled for 4 hours. Then the ether was distilled off, the residue was distilled in vacuo. 6.58 g (yield: 79.5%) of compound (I) are obtained. Bp 165-166aC (2 mm Hg); 1.5878.

IR spectrum, 2953, 2926, - 2866 (CH), 1480, 1442 ().

PMR spectrum S, m, d: 0.91 t. (CH, CH,), 1.24-1.56 m. (11H, CH3, CHg), 2.87 m. (CH, CH2). |

Found,%: C 36.12 (36.44); H 6.18 (6.11); C1 9.20 (6.94); S 8.08 (8.35); Se 39.80 (39.85).

With j H ClSSe.

Calculated,%: C, 36.70; H 5.90; C1 9.02; S 8, t6; Se 40.21,

And pmmere 2. 1-Ethylthio-1,2-bis - - (methyl seleno) -2-chloroethylene (II).

4.13 g of ethylthiochloride acetylene and 6.44 g of dimethyldielenide are dissolved in 65 ml of dry diethyl ether and the resulting solution is boiled for 4 hours. The ether is distilled off and the residue is distilled off in vacuo. 7.0 g (yield: 84.5%) are obtained; nor (ii). . 133-136 (4mmHg) pЈ 1 ,. ,

IR spectrum 3, 2963, 2915, 2856, 2800 (СН), 1485 ().

PMR #, ppm: 1.18 dtr. (ZN, SNV),

0

five

0

, five

2.28 s., 2.25 s ,, 2.33 s. (6H, CH3), 2.77 dq. (2H, CH3).

Found,%: C 23.02 (23.28); H 3.90 (3.70); C1 11, IO (11.81); S 10.65 (11.70); Se 52.31 (51.08).

С6Н „С138ег.

Calculated,%: C 23.35; H 3.60; C1 11.49; S 10.40; Se 51.18.

Example 1-Ispropylthio-1,2- -bis- (methyidseleno) -2-chloroethylene (III).

2.49 g of isopropylthiochloroacetylene and 3.37 g of dimethyldielenide are dissolved in 25 ml of dry diethyl ether and boiled for 3 hours. After removal of the ether, the residue is distilled in vacuum. 5.20 g (87%) of compound (III) are obtained. Bp 130 - 131 ° C (3 mm Hg); n ° 1.6402

IR spectrum;), 2960, 2924, 2860, (CH), 1480, 1440, 1416 ().

PMR, ppm: 3.31 dq. (1H, CH), 2.30 d. (6H, CH3), 1.31 s. (GH, CH3), 1.24 s. (ZN, CH3).

Found,%: C 26.28; H 4.50; 1C1 11.02; S 9.97; Se 49.01.

C, H 4 "ClSSeg

Calculated,% C 26.06; H 4.06; C1 10.99; S 9.94; Se 48.95.

Example4. Isopropylthio-1,2- -bis- (butylseleno) -2-chloroethylene (IV).

2.59 g of isopropylthiochloroacetylene and 5.24 g of dibutyldielenide are dissolved in 25 ml of dry diethyl ether and the resulting solution is boiled for 4 hours. After removal of the ether, the residue is distilled in vacuum. 6.8 g (87%) of compound (IV) are obtained. Bp 166 ° C (3 mmHg); nj- 1.5795.

IR spectrum), cm; 2930, 2900, 2840 (СН),, 1448 ().

Spectrum IMP 0 ppm: 3.31 sq. M. (1H, CH), 2.93 d. (4H, CHg), 1.56 (8H, SNg), 1.26 d (6H, OC), 0.91 t. (6H, CH3).

Found,%: C 38.70; H 6.50; C1 8.77; S 7.84; Se 38.68.

With i / jH j-ClSSe.

Calculated,%; C 38.39; H 6.20; C1 8.71; S 7.88; Se 38.82.

Example 1-Isopropylthio-1,2- -bis- (butylseleno) -2-chloro-ethene (IV) at 20 ° C.

3.70 isopropylthiochloroacetylene and 7.48 g of dibutyldielenide are dissolved in 30 ml of dry diethyl ether and the resulting solution is vigorously stirred at 20-22 ° C, sampled for analysis by the method of GHM. The progress of the reaction is followed by the value of 100Snp0% uicTq / (s proednl +

546435346

+ Sfct "Se9eBu i r" e project 15 seu5eSeBu. The resulting solution is boiled

The peak areas of the product and BuSeSeBu, respectively, in the chromatogram of the reaction mixture. After 3.5 hours, this value is 13%, after 6.5 hours - 16.5%. E jJjjH the reaction is then boiled. After 1.5 hours of boiling, the conversion is 63%, after 2, 5 h - 85%, after 4 h - 91%. Ether, 0 distilled, the residue is distilled in vacuo. The first fraction: 1.46 g, b.p. 86-110 ° C (3 mm Hg); , 5456 (by GLC BuSeSeBu: IV 70:30), after the fraction: 8.97 g (80%), bp. 160 - ts 162 ° С (3 mm Hg)} 1.5774 (GLC IV-100%).

PRI me R 6. 1 Isopropylthio-1,2- -bis- (butylseleno) -2-chloroethene (IV) at 10-15 ° C.20

1.58 g of isopropylthiochloroacetylene and 3.19 g of dibutyldielenide are dissolved in 15 ml of dry diethyl ether and the resulting solution is stirred at 10-15 ° C, sampled for analysis 25 by GLC. The complete conversion of the reagents is determined as in Example 6. After 1.5 hours, the conversion is 7%, after 3 hours - 8.5%. To complete the reaction, the mixture is boiled. After 3 h, the overgrowth reaches 79% (by GLC). The ether is distilled off. The residue is distilled in vacuo. 3.64 g (GLC, BuSeSeBu: IV 18:82) are obtained, b.p. 89-160 С

according to HMH (chromatograph LXM 2000x3 mm, 15% silico I on chomaton NAW (0.200-0 mode - programming from 150 to 220 ° C, 8 ° / min, helium gas, flow rate 50 ml / min, tarometer) After removal of the solvent, it is distilled under vacuum. Regen 1.12 g of dibutyl disulfide. T 91-1050 ° C, 3.0 g are isolated (5% (IV) 89% pure 164-176 ° C (3 mm Hg) Thus, the proposed simple method allows for new selenium derivatives to find a variety of different uses.

Claims (1)

Formula invented The method of obtaining 1-alkyl-bis- (alkylseleno) -2-chloroeth formula RSC (SeR) C (Cl) SeR ,, (3 mm Hg), p5, ° 1.5680. Example 7. 1-Isopropylthio-1,2- -bis- (butyl seleno) -2-chloroethene (IV). 1.83 g of isopropylthiochloroacetylene and 3.58 g of dibutyl diselenide are dissolved in 20 ml of dry methylene chloride. where R is ethyl and R4 is butyl and R is ethyl and RJ is methyl, R is isopropyl and R is me R is isopropyl, and R is bu different kiltyochloroacetylene total photo RSC2CC1, where R have the indicated meanings they are reacted with dialing ether dialicyl ether at boiling. 35 The resulting solution is boiled. 18.5 hours. By GMH data (LHM 8-MD chromatograph, 2000x3 mm column, 15% silicone DC550 at chomaton NAW (0.200-0.250 mm), mode — temperature programming from 150 to 220 ° C, 8 ° / min, carrier gas helium, flow rate 50 ml / min, detector catarometer), the reaction is 71%. After removal of the solvent, the residue is distilled in vacuo. Regenerate 1.12 g of dibutyl disulfide. Bp 91-1050 ° C, 3.0 g (55%) of compound (IV) are isolated with 89% purity. Bp 164-176 ° C (3 mm Hg); 1.5775. Thus, the proposed new simple method allows obtaining new selenium derivatives, which can find various practical applications. Invention Formula The method of obtaining 1-alkylthio-1,2- -bis- (alkylseleno) -2-chloroethenes of the general formula RSC (SeR) C (Cl) SeR ,, where R is ethyl and R4 is butyl or R is ethyl and RJ is methyl, or R is isopropyl and R is methyl, or R is isopropyl and R is butyl, characterized in that alkylthiochloroacetylene of the general formula RSC2CC1, where R has the indicated meanings, is reacted with the corresponding dialkyl di-selenide in diethyl ether at reflux.