SU420621A1 - - Google Patents

Description

one

The invention relates to a new process for the preparation of bis- (organylthio) acetylenes of the general formula RSC CSRi, where R and Ri are the same or different alkyl, alkenyl, aralkyl or aryl radicals substituted in the aromatic core or substituted x, which can be used as monomers, intermediates of organic synthesis and biologically active compounds.

A known method of producing bis (alkylthio) acetylenes by the action of chlorine on bis (alkylthio) ethylene followed by dehydrochlorination with an alcoholic KOH solution.

The yield of the target product based on bis (alkylthio) -ethenes is 29%.

However, the known method has a low yield of the target products, multistage.

The purpose of the invention is to simplify the process technology and increase the yield of the target product.

For this, bis- (organicthio) acetylenes are obtained by reacting β, β-dichlorovinyl organosulfide with a thiol in the presence of a base. As the base, metal hydroxides, К2СОз or МазСОз in the amount of 2-2.5 mol per 1 mol | 3, p-dichlorovinyl organosulfide are used. The reaction is carried out at 80-140 ° C for 3-5 hours depending on the structure of vinyl sulfide.

The yields of bis (organylthio) acetylenes are 60-80%.

Example 1. | 3, p-di. Chlorovinyl butyl sulfide. 256 g (1 g-mol) a, p, | 3, p-tetrachloroethyl butyl sulfide in 200 ml of methanol and 70 ml of acetic acid are added dropwise to a suspension of 97 g of zinc dust in 150 mt of methanol in a three-necked flask. The reaction is exothermic. Cooled in a steam bath. After the treatment, 166.5 g (90%) were isolated by vacuum distillation at m. Of CAT. 68 ° / 2 mmHg Art., “2, ° 1,5130; uff 1.1678; MRo ,,,,,, 47,64; MRo, 47.06.

Found,%: Cl 38.31; S 16.85.

CeHioCbS.

Calculated 0.0: Cl 38.30; S 17.32.

Example 2. 1-Butylthio-2-isopropylthioacetylene. 12 g of p, p-dichlorovinylisopropylsulfide, 7.5 ml (6.3 g) of n-butylmercaptan and 9 g of calcined caustic potash (excess of 1.2 g) are shifted. Heated with stirring in a flask with reflux condenser NPH 90-110 ° C for 4-5 hours. Then it is washed with water, extracted with ether, and MgSO4 is dissolved. After distilling off the solvent by distillation in vacuo, 10.3 g (78%) of 1-butylthio-2-isopropylthio-acetylene were isolated with a batch. PZ-115 ° C /

1.5340; 20 0.9810;

,20 -

/ 4 mm Hg.

. 59.68; MRo, 57.98. Found,%: S 34.03.

CgHigSo.

Calculated,%: S 34.04.

3

IR spectrum: vC C 2080 cm-.

According to GLC, the purity of the product is -98%.

Example 3. Bis- (isopropylthio) -acetylene. 12 g of ppd-dichlorovinylisopropylsulfide, 6.5 ml {5.3 g) of isonropylmercaptap and 9 g of potassium hydroxide are mixed. Heated at 80-100 ° C for 4-5 hours. After treatment, the residue is distilled off at 74 ° C / 2 mmHg. Art. 9.9 g (81.1%) of bis- (isopropylthio) -acetylene g 1.5380; df 0.9916. MCO. ,, 54,99; MRo ,, 53,33.

Found,%: C 53.92; H 7.92; S 36.83.

Calculated,%: C 54.79; H 8.62; S 36.79.

According to GLC, the purity of the product is 98%.,

IR spectrum: vC C 2080 cm-.

Example 4. 1-Fennlthio-2. butylthioacetylene. 19.9 g (0.107 g-mol) p, | 3-dichlorovinylbutylsulfide, 11 ml of thiophenol and 13 g of KOH are mixed. Heated at 90-135 ° C for 5 hours. After the usual treatment, 11.8 g (50%) of 1-phenylthio-2-n was isolated. butylthioaceticum. 141 -142 ° C / 2 mm Hg. v .;

tplen with t., 1339; yd 67.69,

20

1.6075; 68.43.

Mro,

.

Found,%: S 28.44.

Ci2Hi4S2.

Calculated,%: S 28,84. NC-spectrum: v С С 2080 cm-.

Subject invention

1. The method of obtaining bis- (organicthio) -acetylenes is distinguished by the fact that, in order to simplify the process technology and increase the yield of the target product, p-dichloroylorganic sulfide is reacted with a thiol in the presence of a base, followed by release of the desired product known techniques.

2. Method for and. 1, characterized in

base in quantity

that 2-2.5 mol per 1 mol of the starting material is used and

the process is carried out at 80-140 ° C.