SU478010A1 - The method of obtaining-substituted unsaturated cyclic bis (2-benzthiazolyl) sulfenamides - Google Patents

Description

one

A method is proposed for the preparation of new compounds, N-substituted unsaturated cyclic bis- (2-benzthiazolyl) sulfenamides, which can be used as rubber vulcanization accelerators.

The method is based on the well-known reaction of producing N-substituted cyclic bis- (2-benzthiazolyl) sulfenamides by reacting benzthiazolyl-2-sulfene chloride and cyclicIX) amine in the presence of a tertiary amine as a hydrogen chloride acceptor, using aliphatic, Schlc; pictic or aromatic amines.

According to a known reaction, it is proposed to prepare N-substituted unsaturated cyclic bis (2-benzthiazolyl) sulfenamides.

The proposed method is

that benzthiazolyl-2-sulfenyl chloride is treated with unsaturated cyclic amine at minus 15 - minus 5 ° C, followed by temperature up to 25 ° C in the presence of tertiary amine

in the selection of the target product by known techniques.

Preferably, the process should be carried out at a milf (f) yum ratio of benzthiazod-2-sul.) - fenchloride and unsaturated) 2: 1 cycrous-KOI-o amine.

The use of bis- (2-benzthiazolyl) sulfenamide ps prepared in this way allows the preparation of rubber with higher physicomechanical indicators compared to the known bis- (2-benthi-thiazolyl) sulfenamides based on saturated cyclic amines.

Unsaturated cyclic amine can be obtained by hydrogenation of anilium 1 with sodium in liquid ammonia and methyl alcohol.

Example. In a three-phase cooling chamber equipped with a reflux condenser with a calcium chloride tube, an electric mixer and an addition funnel, a solution of 80 g (0.4 mol) of benzthiazolyl-2-c; ulfenchloride in 40 O ml of dehydrated IH101X) dichloroethane (DCE) was obtained by proguskanii i-yXXXI ) chlorine through a suspension of 66.4 g (O, 2Moju altax in 400 ml of DCE at 55 ° C with a speed of 1O l / hour for 0.5-1 hour to obtain a clear brown solution of sulfenyl chloride. To remove the reaction mixture of chlorine through the resulting solution is blown for 15 minutes carbon dioxide, pre-dried after which the reaction mixture is cooled to minus 10 ° C, the solution gradually (dropwise) pour in a solution of 19 g (0.2 mol) of 1,4-cyclohex deeschamine and 40.4 g (0.4 mol) of triethylamine (TEA) in 10O ml of anhydrous | DCE; after cegche, the contents of the flask are weighed for 1 hour at 25-30 C. The precipitate of the triethylakish hydrochloric precipitate together with the altaxa is filtered off, the filtrate is washed, washed with a successively small amount of water, with a solution of SI S ( water, 5O% solution of CaON. water and dried over sodium sulfate. The solvent (DCE) is distilled off from fiy1: waste under vacuum at a temperature not higher than 50 ° C, the residue of the solvent is evaporated in a vacuum-drying I CFU. ... N-cyclohexadienyl-154bis- (2-benzthiazolyl) sulfenamide is obtained in a greenish-brown viscous liquid, and the yield is obtained. 63% of theoretical. Count on common altax, they say, in: found 426, calculated 425, Found,%: N 9.95; S 27.8. Calculated,%: N9.88, S DA, 1. The subject of the invention. A method for the preparation of N -mixed unsaturated cyclic bis- (2-benzthiazolyl) sufenamides, with a mixture of benzthiazolyl-2-sulfenyl chloride and non-saturated cyclic amine at minus 15 minus 5 C by subsequent evaporation to 25–30 ° C in the presence of one-third of the amine and isolation of the desired product by known methods. 2. The method according to claim 1, of which is the fact that the process is carried out in a molar ratio of benzthiazolyl-2-sulfenchloride and unsaturated with 1: 1: 1 Ayuyia equal to 2: 1,