Patent GB-551681-A (GB)
Title: Improvements in and relating to the manufacture of organic sulphur compounds
IPC: C07D277/52
Filed: 1941-05-29
Abstract: 551,681. Thiazole derivatives. MANCHESTER OXIDE CO., Ltd., BANN, B., KRUG, P.. WHEELER, D. E., TAYLOR, W., and GLADDING, G. May 29, 1941, Nos. 7280/42 and 7281/42 [both divided out of 553,269], 7047/42 and 7080/42. Samples furnished. Drawings to Specification. [Class 2 (iii)] Benzenesulphenyl derivatives of aminothiazole are prepared by reacting a 2 - aminothiazole with a benzenesulphenyl chloride, ester or amide. The reaction of the chloride is effected in the absence of water or other hydroxyl-containing solvent, and an acidbinding agent, which may be additional aminothiazole, may be present. When using the amide, there must be no substituent in the amide group. The benzenesulphenyl chlorides may be obtained by chlorinating diphenyldisulphides, which latter may be prepared by heating thiocyanobenzenes, obtainable according to Specifications 513,473 and 514,203, with aqueous caustic alkali. Some of the products are capable of existence in two isomeric forms. According to the examples, (1) a p - nitrobenzenesulphenyl derivative of 2 - aminothiazole is prepared by reacting p - nitrobenzenesulphenyl chloride, obtained by chlorinating 4 : 4<SP>1</SP> - dinitrodiphenyldisulphide in chloroform, with 2 - aminothiazole in benzene solution ; (2) a p - - nitrobenzenesulphenyl derivative of 2 - amino - 4 - methylthiazole is obtained as in (1) using 2 - amino - 4 - methylthiazole ; the same derivative is also obtained by heating p - nitrobenzenesulphenamide with 2 - amino - 4 - methylthiazole in benzene, or by adding p - nitrobenzenesulphenic acid ethyl ester, prepared by treating the sulphenyl chloride with sodium ethylate, to an ethereal solution of 2 - amino - 4 - methylthiazole ; by heating under reflux with pyridine and benzene, the derivative is isomerized ; (3) a p - - nitrobenzenesulphenyl dreivative of 2 - acetylamino - 4 - methylthiazole is formed by interaction of p - nitrobenzenesulphenyl chloride with the thiazole in benzene ; the product may be reduced with alkaline ferrous sulphate to the corresponding p - amino derivative ; (4) the p - chlorbenzene- and p - toluene-sulphenyl derivatives of 2 - aminothiazole are prepared by reacting 2 - aminothiazole in benzene solution with p - chlorobenzene- and p - toluene - sulphenyl chlorides respectively ; the latter are obtained by chlorination of 4 : 4<SP>1</SP> - dichloro - and dimethyl - diphenyldisulphides : (5) the 4 - acetylamino - 3 - chlorobenzenesulphenyl derivative of 2 - amino - 4 - methylthiazole is formed when p - acetylamino - m - chlorobenzenesulphenyl chloride, obtained by chlorinating 4:4<SP>1</SP>-diacetylamino-3:3<SP>1</SP>-dichrolodiphenyldisulphide in chloroform, is added to a benzene solution of the thiazole ; (6) p-acetylaminobenzenesulphenyl chloride, prepared by chlorination of 4:4<SP>1</SP>-diacetylaminodiphenyldisulphide, is added to a benzene solution of 2-amino-4-methylthiazole or 2-acetylamino-4- methylthiazole to yield the corresponding sulphenyl derivative. Specification 379,683 also is referred to. Samples have been furnished under Sect. 2(5) of the benzenesulphenyl derivative of 2-amino- 4-methylthiazole prepared by interaction of the thiazole with (1) benzenesulphenyl chloride, obtained by chlorinating diphenyldisulphide in chloroform, and (2) benzenesulphenyl ethyl ester, obtained by treating benzenesulphenyl chloride with sodium ethoxide.