GB546301A - Improvements in the manufacture of aromatic compounds containing sulphur - Google Patents

Abstract

546,301. Aromatic sulphonyl chlorides. MANCHESTER OXIDE CO., Ltd., CLAYTON, J. H., and BANN, B. Sept. 27, 1940, No. 14617. Samples furnished. [Class 2 (iii)] Nuclear substitution products of benzenesulphonyl chloride, in which the substituent is an alkyl-, aryl- or acyl-substituted hydroxy group or an acyl-substituted amino group, are obtained by treating, in a medium containing water, a correspondingly substituted symmetrical diphenyl. disulphide with chlorine or a substance yielding chlorine. The medium may be, for example, aqueous acetic, formic or propionic acid or an organic liquid not completely miscible with water, such as benzene, carbon tetrachloride or chloroform, containing a small proportion of water. The products may be converted into sulphonamides by treatment with ammonia or primary or secondary amines or may be converted into sulphones by reduction to the sulphinic acids and treating the alkali salts of these with an alkylating or arylating agent such as an alkyl halide or sulphate or a dinitrochlorobenzene. Examples relate to the production of (1) 4-acetylamino-3- methoxybenzenesulphonyl chloride by passing chlorine into aqueous acetic acid containing 4:41 - di - acetylamino - 3:31 - di - methoxy - diphenyl disulphide, the temperature not being allowed to rise above 40‹ C., and pouring the reaction mixture into water to precipitate the sulphonyl chloride ; there may be similarly obtained 4 - acetylaminobenzenesulphonyl chloride and its 3-methyl-, 2- or 3-chloro-, 3:6- dimethyl-, 3-ethoxy-, 3:6-diethoxy-, 3-methyl- 6-chloro-, 3:6-dichloro-, 3-methoxy- or ethoxy- 6-methyl-, 2-methoxy-, 3-methoxy or ethoxy-6- chloro-, 3-chloro-6-methyl-, 2-methyl-3- ethoxy-, 3-phenoxy- and 2-chloro-3-methylderivatives; (2) 4-methoxybenzenesulphonyl chloride similarly by passing chlorine into aqueous acetic acid containing 4:4<SP>1</SP>-dimethoxydiphenyl disulphide ; (3)4-acetylaminobenzenesulphonyl chloride by passing chlorine into wet benzene at 25-30‹ C. containing 4:4<SP>1</SP>-di-acetylaminodiphenyl disulphide. Samples have been furnished under Sect. 2 (5) of (1) 4-acetoxyphenylsulphonyl chloride, as prepared from 4:4<SP>1</SP>-diacetoxy diphenyl disulphide (obtained by the action of acetic anhydride on 4:4<SP>1</SP>-dihydroxydiphenyl disulphide in dry pyridine) (2) 4-benzoyloxyphenylsulphonyl chloride, as prepared from 4:4<SP>1</SP>-dibenzoyloxydiphenyl disulphide (obtained by the action of benzoyl chloride on the disodium salt of 4:4<SP>1</SP>-dihydroxydiphenyl disulphide). Diphenyl disulphides substituted symmetrically as above in 4:41-positions are obtainable by the action of caustic alkali on the corresponding thiocyano compounds, obtainable as described in Specifications 513,473 and 514,203,