申请人:Hoechst Celanese Corporation
公开号:US05157142A1
公开(公告)日:1992-10-20
A process is provided for preparing N-acyl-aminothiophenols, e.g., N-acetyl-para-aminothiophenol, or aminothiophenols, e.g., para-aminothiophenol, by reacting a hydroxy aromatic ketone, e.g., 4-hydroxyacetophenone (4-HAP), with hydroxylamine or a hydroxylamine salt, to form the oxime of the ketone, subjecting the oxime to a Beckmann rearrangement in the presence of a catalyst to form the N-acyl-hydroxy aromatic amine, e.g., N-acetyl-para-aminophenol (APAP), reacting the N-acyl-hydroxy aromatic amine with an N,N-di (organo) thiocarbamoyl halide, e.g., N,N-dimethylthiocarbamoyl chloride, to form an O-(N-acyl-aminoaryl)-N,N-di (organo) thiocarbamate, e.g., O-(N-acetyl-para-aminophenyl)-N,N-dimethylthiocarbamate, pyrolytically rearranging the O-(N-acyl-aminoaryl)-N,N-di (organo) thiocarbamate to form an S-(N-acyl-aminoaryl)-N,N-di (organo) thiocarbamate, e.g., S-(N-acetyl-para-aminophenyl)-N,N-dimethylthiocarbamate, and hydrolyzing the latter compound to obtain the N-acyl aminothiophenol or aminothiophenol. The N-acyl aminothiophenol may be reacted with an acylating agent to form the N,S-diacyl-aminothiophenol, e.g., N,S-diacetyl-p-aminothiophenol, or may be further hydrolyzed to the aminothiophenol, e.g., p-aminothiophenol.
提供了一种制备N-酰基氨基硫酚,例如N-乙酰基对氨基硫酚,或氨基硫酚,例如对氨基硫酚的方法,通过将羟基芳香酮,例如4-羟基乙酰苯酮(4-HAP),与羟胺或羟胺盐反应,形成酮的肟,将肟在催化剂存在下进行贝克曼重排反应,形成N-酰基-羟基芳香胺,例如N-乙酰基对-氨基苯酚(APAP),将N-酰基-羟基芳香胺与N,N-二(有机)硫代氨基卤化物,例如N,N-二甲基硫代氨基氯化物,反应形成O-(N-酰基氨基芳基)-N,N-二(有机)硫代氨酸酯,例如O-(N-乙酰基对-氨基苯基)-N,N-二甲基硫代氨酸酯,通过热解重排O-(N-酰基氨基芳基)-N,N-二(有机)硫代氨酸酯形成S-(N-酰基氨基芳基)-N,N-二(有机)硫代氨酸酯,例如S-(N-乙酰基对-氨基苯基)-N,N-二甲基硫代氨酸酯,将后一化合物水解得到N-酰基氨基硫酚或氨基硫酚。N-酰基氨基硫酚可以与酰化剂反应形成N,S-二酰基氨基硫酚,例如N,S-二乙酰-p-氨基硫酚,或进一步水解为氨基硫酚,例如p-氨基硫酚。