Patent GB-581932-A (GB)
Title: Manufacture of para-aminobenzene sulphonacylamides
IPC: C07C311/45
Filed: 1944-02-16
Abstract: Para - aminobenzenesulphonacylamides are prepared by reacting a sulphonamide of the benzene series substituted in the para position by a group containing nitrogen which is convertible into an amino group by hydrolysis or reduction with a carboxylic acid of the benzene series or a functional derivative thereof containing an alkyl residue of more than one carbon atom with or without an alkoxy or alkylthio residue.  The condensation is preferably conducted in the presence of an acid binding agent and, if desired, a catalyst for splitting off hydrogen halides such as powdered copper or aluminium chlorides.  The preferred functional derivatives referred to above are the acid chloride or the acid amide.  The sulphonamides which may be used in the present invention are the same as those named in the parent Specification.  In an alternative form of the invention a sulphonic acid halide of the benzene series containing in the para position an amino group or a group containing nitrogen which is convertible into an amino group by hydrolysis or reduction is treated with an amide of a carboxylic acid of the benzene series containing as a substituent an alkyl residue of more than one carbon atom with or without an alkoxy or alkyl-thio residue. Carboxylic acids there are named 4-ethyl benzoic acid, 4-isopropyl benzoic acid, 3-alkyl-4-methoxy benzoic acid, 3-n-propyl-4-methoxy benzoic acid, 3-allyl-4-ethoxy benzoic acid, 4-ethyl-3-methylmercaptobenzoic acid, 4-n-butyl benzoic acid, 4-isobutyl benzoic acid, 4-tertiary butyl benzoic acid, 4-amyl benzoic acid, 4-n-hexyl benzoic acid, 4-n-heptyl benzoic acid, 4-octyl benzoic acid, 4-dodecyl benzoic acid.  In examples: (1) a pyridine suspension of p-nitrobenzene sulphonamide is treated with p-ethyl benzoyl chloride to give p - nitrobenzene - N - (p - ethylbenzoyl) -sulphonamide which is reduced to the corresponding amino compound with iron.  (2) p - nitrobenzenesulphonamide is mixed with 3-allyl-4-methoxy benzoic acid chloride in chlorbenzene solution, copper powder is added and the mixture refluxed.  (3) p-Nitrobenzene-sulphonamide is reacted with 4-isopropyl benzoic acid chloride as in example (2) and the product reduced with iron powder and acetic acid.  (4) p-Nitrobenzenesulphonamide is reacted with 4 - methoxy - 3 - allyl - benzoyl chloride in pyridine solution, and the product hydrogenated with the acid of a nickel catalyst to give 4-amino-benzene-N-(41-methoxy-31-propylbenzoyl) -sulphonamide.  (5) p-Nitro-benzene-sulphonamide is reacted with 4-tertiarylbutyl-benzoyl chloride in pyridine solution and the product reduced with iron to give 4-aminobenzene-N-(41-tertiarylbutyl benzoyl)-sulphonamide. (6) p-Nitrobenzene sulphonamide is reacted with 4-propylbenzoyl chloride in pyridine solution and reduced with iron to give 41 - propylbenzoyl - 4 - aminobenzene sulphonamide.  (7) p-Nitrobenzene sulphonamide is reacted in pyridine solution with 4-n-butyl benzoyl chloride and the product reduced with iron to give 4 - amino - benzene - N - (41 - butylbenzoyl)sulphonamide.  (8) p-Nitrobenzenesulphonamide is reacted in pyridine solution with 4-ethyl-3-methyl benzoyl chloride and the product reduced to 4-aminobenzene-N-(41-ethyl-31-methylbenzoyl) sulphonamide.  Para-ethylbenzoyl chloride is obtained from the corresponding acid by treatment with thionyl chloride. 4-Methoxy-3-allyl-benzoyl chloride is obtained from the corresponding acid by treatment with thionyl chloride.  4-Tertiarylbutyl-benzoyl chloride is obtained from the corresponding acid by treatment with thionyl chloride.  Para-propylbenzoyl chloride is obtained by treating the corresponding acid with thionyl chloride. 4-n-Butylbenzoyl chloride is obtained by treating n-butylbenzene with acetyl chloride in carbon disulphide solution in the presence of aluminium chloride to give 4-n-butylacetophenone which is then mixed with an aqueous hypochlorite solution, allowed to stand, treated with sodium bisulphite, and the para-butylbenzoic acid so obtained treated with thionyl chloride.  Ethyl-methylbenzoyl chloride is prepared by converting 3-methyl-4-ethylaniline into the nitrile, saponifying to the acid and treating with thionyl chloride.