GB347774A - Process for the manufacture of monoacyl diamines of the benzene series - Google Patents

Abstract

Monoacyldiamines of the benzene series, derived from 1 : 3- or 1 : 4-diaminobenzene in which the other positions may be occupied by hydrogen, halogen, alkyl or alkoxyl radicals, are made from the corresponding nitrophenylamides of aromatic sulphonic acids by reduction with iron or other reducing agent, acylating with an aromatic or aromatic-aliphatic carboxylic acid halide and treatment with concentrated sulphuric acid to hydrolyse off the arylsulphonic group. In examples:-5 - nitro-4-methyl-2-benzenesulphamido-1-methoxybenzene is reduced by means of iron and hydrochloric acid, the mixture made alkaline with caustic soda and the amino compound recovered, benzoyl chloride is added and the benzoyl compound filtered off and hydrolysed with sulphuric acid; the 5 - benzoylamino-4-methyl - 2 - amino - 1 - methoxy - benzene separates out as the sulphate which is washed neutral with sodium chloride and the free base liberated with sodium carbonate. 2-4-Dichlorbenzoyl chloride, phenylacetyl chloride, 2-chlorphenoxyacetic acid chloride or cinnamic acid chloride may replace the benzoyl chloride to give the corresponding derivatives. In a similar manner 5-nitro-4-methyl- 2 - benzenesulphamido - 1 - ethoxybenzene is converted into 5-benzoylamino-4-methyl-2-amino - 1 - ethoxybenzene; 5-nitro - 4 -methyl-2-benzenesulphaminophenylbutylether to 5-benzoylamino - 4 - methyl - 2 - aminophenylbutylether; 2-methyl-4-nitro-1-toluenesulphamidobenzene to 2-methyl - 4 - benzoylphenylenediamine; 6-nitro-4-benzenesulphamino-1 : 3-dimethylbenzene to 6-benzoylamino-4-amino-1 : 2-dimethylbenzene; 4-nitro-2-toluenesulphamino-1-methoxybenzene to 4-benzoylamino-2-amino-1-methoxybenzene; 5-nitro-2-benzenesulphamino-1 : 4 - hydroquinonedimethyl - ether to 5 - benzoylamino - 2 - amino - 1 : 4-hydroquinonedimethylether and 5-nitro-2-benzenesulphamino-1 : 4-hydroquinonediethylether; 5-nitro-2-amino-4-ethoxy-1-methoxybenzene is condensed with benzenesulphochloride in pyridine and the resulting compound converted to 5-benzoylamino-2-amino-4-ethoxy - 1 - methoxybenzene; 5-nitro-4-chloro-2-toluenesulphamido - 1 - methoxybenzene is reduced with iron and formic acid and converted to 5-benzoylamino-4-chloro-2-amino - 1 - methoxy - benzene. Specification 303,838, [Class 2 (iii), Dyes &c.], is referred to. 5-Nitro-4-methyl-2-benzenesulphaminophenylbutylether is prepared by heating the sodium salt of 2-nitro-4-methylphenol with butylbromide, reducing and treating the product according to Specification 6741/04, [Class 2, Acids and salts, Organic &c.]. 6-Nitro-4-benzenesulphamino-1 : 3-dimethylbenzene is prepared by treating 6-nitro-4-amino-1 : 3-dimethylbenzene dissolved in pyridine with benzene sulphochloride. 4-Nitro-2-toluenesulphamino-1-methoxybenzene is prepared by treating 4-nitro-2-anisidine dissolved in pyridine with p-toluenesulphochloride.