Acetic Acid → N-(3-chloro-2-methylphenyl)acetamide

Participants

Reaction Steps

3-Chloro-o-toluidine (90 g) in a mixture of glacial acetic acid (90 ml) and acetic anhydride (90 ml) was heated on a steam bath for 10 minutes. The solution obtained was then poured into water. A colourless powder precipitated, which was filtered off and dried to give 3-chloro-2-methylacetanilide (104 g), m.p. 156°-159° C., which was then dissolved with stirring in concentrated sulphuric acid (230 ml), while maintaining the temperature at not more than 30° C. The stirred solution was maintained at 5°-10° C. whilst concentrated nitric acid (38 ml; S.G. 1.42) was added during 30 minutes. The solution obtained was then stirred at 0° C. for one hour and then poured on to ice. The solid precipitate which was obtained was separated by filtration, washed with water and dried, to give a mixture of nitro-acetanilides (145 g), m.p. 135°-147° C., in the form of a yellow powder. This mixture of nitroacetanilides (94 g) was then heated at reflux for 6 hours in a mixture of glacial acetic acid (560 ml) and concentrated hydrochloric acid (370 ml). The mixture was then cooled, poured into water (1200 ml) and basified by the addition of aqueous 50% sodium hydroxide solution. The yellow precipitate which was obtained was separated by filtration, washed with water and dried, to give a mixture of nitroanilines (72 g), m.p. 150°-164° C. This mixture was then steam-distilled in the presence of concentrated hydrochloric acid (200 ml). The solid which separated from the distillate was filtered off to give 3-chloro-2-methyl-4-nitroaniline (19.1 g), m.p. 152°-154° C., in the form of a yellow solid. Further steam distillation gave a distillate containing a mixture of products (8.6 g), m.p. 134°-138° C. The insoluble material, which had not been distilled, was separated from the acid solution to give 3-chloro-2-methyl-6-nitroaniline (18 g), m.p. 164°-165° C., in the form of a brown powder.

Provenance & Evidence