Acetanilide, nitration rearrangement

Preparation of diazoketones and their rearrangements during hydrolysis (method 271) and alcoholysis (method 295) are discussed elsewhere. Ammonolysis of diazoketones leads to amides of acids containing one more carbon atom than the original acyl halide. Halogen atoms may be present in a remote position on an aliphatic chain. The reaction is carried out by heating the diazoketone in alcohol or dioxane solution with aqueous ammonia in the presence of silver oxide or silver nitrate catalysts. Substituted acetanilides are formed when aniline is used in place of ammonia. ... 

Several types of Schmidt reaction merit special mention (a) An interesting consequence of the factors governing migratory aptitudes is that acetanilides are the major (typically >95%) products of rearrangement of acetophenones. This leads to a practical alternative to nitration and reduction as a preparative route to aromatic amines , cf. reaction (24). (b) Product analyses showed that... 

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