MINISCI Aromatic amination

The reaction has been extended to the formation of primary aromatic amines, but the scope is narrow Citterio, A. Gentile, A. Minisci, F. Navarrini, V. Serravalle, M. Ventura, S. J. Org. Chem., 1984, 49, 4479. 

Amination refers to the reaction of the aminium radical (NH ) and its dialkyl derivatives (R2NH +) with organic substrates, particularly with olefins and aromatics. The aminium radical itself can be generated by the reduction of hydroxylamine O-sulfonic acid with ferrous ion (147) (Minisci and Galli, 1965). Dialkylaminium radicals are generated in several ways, the most common being the reduction of N-chlorodialkylamines by ferrous ion in acidic solution (148) and... 

The question of ami nation of aromatics by protonated amino radicals has been examined extensively by Minisci and co-workers (16). Benzene is aminated in good yields by a variety of N-chloroamines in acidic solutions, catalyzed by Iron(II) sulfates. With activated aromatics competing chlorination and sulfonation complicates the reactions, but In many cases good yields of the substituted anilines are obtained. In the case of a1kylbenzenes, benzylic chlorination competes with nuclear amlnatlon. The latter is favored by high acid concentrations. Thus, the reaction of toluene with N-chlorodimethyl amine (17) gives 95 percent amination and 6 percent benzylic chlorination in neat H SO., but 100 percent benzylic chlorination In neat acetic acid. The amount of nuclear amination increases with the concentration of H2SO4 in acetic acid. 

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