Benzidine, nitro derivatives

CA 48,5836(1954) 9)Sax( 1957),347-8 Benzidine,Alkylated(Nitro Derivatives). See Vol l,p A129-L and Note under 2,5,3,-Trinitrobenzi-dine... 

Note Higher nitro derivatives of benzidine were not found in Beil or in CA through 1956 but some addnl higher nitro alkylated benzidine derivs which are expl include the following ... 

There continue to be a few examples reported where rearrangement has been used synthetically to develop new products sometimes important in the industrial world. Monomers for polyamides and polyimides (which are used for making moisture sensitive films, fibres and mouldings) have been synthesized24 by the reduction of a nitro compound, followed by a benzidine rearrangement of the resulting hydrazobenzene derivative as outlined in Scheme 5. 

These substances were prepared by Mertens89 in 1886 by the action of nitric acid on dimethylaniline (I, II, and III) and on monomethylaniline (II and III). Van Romburgh90 in the same year proved them to be derivatives of benzidine, and at a much later time91 summarized the work which had been done upon them and synthesized the substances in such manner as to prove the position of the nitro groups. 

Unsymmetrical azo- or azoxy-compoimds on reduction with tin and hydrochloric add produce a mixture of two amines, while hydrazo-compounds may yield amine(s) formed by normal reduction of the hydrazo-link and a diamine produced by a benzidine rearrangement. Nitro-samines, on reduction with tin and acid, give the secondary amines from which they were derived.)... 

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