Some reactions of the nitrobenzene radical-anion and of its halogenated derivatives

Abstract

A technique for preparing and handling stable solutions of the nitrobenzene radical-anion, (PhNo₂·)^–, in dry methyl cyanide is described. The first-order decay of this radical in the presence of a small percentage of an aqueous buffer is ascribed to the diffusion-controlled rate of neutralisation of the anion.

E.s.r. measurements show that the electron-transfer reactions of (PhNO₂·)^– with quinones, diketones, and aromatic nitro-compounds of higher oxidation potential than nitrobenzene are rapid. The anions of ortho-chlorinated nitrobenzenes are unstable and undergo a first-order decay in which the labile chlorine is replaced by hydrogen.