SOME REACTIONS OF NITROBENZENE RADICAL-ANION AND OF ITS HALOGENATED DERIVATIVES

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.