Reaction of Benzene Radical Cation with Water. Evidence for the Reversibility of OH Radical Addition to Benzene

Article abstract of DOI:10.1021/ja00403a042

The thermal decomposition of Na2S2O8 at 80 deg C in aqueous solutions of benzene and nitrobenzene gives phenol, biphenyl, and o- and p-nitrophenol in high yield.In the absence of benzene or if benzene is replaced by toluene or anisole no nitrophenols are formed under otherwise identical conditions.This indicates a direct involvement of the benzene radical cation in the hydroxylation of nitrobenzene.The benzene radical cation reacts with water to give hydroxycyclohexadienyl radical, which in turn can dissociate to benzene and OH radicals.The effect of oxygen, Cu²⁺, pH, and benzene concentration on the product yields has been investigated.