Free Radical Oxidations in Water: Decomposition of Azoinitiators and Oxidation of p-Cresol and p-Isopropylphenol

Article abstract of DOI:10.1021/jo00161a003

The free radical oxidation of p-cresol and p-isopropylphenol using peroxy radicals produced by thermolysis of azoinitiators in oxygen at 50 degC in purified water is considered.The major primary products of oxidation of p-cresol are the peroxycyclohexadienones and the corresponding hydroperoxides; smaller amounts of two phenolic dimers are also found in each case.A variety of other products thought to result from ortho substitution also were observed but not characterized.The general features of the reactions in water are much the same as observed in organic solvents.Cupric ion causes further reaction of the peroxide products, leading to additional oxidation of phenol and possible formation of some p-quinone; Fe²⁺ ion in contrast is a strong inhibitor of phenol oxidation by RO2*.