Peroxy Esters. 9. Base- and Radical-Induced Decomposition of 1-Alkyl-3,5-di-tert-butyl-4-oxo-2,5-cyclohexadienyl 3,5-Di-tert-butyl-4-hydroxyperbenzoates

Article abstract of DOI:10.1021/jo00169a017

The title peroxy esters 1, when deprotonated with t-BuOK in DMF to the corresponding phenolate anions, decompose even at -78 deg C to give compounds 2-10.These compounds result undoubtedly from homolysis of the peroxy bond in 1, indicating that the generation of a carbanion at the α-position of the acyl group in peroxy esters (via resonance in the present case) induces ready homolysis of the peroxy bond.The oxidation of 1 with one-electron oxidizing agents gives rise to the corresponding phenoxy radicals, which also induce homolysis of the peroxy bond.