Absolute rate constants for hydrocarbon autoxidation. 32. On the self-reaction of 1,1-diphenylethylperoxyl in solution

Article abstract of DOI:10.1139/v82-369

The major products of the self-reaction of 1,1-diphenylethylperoxyl have been determined from product studies of the autoxidation of 1,1-diphenylethane, induced decomposition of 1,1-diphenylethyl hydroperoxide, and decomposition of 2,2,3,3-tetraphenylbutane under an atmosphere of oxygen.Overall self-reaction is a complex free-radical process involving the intermediacy of 1,1-diphenylethoxyl and 1-phenyl-1-phenoxyethoxyl which undergo H-atom abstraction, β-scission and, in the case of the former radical, rearrangement.Hydroperoxide decomposition under an atmosphere of (36)O2, has shown that 1,1-diphenylethylperoxyl undergoes β-scission faster than α-cumylperoxyl at 303 K in solution.The values of the rate constants for self-reaction of Ph2C(Me)O2^. relative to those for the tert-butylperoxyl are, however, not affected by this reaction.Furthermore they are not affected to any appreciable extent by the efficiency with which Ph2C(Me)O^. , formed in nonterminating self-reaction, escape from the solvent cage.They are influenced principally by the first-order rate of decomposition of Ph2C(Me)OOOOC(Me)Ph2.