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111 a study of the "induced" decomposition of hydroperoxides by allcoxy radicals, tert-butyl hydroperoxide has been decomposed by the action of di-tert-butyl peroxyoxalate a t 45' . The homolytic cleavage of peroxalate to tert-butoxy was unaffected by the presence of hydroperoxide and 7 to 10 molecules of hydroperoxide were destroyed for each radical thus produced. The kinetics have been analyzed and a mechanism developed which has significance for any system containing peroxy radicals.

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The reductions of n-butyl, sec-butyl, and tert-butyl hydroperoxides by triphenylphosphine in ethanol have been shown to follow second-order kinetics with k2's equal, respectively to 107.2e−8.4/RT, 109.0e−10.8/RT, 108.8e−11.2/RT. Similar results obtain in CH2Cl2, but in hexane the rate equation requires an additional term, k3[Ph3P][RO2H]2, though the overall reaction is somewhat faster than in the other solvents.Retardation, apparently by adventitious impurities, has been observed in some cases, but attempts to inhibit the reaction by free radical traps were unsuccessful. Parallels with reduction of hydroperoxides by organic sulfides suggest a similar non-radical mechanism.

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