The Reaction of Hydroperoxides with Triphenylphosphine

15 May 1971

journal article
Published by Canadian Science Publishing in Canadian Journal of Chemistry

Vol. 49 (10) , 1707-1711
https://doi.org/10.1139/v71-277

Abstract

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 10^7.2e^−8.4/RT, 10^9.0e^−10.8/RT, 10^8.8e^−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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