Thermal decomposition mechanisms of tert-alkyl peroxypivalates studied by the nitroxide radical trapping technique

T Nakamura, WK Busfield, ID Jenkins…

Index: Nakamura, Tomoyuki; Watanabe, Yasumasa; Tezuka, Hiroshi; Busfield, W. Ken; Jenkins, Ian D.; Rizzardo, Ezio; Thang, San H.; Suyama, Shuji Chemistry Letters, 1997 , # 11 p. 1093 - 1094

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Citation Number: 28

Abstract

The thermolysis of a series of tert-alkyl peroxypivalates 1 in cumene has been investigated by using the nitroxide radical-trapping technique. tert-Alkoxyl radicals generated from the thermolysis underwent the unimolecular reactions, β-scission, and 1, 5-H shift, competing with hydrogen abstraction from cumene. The absolute rate constants for β-scission of tert- alkoxyl radicals, which vary over 4 orders of magnitude, indicate the vastly different ...