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 ...
