Kinetic studies on the mechanism of the decomposition of a number of β-substituted tert-butyl α, α -dimethylperpropionates

Abstract

A series of ter-butyl peresters having a general formula corresponding to I were synthesized.[Formula: see text]The thermally initiated rates of decomposition of these peresters were determined at several temperatures and the activation parameters for these thermolyses were calculated.The rates of decomposition were relatively insensitive to the substituents and followed the order I > C2H5 > C6H5S > H > Br > Cl. The activation parameters and product studies were consistent with a simple two bond scission mechanism and no evidence could be found for neighboring group participation in these homolyses.