Thermal Decomposition of 2,2-Bis(<i>t</i>-butyldioxy)-3-methylbutane

Abstract

Abstract The activation parameters for decomposition of 2,2-bis(t-butyldioxy)-3-methylbutane (2) in diphenylmethane are ΔH\eweq=144.8 kJ mol−1 and ΔS\eweq=49.4 JK−1 mol−1. The decomposition products of 2 are t-butyl alcohol, acetone, isopropyl methyl ketone and t-butyl peracetate. t-Butyl peracetate (4) is an intermediate which decomposes during reaction. This peroxide 2 decomposes with homolytic one-bond cleavage at one of the peroxide groups and the resulting 1-(t-butyldioxy)-1,2-dimethylpropoxyl radical (3) decomposes subsequently to t-butyldioxy or isopropyl groups with β-elimination.