A Novel Organic Peroxyester as an Exclusive Source of tert-Butyl Radicals

A novel peroxyester, 1,1,2,2-tetramethylpropyl peroxypivalate 1b, has been synthesized and thermolyzed in cumene. The kinetic data show that the decomposition rate constant of 1b is about three times higher than that of tert-butyl peroxypivalate. The radical trapping technique employing 1,1,3,3-tetramethyl-2,3-dihydro-1H-isoindol-2-yloxyl has been used to study the decomposition mechanism of 1b. The results show that the thermolysis of 1b in cumene generates tert-butyl radicals exclusively.