Methyl and trifluoromethyl radical reactions with methyl acetate and deuterated methyl acetates

Abstract

The reactions of methyl and trifluoromethyl radicals with methyl acetate, methyl acetate-d₃ and methyl-d₃ acetate have been studied. The relative reactivities at 182°C of the acetyl and methoxyl groups in methyl acetate were in the ratio of 10 : 1 for both radicals. CF₃ radicals are ca. 20 times more reactive than CH₃ radicals at both sites. Rate constants and Arrhenius parameters based on Shepp's and Ayscough's values for CH₃ and CF₃ dimerization are as follows: [graphic ommitted]. The results are compared with those for similar reactive groups in other aliphatic compounds.