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.

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