Reactions of radicals containing fluorine. Part 4.—Reactions of trifluoromethyl radicals with fluoroaldehydes
Abstract
The reactions of trifluoromethyl radicals, generated by the photolysis of hexafluoroacetone, with the aldehydes HCOCF3, HCOC2F5 and HCOC3F7 have been studied and the following Arrhenius parameters determined : [graphic omitted] The rate of hydrogen atom abstraction from the fluoroaldehydes at 164°C is independent of the size of the fluoroalkyl group. Direct photolysis of the aldehydes HCOCF3, HCOC2F5 and HCOC3F7 is complicated by the intramolecular elimination reactions : [graphic omitted] A value of 1.95, which is independent of temperature, has been obtained for the cross-combination of CF3 and C2F5 radicals.