The reaction of trifluoromethyl radicals with neopentane. An SH2 reaction at a saturated aliphatic carbon atom

Abstract

When hexafluoroacetone is photolysed in the presence of neopentane at 300°, isobutane is formed as a primary product, and 1,1,1-trifluoroethane is formed in amounts much greater than would be expected from combination of methyl and trifluoromethyl radicals. These results strongly support the occurrence of a homolytic bimolecular substitution reaction (S_H2) by a trifluoromethyl radical at a methyl carbon atom, with the displacement of a t-butyl radical.