Journal of the American Chemical Society p. 1793 - 1796 (1984)
Update date:2022-08-05
Topics:
Barclay, L. R. C.
Lusztyk, J.
Ingold, K. U.
Rate constants for the free radical rearrangement, CF3C(O)CMe2CH2 (1d) -> CF3C(O)OCH2CMe2 (2d), have been measured in CF2ClCFCl2 by kinetic EPR spectroscopy.This reaction is very significantly faster (k175 deg C = 7.0E4 s-1) than the related rearrangement, CH3C(O)OCMe2CH2 (1a) -> CH3C(O)OCH2CMe2 (2a) (k175 deg C = 4.5E2 s-1), in hydrocarbon solvents.The potential cyclic intermediate radical, 2-(trifluoromethyl-4,4-dimethyl-1,3-dioxolan-2-yl (3d), does not undergo ring opening to 2d, at temperatures where the 1d -> 2d rearrangement is very fast.It is concluded that 3d is not an intermediate in the trifluoroacetoxyl migration.It is also concluded on the basis of the k1 values for 1a and 1d that these rearrangements involve a charge-separated transition state.The 1a -> 2a rearrangement is very much faster in water (k175 deg C = 2.1E4 s-1) than in hydrocarbon solvents, which provides additional support for a charge-separated transition state.
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