The electrophilic trifluoromethyl radical cf 3 application of the dual-parameter equation to the correlation analysis of relative rates of the trifluoromethylbromo addition reactions to 14 p-y-substituted phenylacetylenes

Abstract

A rigorous procedure was applied to the measurement of the relative rates, i.e., k r(Y) = k Y/ k H, of the trifluoromethylbromo addition reactions to 14 p-Y-substituted phenylacetylenes ( 1-Y, with Y =F, Cl, Br, Me, Bu, OMe, SMe, SiMe 3, CF 3, CN, NO 2, SOMe, COMe and CO 2Me) . The reaction was run in cyclohexane under nitrogen at 55 ±0.5 °C and was initiated by di-t-butylperoxy-oxalate. Correlation analysis of the data suggests that a spin effect is also operating at the transition state of this addition reaction and that the dual-parameter equation is applicable to this reaction.