POLARITY EFFECTS IN SOLVOLYSIS OF CYCLOHEXANE DERIVATIVES . IMPORTANCE OF FIELD EFFECTS IN DETERMINING RELATIVE REACTIVITIES

The rates of acetolysis of 4-substituted cyclohexyl methanesulfonates are shown to be dependent upon the polarity and conformation of the substituent as well as the conformation of the leaving methanesulfonate group. Rates of solvolysis for cis- and trans-4-chlorocyclohexyl methanesulfonate and for cis- and trans-4-bromocyclohexyl methanesulfonate have been calculated using a field effect model by employing the observed ground-state conformer populations (as determined by infrared spectroscopy) and the appropriate bond dipoles. The good agreement of the kinetic data with rate constants calculated employing a purely field effect model indicates the absence, or at least the very small role, of “through-the-bond” inductive effects. © 1969, American Chemical Society. All rights reserved.