Inductive effects and rate and equilibrium constants of chemical reactions

Abstract

Inductive effects of groups can conveniently be measured by effective charges Q—the hypothetical charges which would be required to give the same effect as the groups. Provided the group is not involved in mesomeric interactions, its inductive effect is reduced by a transmission factor (ϵ=0·5) if an extra atom is introduced between it and the site of the reaction. The relative rates of solvolysis of substituted t‐cumyl chlorides can be calculated from the charge distribution of the benzyl anion and other examples are given of the use of Q and ϵ for the estimation of the effects of substitution upon equilibrium and rate constants.