The Nature and Transmission of Substituent Electrical Effects in Alicyclic Solvolysis

Abstract

The correlation of rate constants taken from the literature for 2-exo- and 2-endo-norbornyl derivatives substituted in positions 1, 4, 5-exo, 6-exo, 6-endo, and 7-anti with the triparametric LDR equation and relationships derived from it has been carried out. A delocalized (resonance) electrical effect has been found in all but the 4-substituted derivatives. The resonance effect may be somewhat greater when the leaving group is exo than when it is endo. Steric effects occur in the 6-endo-substituted derivatives. The transition state resembles a classical carbocation rather than the nonclassical norbornyl carbocation. The correlation of solvolysis rate constants for 2- and 3-substituted 1- and 4-exo-substituted 2-exo-adamantyl derivatives gave no reliable indication that a delocalized electrical effect existed in these systems. A study of solvolysis rate constants for 4-substituted 1-[2.2.2]bicyclooctanyl, 6-exo-substituted [2.2.2]bicyclooctan-2-exo-yl and 6-exo-substituted [2.2.2]bicyclo- octan-2-endo-yl derivatives showed a delocalized electrical effect only in the latter of these systems. Such an effect was also observed in 4-substituted 2-chloro-2-methylbutane solvolyses. The transmission of electrical effects is by a modified field effect. It is dependent on 1/n where n is the number of bonds intervening between substituent and reaction site.