Inductive Charge Dispersal in the Solvolyses of 4- and 5-Substituted 2-Norbonyl p-Toluenesulfonates

Article abstract of DOI:10.1002/hlca.19860690834

The solvolysis rates and products of 4- and 5-exo-substituted 2-exo- and 2-endo-norbornyl tosylates 9 and 10, respectively are reported.The logarithms of the rate constans (log k) correlate linearly with the inductive constans ?_I^q for the substituents.A comparison of the reaction constans ρ_I for the 4-, 5-, 6-, and 7-substituted 2-exo- and 2-endo-tosylates 9, 10, 1, and 2 respectively, indicates that inductivity is higher for 2-exo-ionization than for 2-endo-ionization in all series.This observation is attributed to the more favorable alignment of neighboring C-atoms for dorsal participation in exo-ionization, especially, in the case of C(6).