Norbornanes. Part 18. Inductive Charge Dispersal in the Solvolyses of 4- and 5-Substituted 2-Norbornyl p-Toluenesulfonates

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 constants (log k) correlate linearly with the inductive constants σ for the substituents. A comparison of the reaction constants p₁ 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 neighbouring C-atoms for dorsal participation in exo-ionization, especially, in the case of C(6).