Two CH, groups at C(6) of 2-exo-(10a) and 2-endo-norbornyl p-toluenesulfonate l l a lower their solvolysis rates in 80% EtOH by factors of 28 and 16, respectively. A spirocyclopropyl group including C(6), as in 21s and 22a. reduces the rate ofexo-and endo-ionization by factors of 250 and 8, respectively. The geminally dimethyl-substituted tosylates 10a and l l a yield the 2-em-alcohol lob, whereas the spirocyclopropyl-substituted tosylates 21a and 22a furnish rearranged 3-brendanol 23. These findings are readily rationalized by the inductive model, according to which norbornyl cation formation is controlled by the inductive effect of dorsal substituents.Substituents at C(4), C(5), C(6), and C(7) of 2-exo-and 2-endo-norbornyl p-toluenesulfonate (tosylate) 1 and 2, respectively, control solvolysis rates by their inductive (I) effect only [ 11. This follows from the observed linear correlation of the logarithms of the rate constant logk with the inductive constants of the substituents CT: [2] at these positions according to the equation log k/ko = ploy, which, in addition to other data [3], precludes steric effects as a significant rate and product-controlling factor'). 7

In order to study the effect of C‐6 substituents on the solvolysis of endo‐ or exo‐tosylates, the rate constants for alcoholysis (in 80% ethanol) of (I) and its exo‐isomer are measured conductometrically, showing deceleration factors of 28 and 16, respectively compared with the parent compound.