Solvolysis of exo- and endo-Tricyclo[3,3,0,0^2,8]oct-3-yl p-Nitrobenzoates

Abstract

exo- and endo-Tricyclo[3,3,0,0^2.8]octan-3-ols (7a) and (8a) have been prepared and their structure elucidated. Solvolysis of the derived p-nitrobenzoate of the endo alcohol in 70% aqueous acetone at 100º occurred some ten times faster than the p-nitrobenzoate derived from the exo alcohol. Solvolysis of both p-nitrobenzoates yields a similar range of products which includes the two olefins (11) and (12), the four alcohols (lc), (3b), (7a) and (8a), and the p-nitrobenzoate esters of (1c) and (3b). The product distribution suggest that the intermediate carbonium ions involved in both solvolysis are verysimilar but quite different from those involved in the acetolysis of anti-bicyclo[3,2,l]oct-2-en-8-yl p-toluenesulphonate.