REARRANGEMENT STUDIES WITH 14C: XXIV. SOLVOLYSES OF 2-(α-NAPHTHYL)-1-14C-ETHYL p-TOLUENESULFONATE

Abstract

Acetolysis and formolysis of 2-(α-naphthyl)-1-14C-ethyl p-toluenesulfonate (I-OTs) were interrupted after 50% completion and the products, 2-(α-naphthyl)ethyl acetate and formate (I-OAc and I-OCHO), and the "unreacted" I-OTs were recovered. Rearrangements of the 14C-label from C-1 to C-2 were found to be about 46% and 50%, respectively, in the I-OAc and I-OCHO. A similar rearrangement amounting to about 38% was observed in the I-OTs recovered from the acetolysis, while the I-OTs recovered from formolysis showed less than 1% 14C rearrangement. Titrimetric rates for these reactions were determined and compared with known rates of solvolyses of 2-phenylethyl and ethyl p-toluenesulfonates. Small rate enhancements were indicated. The mechanistic implications of these results in relation to current carbonium ion theory are discussed.