Secondary kinetic isotope effects and the intervention of non-classical ions in the solvolysis of endo-bicyclo[3.2.1]octan-2-yl toluene-p-sulphonate

Abstract

1,2-Dideuterio-endo-bicyclo[3.2.1]octan-2-yl toluene-p-sulphonate has been prepared and the secondary deuterium kinetic isotope effect has been measured in buffered formic acid (k^H/k^D= 1.154 at 29.9°) and in 80% aqueous ethanol (k^H/k^D= 1.116 at 64.4°). These low values are in accordance with a mechanism involving extensive bridging in the solvolytic transition state. The products of the formolysis reaction are also reported.