Rearrangement studies with 14C. XXXII. Solvent effects in the solvolyses of 2-phenyl-1-14C-ethyl tosylate and 2-phenyl-1-14C-ethylmercuric perchlorate

Abstract

The extents of isotope position rearrangement accompanying the solvolyses of 2-phenyl-1-14C-ethyl bromide (I–Br), 2-phenyl-1-14C-ethyl tosylate (I–OTs), and 2-phenyl-1-14C-ethylmercuric perchlorate (I–HgClO4), in three aqueous dioxane solvent pairs with different ionizing power Y were determined. No rearrangement was found for I–Br For I–OTs and I–HgClO4 the results are considered together with similar data previously obtained from ethanolysis, acetolysis, and formolysis. Linear correlations between log % rearrangement and Y are found for the solvolyses in ethanol and the aqueous dioxane solvent pairs. The mechanistic implications of these observations are discussed.