Considerably improved Grunwald–Winstein correlatians for solvolyses of several secondary and tertiary benzylic derivatives upon inclusion of a term governed by the aromatic ring parameter (I)

Abstract

In almost all cases, Grunwald–Winstein treatments of the specific rates of solvolysis of a series of secondary and tertiary benzylic toluene-p-sulfonates, p-nitrobenzoates, chlorides and bromides exhibit a considerably improved correlation coefficient and a higher F-test value on incorporation of an hI term, where h is the sensitivity towards changes in the recently developed aromatic ring parameter (I). The h values increase on introduction of a second aromatic ring at the α-carbon, on introduction of an electron-withdrawing α-trifluoromethyl group, and on introduction of an electron-supplying aromatic-ring substituent.