INTRAMOLECULAR NUCLEOPHILIC PARTICIPATION - A COMPARATIVE-STUDY OF THE NUCLEOPHILIC PARTICIPATING CAPACITY OF SEVERAL NEW ORTHO SUBSTITUENTS IN BENZHYDRYL BROMIDE SOLVOLYSIS

Rate studies for the solvolysis of several new ortho- and para-substit uted benzhydryl bromides in 80% aq. acetone have been conducted at two different temperatures. The carbophenoxy, 4-nitrocarbophenoxy, 4-chlo rocarbophenoxy and 4-methylcarbophenoxy groups present at the ortho-po sition in benzhydryl bromide solvolyse faster than those present at th e para-position. The results are further supported by the activation p arameters evaluated for these compounds. A discussion of the various s olvolysis mechanisms is presented in which it is proposed that the obs erved rate effects of these similarly constituted but electronically d ifferent substituents result from the variation in the nucleophilic ca pacity of these groups.