Bridged polycyclic compounds. 88. Multiple intermediates in solvolysis of certain bridged bicyclic and tricyclic compounds

Abstract

Acetolyses of 7-chloromethyl- and 7-bromomethyldibenzobicyclo[2.2.2]octatrienes, 8-chloro- and 8-bromo-7-methylenedibenzobicyclo[2.2.2]octa-2,5-dienes, 4-bromo-8-methylenedibenzobicyclo[3.2.1]octa-2,6-diene, and 2-chlorodibenzotricyclo[3.2.2.02,4]nonadiene were carried out. The results observed were consistent with the involvement of two carbocations interconverting by a Wagner–Meerwein rearrangement, and with the absence of the 1-dibenzosemibullvalenylcarbinyl cation, which is the cyclopropylcarbinyl isomer of one of the cations produced. The preparations of the reactants and products are described.