Conservation of the skeletal conformation in the ring decomposition of dimethylcyclohexanes

Abstract

By comparing the composition of products formed during the γ-radiolysis of structural and geometrical /cis and trans/ isomers of dimethylcyclohexanes, the relationship between molecular structure and ring decomposition reactions was investigated. The yields of products that exist in geometrical isomeric forms /e.g. 2-butenes, 2-octenes/ were considerably different in the irradiation of cis- and transdimethylcyclohexanes: the products reflected the conformation of the decomposed molecule. It was assumed that the ring decomposition is a very fast process taking place within about 1 ps. If biradical intermediates are involved in the reactions, their further transformations occur before attaining conformational equilibrium.