Homolytic rearrangement and symmetrization of acetone butyl phenyl mercaptole and butyl p-tolyl mercaptole

Abstract

1. Mixed mercaptoles of type CH3C(SAlk) (SAlk)(SAr)CH3 when heated with tert-butyl peroxide undergo homolytic “symmetrization” with the formation of a mixture of the two symmetrical mercaptoles. The reverse reaction — homolytic conversion of a mixture of two symmetrical mercaptoles with the formation of the mixed mercaptole — was accomplished under the same conditions. Together with the indicated reactions, the mercaptoles undergo rearrangement with the formation of 1,2-bisalkyl(aryl)thiopropanes,with a 1,2-migration of the alkyl(aryl)thio groups. 2. In the rearrangement of the mixed acetone alkyl(aryl)mercaptoles it is the arylthio group that migrates preferentially.