Four‐centre skeletal rearrangements in the mass spectra of thioanilides

Publisher Website
Google Scholar
Abstract
Abundant peaks in the mass spectra of thioanilides involve loss of a substituted thiophenoxy radical by a process involving aryl migration from nitrogen to sulfur (a four‐centre skeletal rearrangement). The effects of substituents on this process have been studied. Substituents in the amide ring, in the acid part of the molecule and on the nitrogen atom were studied. Four‐centre aryl migrations seem to be favoured if the aryl group migrates from one atom to either a more polarizable or a more electronegative atom, and in the case of thioanilides this migration is more important in tertiary compounds than in secondary compounds.