Destabilized carbenium ions. Secondary and tertiary α‐acetylbenzyl cations and α‐benzoylbenzyl cations

Abstract

AbstractThe secondary α‐acetylbenzyl and α‐benzoylbenzyl cations, as well as their tertiary analogues, have been generated in a mass spectrometer by electron impact induced fragmentation of the corresponding α‐bromoketones. These ions belong to the interesting family of destabilized α‐acylcarbenium ions. While primary α‐acylcarbenium ions appear to be unstable, the secondary and tertiaiy ions exhibit the usual behaviour of stable entities in a potential energy well. This can be attributed to a ‘push‐pull’ substitution at the carbenium ion centre by an electron‐releasing phenyl group and an electron‐withdrawing acyl substituent. The characteristic unimolecular reaction of the metastaible secondary and tertiary α‐acylbenzyl cations is the elimination of CO by a rearrangement reaction involving a 1,2‐shift of a methyl group and a phenyl group, respectively. The loss of CO is accompanied by a very large kinetic energy release, which gives rise to broad and dish‐topped peaks for this process in the mass‐analysed ion kinetic energy spectra of the corresponding ions. This behaviour is attributed to the rigid critical configuration of a corner‐protonatei cyclopropanone derivative and a bridged phenonium ion derivative, respectively, for this reaction. For the tertiary α‐acetyl‐α‐methylbenzyl cations, it has been shown by deuterium labelling and by comparison of collisional activation spectra that these ions equilibrate prior to decomposition with their ‘protomer’ derivatives formed by proton migration from the α‐methyl substituent to the carbonyl group and to the benzene ring.