Zur McLafferty-Umlagerung bei Radikalkationen von Phenylpyridylalkanonen
Richter, Bernd; Schwarz, Helmut
A detailed investigation concerning the genesis of McLafferty rearrangement products from molecular ions of phenyl pyridyl alkanones reveals the following features: 1) The various products are not formed by competitive dissociations of the molecular ion. Most of the relevant fragment ions are generated from the primary McLafferty product of a hydrogen transfer to the ionized carbonyl group (M+·→m/z 163, ion k). The ion k plays a decisive role for the generation of the abundant product ions at m/z 93 (ion g) and m/z 106 (ion s) both of which are formed by further dissociation of k. Details of the mechanisms for the decomposition of k are obtained by investigating [D]-labelled isotopomers, the analysis of low and high resolution data, the application of MIKE and CA spectra. The problem of keto/enol tautomerism between some ions, relevant in this context, is discussed and it is shown that these isomerization processes are not involved. A detailed description is given for the syntheses of various [D]-labelled phenyl pyridyl alkanones.
