Cycloalkene budding: mass spectrometric studies of competitive and dual cycloalkene extrusion reactions from doubly unsaturated aldehyde N,N-dimethylhydrazones
Db. Weibel et al., Cycloalkene budding: mass spectrometric studies of competitive and dual cycloalkene extrusion reactions from doubly unsaturated aldehyde N,N-dimethylhydrazones, RAP C MASS, 14(13), 2000, pp. 1105-1109
Mass spectral fragmentation pathways of four doubly unsaturated aldehyde N,
N-dimethylhydrazones were investigated using EI-MS and tandem mass spectrom
etry (MS/MS) under electron ionization and collisionally activated decompos
ition (CAD) conditions. Cyclopentene extrusion was found to be slightly fav
ored over cyclohexene loss in a hydrazone capable of losing either cycloalk
ene, Evidence for the regeneration of a chain-shortened iminium radical cat
ion as a result of cycloalkene extrusion was provided by studying substrate
s capable of undergoing successive cycloalkene budding sequences. EI-MS of
these compounds shows sequential loss of both cyclopentene and cyclohexene,
in accord with expectations for a cascade mechanism. Although these MS/MS
experimental results are also compatible with alternative mechanisms which
would entail the simultaneous loss of both neutral cycloalkenes or of a mac
rocyclic diene, a rapid cascade of cycloalkene budding accounts best for th
e experimental observations. Copyright (C) 2000 John Wiley & Sons, Ltd.