Cycloalkene budding: Mass spectrometric studies of competitive and dual cycloalkene extrusion reactions from doubly unsaturated aldehyde N, N- dimethylhydrazones

Douglas B. Weibel, Athula B. Attygalle, Laura E. Shevy, Jerrold Meinwald

Research output: Contribution to journalArticlepeer-review

Abstract

Mass spectral fragmentation pathways of four doubly unsaturated aldehyde N, N-dimethylhydrazones were investigated using EI-MS and tandem mass spectrometry (MS/MS) under electron ionization and collisionally activated decomposition (CAD) conditions. Cyclopentene extrusion was found to be slightly favored over cyclohexene loss in a hydrazone capable of losing either cycloalkene. Evidence for the regeneration of a chain-shortened iminium radical cation as a result of cycloalkene extrusion was provided by studying substrates 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 macrocyclic diene, a rapid cascade of cycloalkene budding accounts best for the experimental observations. Copyright (C) 2000 John Wiley and Sons, Ltd.

Original languageEnglish
Pages (from-to)1105-1109
Number of pages5
JournalRapid Communications in Mass Spectrometry
Volume14
Issue number13
DOIs
StatePublished - 2000

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