
Organic Mass Spectrometry p. 423 - 427 (1992)
Update date:2022-08-17
Topics:
Jensen, Nancy J.
Haas, George W.
Gross, Michael L.
Fatty acid carboxylates desorbed into the gas phase by fast atom bombardment (FAB) undergo both metastable-ion and collisionally activated dissociation (CAD) to eliminate water.Upon CAD, the water elimination competes with charge-remote fragmentation.Deuterium labeling results are in accord with the elimination occurring via an ion-neutral complex involving hydroxide ion and neutral ketene.Evidence that the precursor of the ion-neutral complex is the enol form of the carboxylate was obtained by forming the enolate directly by decarboxylation of appropriate dicarboxylic acids.The <(M-H-CO2>(1-) ions of these species undergo a more facile elimination of water than do carboxylates desorbed directly upon FAB.
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