Double Bond Migration to Methylidene Positions During Electron Ionization Mass Spectrometry of Branched Monounsaturated Fatty Acid Derivatives

Overview

Journal J Am Soc Mass Spectrom

Specialty Chemistry

Date 2009 Sep 15

PMID 19747846

Citations 1

Authors

Jean-Francois Rontani

Nathalie Zabeti

Claude Aubert

Affiliations

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Abstract

Electron ionization mass spectra of several monounsaturated methyl-branched fatty acid methyl and trimethylsilyl esters were examined. These spectra exhibited some intensive fragment ions, whose formation could be explained after double-bond migration to methylidene position. This preferential migration (substantiated by deuterium labeling) acts significantly in the case of monounsaturated fatty acid methyl and trimethylsilyl esters possessing a methyl branch localized between the penultimate and the C(4) positions (relative to the ester group), whatever the position of the double-bond. Allylic cleavage and gamma-hydrogen rearrangement of the ionized methylidene group thus formed afforded very interesting fragment ions, which could be particularly useful to determine branching positions of monounsaturated methyl-branched fatty acid methyl and trimethylsilyl esters without additional treatment.

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