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Electron impact mass spectrometric analysis of mercapturic acid methyl esters. Fragmentation of mercapturic acid methyl esters according to ‘retro‐Michael’ reactions
Author(s) -
Onkenhout W.,
Vermeulen N. P. E.,
Luijten W. C. M. M.,
de Jong H. J.
Publication year - 1983
Publication title -
biomedical mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 0306-042X
DOI - 10.1002/bms.1200101107
Subject(s) - mercapturic acid , chemistry , fragmentation (computing) , mass spectrometry , electron ionization , ion , organic chemistry , cysteine , chromatography , ionization , computer science , enzyme , operating system
The electron impact mass spectral behaviour of 14 synthetically prepared mercapturic acid methyl esters was examined. The most important and characteristic fragmentation reactions are discussed and special emphasis is made on the occurrence and the mechanism of two fragmentation pathways, which were recognized as ‘retro‐Michael’ reactions. In principle, each reaction may result in the formation of two typical ions. In addition, three characteristic ‘key‐ions’ originating from the N ‐acetyl(‐ l ‐)cysteine methyl ester part of the mercapturic acids were recognized in all mercapturic acid methyl esters investigated; these ‘key‐ions’ can most probably be used as a tool for the qualitative as well as the quantitative analysis of mercapturic acids by gas chromatogra–phy mass spectrometry in biological fluids.