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Intramolecular transacylation: fragmentation of protonated molecules via ion‐neutral complexes in mass spectrometry
Author(s) -
Tu YaPing,
Huang Yingying,
Atsriku Christian,
You You,
Cunniff Jack
Publication year - 2009
Publication title -
rapid communications in mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.528
H-Index - 136
eISSN - 1097-0231
pISSN - 0951-4198
DOI - 10.1002/rcm.4108
Subject(s) - chemistry , fragmentation (computing) , protonation , intramolecular force , mass spectrometry , molecule , ion , computational chemistry , collision induced dissociation , polyatomic ion , tandem mass spectrometry , stereochemistry , chromatography , organic chemistry , computer science , operating system
An intramolecular transacylation reaction was observed in the mass spectrometry of molecules containing both benzoyl and carboxymethyl groups on an aromatic heterocyclic core. The reaction is triggered by a dissociative protonation on the heterocyclic ring at the atom (carbon or nitrogen) that bonds to the benzoyl group, leading to an intermediate ion‐neutral complex. The incipient benzoyl cation in the complex migrates to attack the carboxyl group of the neutral partner at the carbonyl or hydroxyl oxygen under thermodynamic or kinetic control, respectively. Elimination of benzoic acid followed by loss of carbon monoxide takes place as a result of the transacylation. Copyright © 2009 John Wiley & Sons, Ltd.