Intramolecular transacylation: fragmentation of protonated molecules via ion-neutral complexes in mass spectrometry.
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.
Tu
Ya-Ping
YP
Drug Metabolism and Pharmacokinetics, Genelabs Technologies, Inc., 505 Penobscot Drive, Redwood City, CA 94063, USA. Yaping.5.Tu@gsk.com
Huang
Yingying
Y
Atsriku
Christian
C
You
You
Y
Cunniff
Jack
J
D000215:Acylation; D006841:Hydrocarbons, Aromatic / Q000737:chemistry*; D007477:Ions / Q000737:chemistry*; D013058:Mass Spectrometry / Q000379:methods*; D011522:Protons
D006841:Hydrocarbons, Aromatic; D007477:Ions; D011522:Protons