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3‐Aroyl‐5‐hydroxyflavones: synthesis and mechanistic studies by mass spectrometry
Author(s) -
Cardoso Ana M.,
Silva Artur M. S.,
Barros Cristina M. F.,
Almeida Lúcia M. P. M.,
FerrerCorreia A. J.,
Cavaleiro José A. S.
Publication year - 1997
Publication title -
journal of mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 1076-5174
DOI - 10.1002/(sici)1096-9888(199709)32:9<930::aid-jms549>3.0.co;2-e
Subject(s) - chemistry , mass spectrum , fragmentation (computing) , mass spectrometry , ion , molecule , deuterium , hydrogen atom , anisole , polyatomic ion , photochemistry , computational chemistry , medicinal chemistry , stereochemistry , organic chemistry , catalysis , physics , alkyl , chromatography , quantum mechanics , computer science , operating system
The synthesis and mass spectra of three 3‐aroyl‐5‐hydroxyflavones are reported. The interpretation of the mechanistic pathways for the fragmentation of the metastable molecular ions of these compounds was achieved through the analysis of their mass‐analysed ion kinetic energy (MIKE) spectra and of the B 2 / E spectra of a few fragment ions. Labelling of the hydroxyl proton with deuterium and the analysis of the MIKE spectra of a model compound with chlorine atoms in the 2′,6′‐ and 2″,6″‐positions led to a mechanism for the losses of OH • and HCO • which involves hydrogen migration from the 2″‐ or 6″‐position to the 4‐carbonyl oxygen atom. A mechanism for the loss of a neutral molecule of anisole from the molecular ion of the 3‐aroyl‐5‐hydroxyflavone with a methoxyl group in the 4′‐ and 4″‐positions is also suggested. For the flavones with hydrogen or chlorine substituents at these positions, loss of a phenyl (or chlorophenyl) radical occurs instead. © 1997 John Wiley & Sons, Ltd.