Mass Spectrometric Study of the Gas-Phase Difluorocarbene Expulsion of Polyfluorophenyl Cations via F-Atom Migration

An increasing number of fluorinated drugs, pesticides, and fine chemicals are now produced and applied, especially those containing polyfluorinated aromatic moieties. However, at present, the extent of literature covering the special mass spectrometric behaviors of these compounds remains limited. H...

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Bibliographic Details
Published in:Journal of the American Society for Mass Spectrometry 2013-12, Vol.24 (12), p.1919-1926
Main Authors: Wang, Hao-Yang, Gao, Ying, Zhang, Fang, Yu, Chong-Tian, Xu, Chu, Guo, Yin-Long
Format: Article
Language:English
Subjects:
Analytical Chemistry
Aromatic compounds
Bioinformatics
Biotechnology
Cations - chemistry
Chemistry
Chemistry and Materials Science
Density functional theory
Expulsion
Fine chemicals
Fluorination
Gases - chemistry
Halogenation
Hydrocarbons, Aromatic - chemistry
Hydrocarbons, Fluorinated - chemistry
Ionization
Ions
Mass spectrometry
Models, Molecular
Organic Chemistry
Pesticides
Proteomics
Research Article
Scientific imaging
Spectrometry, Mass, Electrospray Ionization
Spectroscopy
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Summary:An increasing number of fluorinated drugs, pesticides, and fine chemicals are now produced and applied, especially those containing polyfluorinated aromatic moieties. However, at present, the extent of literature covering the special mass spectrometric behaviors of these compounds remains limited. Herein, we report an unexpected but also general gas-phase dissociation mode of polyfluorinated aromatics in mass spectrometry: expulsion of difluorocarbene (50-Da neutral loss). Results from accurate mass measurements, tandem mass spectrometric experiments, and density functional theory (DFT) calculations support an intramolecular F-atom “ring-walk” migration mechanism for gas-phase CF 2 loss. Based on an assessment of the electron ionization-mass spectrometry (EI-MS) data of more than 40 polyfluorinated aromatic compounds from the National Institute of Standards and Technology data bank, we generalized on the substitution group effects on the difluorocarbene dissociation process of polyfluorinated aromatic compounds in EI-MS. These studies have enriched our knowledge of the special gas-phase reactivity of polyfluorinated aromatics and will provide valuable information in further analytical research of these compounds by mass spectrometry. Figure ᅟ
ISSN:1044-0305
1879-1123
DOI:10.1007/s13361-013-0743-5