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On the Loss of SH • from the Molecular Ions of S ‐Alkyl Thioformates: Experimental Evidence for the Generation of Hydroxycarbenium Ions
Author(s) -
Lahem Driss,
Flammang Robert,
Van Haverbeke Yves,
Nguyen MinhTho
Publication year - 1997
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/(sici)1097-0231(19970228)11:4<373::aid-rcm809>3.0.co;2-x
Subject(s) - chemistry , ion , formylation , alkyl , electron ionization , mass spectrum , mass spectrometry , tandem mass spectrometry , alkane , photochemistry , polyatomic ion , tandem , ionization , hydrocarbon , organic chemistry , catalysis , chromatography , materials science , composite material
A series of S ‐alkyl thioformates, HC(O)SR, has been synthesized by formylation of alkane thiols and their behaviour upon electron impact has been investigated by using tandem mass spectrometry methodologies. When R > CH 3 , a prominent loss of a SH • radical is observed in the ion source as well as in the field‐free regions. This reaction, which requires an important preliminary rearrangement of the molecular ion, gives hydroxycarbenium ions as evidenced by collisional‐activation spectra and consecutive collisional‐activation experiments. A mechanism involving ionized thietane intermediates is proposed. © 1997 John Wiley & Sons, Ltd.