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Dissociation of protonated N ‐(3‐phenyl‐2 H ‐chromen‐2‐ylidene)‐ benzenesulfonamide in the gas phase: cyclization via sulfonyl cation transfer
Author(s) -
Wang Shanshan,
Dong Cheng,
Yu Lian,
Guo Cheng,
Jiang Kezhi
Publication year - 2015
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.7420
Subject(s) - chemistry , sulfonyl , protonation , dissociation (chemistry) , imine , medicinal chemistry , electron transfer , photochemistry , radical ion , polar effect , ion , tandem mass spectrometry , mass spectrometry , organic chemistry , catalysis , alkyl , chromatography
Rationale In the tandem mass spectrometry of protonated N ‐(3‐phenyl‐2 H ‐chromen‐2‐ylidene)benzenesulfonamides, the precursor ions have been observed to undergo gas‐phase dissociation via two competing channels: (a) the predominant channel involves migration of the sulfonyl cation to the phenyl C atom and the subsequent loss of benzenesulfinic acid along with cyclization reaction, and (b) the minor one involves dissociation of the precursor ion to give an ion/neutral complex of [sulfonyl cation/imine], followed by decomposition to afford sulfonyl cation or the INC‐mediated electron transfer to give an imine radical cation. Methods The proposed reaction channels have been supported by theoretical calculations and D‐labeling experiments. Results The gas‐phase cyclization reaction originating from the N ‐ to C ‐sulfonyl cation transfer has been first reported to the best of our knowledge. Conclusions For the substituted sulfonamides, the presence of electron‐donating groups (R 2 ‐) at the C‐ring effectively facilitates the reaction channel of cyclization reaction, whereas that of electron‐withdrawing groups inhibits this pathway. Copyright © 2015 John Wiley & Sons, Ltd.