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Electron ionization‐induced loss of SO 2 from 2‐nitrodiaryl sulfides
Author(s) -
Lambert P.H.,
Bertin S.,
Lacoste J.M.,
Volland J.P.,
Krick A.,
Furet E.,
Botrel A.,
Guenot P.
Publication year - 1998
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(199803)33:3<242::aid-jms627>3.0.co;2-g
Subject(s) - chemistry , dissociation (chemistry) , ion , electron ionization , aryl , nitrene , moiety , mass spectrum , sulfide , ionization , mass spectrometry , computational chemistry , medicinal chemistry , stereochemistry , organic chemistry , alkyl , catalysis , chromatography
Electron ionization‐induced loss of SO 2 from 2‐nitrodiphenyl sulfide leads to the same ionic structure, or mixture of structures, as loss of N 2 from the molecular ion of N 1 ‐phenylbenzotriazole. Ab initio calculations are in favor of the [C 6 H 4 —N—C 6 H 5 ] + • distonic nitrenium radical cation instead of the N ‐phenylbenzo‐Δ 2 ‐azirinium structure for the product ion. Collisionally activated dissociation mass‐analyzed ion kinetic energy (CAD‐MIKE) spectra of the four chloro isomers [3‐ or 4‐Cl—C 6 H 3 —N—C 6 H 5 ] + • and [C 6 H 4 —N—C 6 H 4 ‐3 or 4‐Cl] + • show that these ions are non‐interconverting structures and eliminate regioselectively their nitrene moiety. Comparison with the CAD‐MIKE spectra of the product ions of the elimination of N 2 from N 1 –3(or 4)‐chlorophenylbenzotriazoles demonstrates that the loss of SO 2 from 2‐nitrophenyl aryl sulfides occurs in the gas phase via an ipso rearrangement involving a [1,4] migration of the aryl group. © 1998 John Wiley & Sons, Ltd.