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Methylene radical cation transfer from ionized oxirane to CH 3 SCH 3 and C 6 H 5 SCH 3 in the gas phase: Formation of sulphur distonic ions and/or insertion in a carbon–sulphur bond
Author(s) -
van Amsterdam Margot W.,
Zappey Herman W.,
Ingemann Steen,
Nibbering Nico M. M.
Publication year - 1993
Publication title -
organic mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 0030-493X
DOI - 10.1002/oms.1210280108
Subject(s) - thioether , methylene , chemistry , dissociation (chemistry) , polyatomic ion , isomerization , ion , photochemistry , ionization , medicinal chemistry , stereochemistry , organic chemistry , catalysis
The α‐distonic sulphur‐containing ion \documentclass{article}\pagestyle{empty}\begin{document}$ {}^ \cdot {\rm CH}_2 \mathop {\rm S}\limits^ + \left({{\rm CH}_3 } \right)_2 $\end{document} has been generated by transfer of CH 2 +˙from ionized oxirane to dimethyl thioether and distinguished from the molecular ion of ethyl methyl thioether by collision induced dissociation (CID) experiments. In particular, the α‐distonic ion expels CH 2 to a minor extent following collision, whereas the molecular ion of ethyl methyl thioether does not undergo this reaction. The metastable C 3 H 8 S +˙ ions formed by CH 2 +˙transfer to dimethyl thioether and ionization of ethyl methyl thioether decompose by competing losses of CH 3 R˙, CH 4 and C 2 H 4 . The elimination of ethene is taken as evidence for isomerization of the α‐distonic ion to the molecular ion of ethyl methyl thioether prior to spontaneous dissociation. Evidence for the formation of stable α‐distonic sulphur‐containing ions by transfer of CH 2 +˙from ionized oxirane to methyl phenyl thioether has not been obtained. The collision‐induced and spontaneous reactions of the ions formed by CH 2 +˙transfer to methyl phenyl thioether indicate that a mixture of the radical cations of CH 3 C 6 H 4 SCH 3 , C 6 H 5 SCH 2 CH 3 and C 6 H 5 CH 2 SCH 3 is generated implying that attack on the phenyl group occurs in addition to a formal insertion of a methylene entity in a CS bond.