Experimental and theoretical study of the gas-phase interaction between ionized nitrile sulfides and pyridine |
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Authors: | Gerbaux Pascal Haverbeke Yves Van Flammang Robert |
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Affiliation: | Organic Chemistry Laboratory, University of Mons-Hainaut, Mons, Belgium. pascal.gerbaux@umh.ac.be |
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Abstract: | The gas-phase reactivity of ionized nitrile sulfides, R-C≡N+-S·, towards neutral pyridine was studied both experimentally (six sector hybrid mass spectrometer) and theoretically (density functional theory and Møller-Plesset ab initio calculations). An ionized sulfur atom transfer and a cycloaddition process respectively yielding ionized pyridine N-thioxide and a thiazolopyridinium cation were observed. Whereas the very efficient S·+ transfer reaction probably involves the intermediacy of several ion-molecule complexes, the thiazolopyridinium ion formation is likely to be initiated by an electrophilic attack of the R-C≡N+-S· ion on the nitrogen atom of pyridine; the resulting intermediate then undergo an intramolecular substitution of an α-hydrogen atom by the sulfur atom. |
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