Tautomerism of several thioamides was studied by mass spectrometry. The analysis of the corresponding mass spectra allowed some fragmentations to be assigned to specific tautomers and heats of tautomerization to be determined through temperature effects and electron energy studies. Experimental determinations were strongly supported by theoretical calculations. AM1 semi-empirical results indicate that the thioamide-thioimidol equilibrium can be studied by mass spectrometry. Also, additional evidence was obtained regarding tautomerism occurrence between neutral species.
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