Tautomerism of Aza Cycles: II.1 Synthesis and Structure of 5-Substituted 3-(2-HydroxyethylsulfanyI)-1H-1,2,4-triazoles and Their Salts. Preference of the 1H,4H-1,2,4-Triazolium Tautomers

摘要

New complexing agents, potentially tautomeric 3-(2-hydroxyethylsulfanyl)-1H-1,2,4-triazole, its 5-methyl-and 5-phenyl-substituted analogs, and some their salts, were synthesized, and their structure was discussed on the basis of the ~1H and ~(13)C NMR, IR, and mass spectra, X-ray diffraction data, and published data. In keeping with the rule formulated previously for N-unsubstituted 1,2,4-triazoles having dissimilar substituents, the synthesized compounds were found to exist as 3-(2-hydroxyethylsulfanyl)-5-R-1H-1,2,4-triazole tautomers (3-RA-5-RD-1H-1,2,4-triazoly). They are protonated at the nitrogen atom in position 4 of the triazole ring. The ~1H and ~(13)C NMR spectra of these compounds in trifluoroacetic acid suggest the presence of two forms due to equilibrium between the neutral and protonated species. Analysis of the crystallographic data for the triazolium salts and published data showed preference of the 1H,4H-1,2,4-triazolium tautomer.