Thione-thiol tautomerism and stability of 2- and 4-mercaptopyridines and 2-mercaptopyrimidines

The possible thione-thiol tautomerism of 2- and 4-mercaptopyridines, 2-mercaptopyrimidine, and 4,6-dimethyl-2-mercaptopyrimidine in solution is studied by means of absorption (UV-VIS) spectroscopy. In accordance with earlier observations, polar solvents and self-association shift the apparent tautom...

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Veröffentlicht in:Canadian journal of chemistry 1990-09, Vol.68 (9), p.1482-1489
Hauptverfasser: Stoyanov, Stefan, Petkov, Ivan, Antonov, Liudmil, Stoyanova, Tatyana, Karagiannidis, Petros, Aslanidis, Paraskevas
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container_end_page 1489
container_issue 9
container_start_page 1482
container_title Canadian journal of chemistry
container_volume 68
creator Stoyanov, Stefan
Petkov, Ivan
Antonov, Liudmil
Stoyanova, Tatyana
Karagiannidis, Petros
Aslanidis, Paraskevas
description The possible thione-thiol tautomerism of 2- and 4-mercaptopyridines, 2-mercaptopyrimidine, and 4,6-dimethyl-2-mercaptopyrimidine in solution is studied by means of absorption (UV-VIS) spectroscopy. In accordance with earlier observations, polar solvents and self-association shift the apparent tautomeric equilibrium significantly towards the thione form. In dilute solutions of nonpolar solvents the thiol form predominates. On standing, significant changes are observed in the absorption spectra of these tautomeric compounds in ethanol, dioxane, and water. The time course of the tautomerization, followed spectrophotometrically, reveals quantitative transformation of the thiol form to the corresponding symmetrical disulfides. The influence of concentration, temperature, and irradiation with indirect sunlight are discussed. This thione-disulfide process is reversible in water, starting either from the tautomeric thione or from its symmetrical disulfide, implying a possible importance in biological systems. Keywords: thione-thiol tautomerism, absorption spectra, thiol-disulfide oxidation, mercaptopyridines and pyrimidines.
doi_str_mv 10.1139/v90-227
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subjects Chemistry
Exact sciences and technology
Miscellaneous
Organic chemistry
Reactivity and mechanisms
title Thione-thiol tautomerism and stability of 2- and 4-mercaptopyridines and 2-mercaptopyrimidines
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