A theoretical study of solvent effects on tautomerism and electronic absorption spectra of 3‐hydroxy‐2‐mercaptopyridine and 2,3‐dihydroxypyridine

Abstract

AbstractThe tautomerization equilibria of 3‐hydroxy‐2‐mercaptopyridine (HMP) and 2,3‐dihydroxypyridine (DHP) in vacuo and in ethanol solution have been studied using the density functional theory (DFT) at B3LYP/6‐31G(d) level. The results indicate that the thione form of HMP and the keto form of DHP are the most stable tautomers in the equilibrium, and the energy barrier for the thiol–thione and enol–keto proton transfer decreases significantly when the tautomerism is mediated by a specific ethanol molecule in solution. The time‐dependent density functional theory—polarizable continuum model (TDDFT‐PCM) calculations on all tautomers of HMP and DHP in vacuo and in ethanol have assigned the lowest π → π* excitations of thione and keto tautomers to the observed absorption bands of HMP and DHP in solutions. The solvation is predicted to have relatively small effect on these π → π* excitations in ethanol. © 2004 Wiley Periodicals, Inc. J Comput Chem 25: 1833–1839, 2004