Journal of Physical Chemistry, Vol.100, No.40, 16141-16146, 1996
Tautomeric Equilibria of Hydroxypyridines in Different Solvents - An Ab-Initio Study
The solvent dependence of the tautomeric equilibria of 2-, 3- and 4-hydroxypyridines is investigated by means of self-consistent reaction field (SCRF) theory. The tautomeric equilibrium constants (K-T) in cyclohexane, chloroform, and acetonitrile are predicted at both the Hartree-Fock (HF) and the second-order Moller-Plesset perturbation theory (MP2) levels, It is found that log K-T is linearly dependent upon the solvent polarity as measured by the Kosower Z parameter, in agreement with earlier experimental findings. Based on this relation, log K-T is predicted to be 1.72, 0.86, and 5.65 for 2-, 3-, and 4-hydroxypyridines, respectively, in aqueous solutions.