J. Org. Chem. 67, 1515-1519 (2002)

DOI: 10.1021/jo016069m

Influence of Intermolecular Hydrogen Bonds on the Tautomerism of Pyridine Derivatives 

The effect of the dimerization, by hydrogen-bond (HB) complexation, on the tautomerism of 2-hydroxypyridine and a series 2-aminopyridines has been carried using ab initio methods. The results obtained for 2-hydroxypyridine fit satisfactorily with the experimental data and show that the 2-pyridone/2-pyridone homodimer complex is the most stable. For 2-aminopyridines, the effect of the substituent on the amino group has been investigated. For the monomers studied, the most favorable tautomer is the 2H; however, with electronegative substituents, the 1H/1H homodimers are more stable than the corresponding 2H/2H ones. The atom in molecule methodology has been used to characterize the HBs formed. Exponential relationships have been found between the electron density and its laplacian at the HB critical point vs the HB distance.