Substituent effect on the tautomerism of 5-acetyl-2-methoxydihydropyrimidines: experimental NMR and computational DFT studies

Abstract

Some selected 5-acetyl-2-methoxydihydropyrimidines (DHPMs) are synthesized and the electronic effect of the substituent on the 4-position of the heterocyclic ring on the ratio of the possible tautomeric forms is investigated using dynamic NMR experiments. The results of this study indicate that these compounds coexist in two tautomeric 1,4- and 3,4-forms in the solution and their tautomeric ratios depend on the electronic nature of the additional substituent on the 4-phenyl substituent, the nature of solvent used for NMR study and also on the temperature. B3LYP/6–31 ++G** computational studies in the gas and solution phases elucidate the effect of the additional substituent on the phenyl ring on the structural, electronic and bonding characteristics of the tautomeric forms in these compounds. Furthermore, solvation of these DHPMs determines the relative stabilities of the two tautomers in the solution phase, which cannot be probed by model solvents adopted in SCRF calculations.