Andrea Szabó, V. I. Češljević, and Attila Kovács

Tautomerism, hydrogen bonding and vibrational properties of 4-acetyl-3(5)-amino-5(3)-methylpyrazole.

Chemical Physics, 270 (2001) 67-78.

The structure and molecular vibrations of 4-acetyl-3(5)-amino-5(3)-methylpyrazole have been investigated by quantum chemical calculations and vibrational spectroscopy. The calculations predicted a predominance of the 5-amino-3-methyl form in the tautomeric equilibrium, however, the energy difference between the two tautomers is rather small, 2 kJ/mol at the B3-LYP/6-311++G** level of the theory. The most stable conformers of each tautomer are stabilized by intramolecular hydrogen bonding. This interaction plays an important role also in the tautomeric equilibrium contributing significantly to the stability of the 5-amino-3-methyl tautomer. Another characteristics of the hydrogen bonding is its strengthening effect on the conjugation of the NH₂ and C=O groups with the pyrazole ring.

The molecular vibrations of the title compound have been analysed by means of the scaled quantum mechanical (SQM) method. Using joint theoretical and experimental information the FT-IR and FT-Raman spectra of solid 4-acetyl-3-amino-5-methylpyrazole have been assigned.