Density functional theory study of tautomerization of 2‐aminothiazole in the gas phase and in solution

The amino/imino tautomeric equilibrium in the isolated, mono‐, di‐, and trihydrate forms and dimer of 2‐aminothiazole, and the effects of hydration or self‐assistance on the transition state structures corresponding to proton transfer from the amino to imino form, have been investigated by the B3LYP method in conjunction with 6‐31+G( d,p ) and 6‐311+G(3 df ,2 p ) basis sets in the gas phase and in solution. The amino form has been found to be the predominant tautomer. The tautomeric barrier heights for water‐ and self‐assisted tautomerization reactions are significantly lower than that from the amino to imino form by the intramolecular proton transfer, showing the catalytic effect of water molecule(s) and the important role of 2‐aminothiazole itself for intermolecular proton transfer. Comparison between the tautomeric barriers demonstrates that the self‐association tautomerization through the dimerization is the most favorable pathway. Bulk solvent effects have been taken into account using the polarizable continuum model (PCM) of water and CCl 4 . The polar medium is favorable for the population of the imino form. The amino/imino equilibrium is also analyzed using the aromaticity index nucleus‐independent chemical shift (NICS); the NICS values for the amino form (about −10 ppm) are more negative than the imino species (about −8 ppm), showing that the amino form is more stable. The time‐dependent density functional theory (TDDFT) calculations of electronic absorption spectra suggest that the λ max of dimer is 255 nm. The oscillator strength of the imino forms is less than the amino form, and increases with the polarity of the solvents. All calculations for the tautomerization of 2‐aminothiazole are in reasonable line with the available experiments. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007