DFT investigation of the amino/imino proton transfer process of 2-amino-2-oxazolin-4-one in gas phase and solution

Abstract

Density functional theory (DFT) at the B3LYP-6-311[Formula: see text]G(3df,2p)//6-311[Formula: see text]G(d,p) level of theory in the gas phase and solution was performed to investigate the relative stabilities of all possible tautomers of 2-amino-2-oxazolin-4-one. Five different paths have been proposed to investigate the amino/oxo [Formula: see text] imino/oxo proton transfer (PT) process. These paths are direct, mono-, di- and tri-water-assisted and self-assistance (dimerization) PT process. A clear catalytic effect has been observed when the introduction of water molecules and self-dimerization are taken place. Furthermore, barrier energies, equilibrium constants and reaction rate constants of the PT process between amine/oxo and imine/oxo tautomers of the self-assistance and in the presence of one, two and three water-assisted molecules were calculated. The computed activation barriers in the presence of water molecules are about 35–45 kcal/mol lower than those in the isolated case. In addition, the effective rate of the T1 [Formula: see text] T2 processes were also recorded, compared and discussed. Finally, time-dependent–DFT (TD–DFT) was performed to determine the electronic absorption spectra of all species under probe. A reasonable agreement with the available experiments was also achieved.