Theoretical studies on the hydrolysis of urea in acid solution

Mechanisms of the hydrolysis of urea have been investigated using the MNDO and AMI methods. All geometries were fully optimized and the transition states were characterized by calculating force constants. The results showed that: (i) The unimolecular decomposition process via the direct intramolecular proton transfer is preferred to both the A1 and the bimolecular nucleophilic attack by water, in agreement with the experimental results of Shaw et al. in the low acidity medium. (ii) The diprotonated form of urea exists as an equilibrium species, which undergoes the A2 type hydrolysis more favorably than the monoprotonated form, as Moodie et al. found in the intermediate acidity medium. (iii) The A2 hydrolysis of the monoprotonated form is very similar to those of acetamide and methyl carbamate. (iv) As the number of the solvate water molecules increases, the activation barrier for the A2 process of the monoprotonated form increases while that for the unimolecular decomposition of the free base form decreases, indicating a possibility of the barrier height reversal in the bulk solvent in favor of the latter process, thus accommodating all the experimentally found trends in the urea hydrolysis. The A1 mechanisms involving six‐membered ring type intermediates can be ruled out as untenable since no such equilibrium species was obtained by both the MNDO and AM1 calculations.