Theoretical study of the hydrolysis of ethyl benzoate in acidic aqueous solution using the QM/MC/FEP method

Comparative Analysis of Acyclovir Esters Stability in Solutions: The Influence of the Substituent Structure, Kinetics, and Steric Effects

“…A similar two‐step mechanism was proposed for acidic hydrolysis of ethyl acetate and ethyl benzoate studied by a model cluster consisting of an ester, a H 3 O + cation and 15 water molecules . However, in case of three explicit water molecules included in the modeled reaction, the hydrolysis proceeds in one step and the tetrahedral intermediate does not form in the acid‐catalyzed hydrolysis of ethyl benzoate . Calculated values of activation energy (Δ E ‡ ) of the hydrolysis reaction of methyl acetate, ethyl acetate, and ethyl benzoate in the proposed models of reaction were 18.3 , 19.18 , and 25.10 kcal mol −1 , respectively.…”

“…Computational studies suggest that the ester hydrolysis mechanisms of aliphatic and aromatic acids for the destruction of the ester bond could be different depending on the accepted model of the reaction . The mechanism proposed for hydrolysis of methyl acetate in acidic conditions assumes the involvement of two water molecules and the formation of a tetrahedral intermediate.…”

Theoretical and experimental mechanistic study of water molecule involvement in the Prilezhaev reaction

“…We adopted the QM/MC/FEP method, [20][21][22][23][24][25] wherein quantum chemical calculations are applied to explain the implicit solvent effects on chemical reactions. This method considers the changes in the interactions between the solute and solvent along the IRCs.…”

“…We have provided results that are in good agreement with experimental results. [21][22][23][24][25] The present study incorporates the explicit solvent effects of water molecules present in the reaction system of the Prilezhaev reaction and analyses the reaction mechanism, including implicit solvent effects on the reaction, using QM/MC/FEP and SCRF methods. The effects of water and solvent molecules on the reaction mechanism are discussed based on a comparison of the calculated and experimental results.…”