Conclusions
-
1.
The mechanisms of the reaction of aminolysis of esters in aprotonic medium were analyzed by the CNDO/BW method. The profiles of the potential surfaces of the noncatalytic and catalytic pathways of the reaction were calculated, and an estimate was given for the values of their activation energy, which agree with the experimental data.
-
2.
The limiting step in the reaction is intramolecular transfer of a proton from a nucleophilic reagent to a leaving group; the noncatalytic reaction practically cannot take place. Catalysis according to the mechanism of cyclic proton transfer and with the participation of a proton acceptor is the most effective.
Similar content being viewed by others
Literature cited
M. Bender, Mechanisms of the Catalysis of Nucleophilic Reactions of Carboxylic Acid Derivatives [Russian translation], Mir (1964).
T. Bruce and S. Benkovich, Mechanisms of Bioorganic Reactions [Russian translation], Mir (1970).
V. Jenks, Catalysis in Chemistry and Enzymology [Russian translation], Mir (1972).
K. Ya. Burshtein and Yu. I. Khurgin, Izv. Akad. Nauk SSSR, Ser. Khim., 579 (1974).
M. G. Dmitrieva and Yu. I. Khurgin, Izv. Akad. Nauk SSSR, Ser. Khim., 1174 (1965).
F. M. Menger and J. H. Smith, J. Amer. Chem. Soc.,94, 3824 (1972).
R. J. Boyd and M. A. Whitehead, J. Chem. Soc., Dalton Trans., 73 (1972).
M. Gordon, J. G. Miller, and A. R. Day, J. Amer. Chem. Soc.,70, 1946 (1948).
Ya. K. Syrkin and I. I. Moiseev, Usp. Khimii,27, 717 (1958).
L. M. Litvinenko, D. M. Aleksandrova, and N. I. Pilyuk, Ukr. Khim. Zh.,25, 81 (1959).
M. G. Dmitrieva, Dissertation [in Russian], Moscow (1966).
Author information
Authors and Affiliations
Additional information
Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1687–1692, August, 1974.
Rights and permissions
About this article
Cite this article
Burshtein, K.Y., Khurgin, Y.I. Quantum chemical study of the mechanisms of the reaction of aminolysis of esters in aprotonic medium. Russ Chem Bull 23, 1613–1617 (1974). https://doi.org/10.1007/BF00923174
Received:
Issue Date:
DOI: https://doi.org/10.1007/BF00923174