Conclusions
-
1.
It was shown on the basis of quantum-chemical analysis by the LCAO-MO SCF method in the INDO approximation that the complexation of acyloxyl radicals with copper(II) salts and also their combination with chlorine atoms are factors which lead to the stabilization of these radicals and to the possibility of the realization of reactions with retention of the carboxy1 function.
-
2.
In the radical-cation RC(O)OH+ generated during the one-electron oxidation of carboxylic acids RCOOH the unpaired electron is concentrated mainly at the carbonyl oxygen atom, while in the acyloxyl radical RC(O)O it is delocalized at both oxygen atoms.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
Literature cited
Yu. A. Serguchev and I. P. Beletskaya, Usp. Khim.,49, 2257 (1980).
R. A. Sheldon and J. K. Kochi, J. Am. Chem. Soc.,92, 493 (1970).
P. S. Skell and D. D. May, J. Am. Chem. Soc.,105, 3999 (1983).
G. L. Nikishin, I. V. Svitanko, and E. I. Troyanskii (Troyansky), J. Am. Chem. Soc., Perkin Trans.,2, 595 (1983).
A. I. Ioffe, É. I. Troyanskii, and G. I. Nikishin, Izv. Akad. Nauk SSSR, Ser. Khim., 1661 (1987).
V. E. Zubarev, É. I. Troyanskii, and G. I. Nikishin, Izv. Akad. Nauk SSSR, Ser. Khim., 2630 (1986).
G. M. Zhidomirov, P. V. Schastnev, and N. D. Chuvylkin, Quantum-Chemical Calculations of Magnetic-Resonance Parameters. Free Radicals [in Russian], Nauka, Novosibirsk (1978), Chap. 2.
N. D. Chuvylkin, Zh. Fiz. Khim.,59, 1085 (1985).
L. L. Miller and V. Ramachandran, J. Org. Chem.,39, 369 (1974).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Troyanskii, É.I., Chuvylkin, N.D., Khanchina, T.Y. et al. Quantum-chemical analysis of the factors affecting the stabilization of acyloxyl radicals in oxidizing systems. Russ Chem Bull 37, 1393–1396 (1988). https://doi.org/10.1007/BF00962748
Received:
Issue Date:
DOI: https://doi.org/10.1007/BF00962748