Abstract
The geometric, charge, and electronic characteristics of 7-substituted pyrido[1,2-a]benzimidazoles and their cations were calculated using the DFT method with the B3LYP functional in the 6-31G** basis set. High regioselectivity of the reactions between the condensed imidazole derivatives and electrophilic agents was explained by the results of quantum chemical simulation. It was concluded that the S EAr reaction was orbitally controlled. According to Fukuís concept, the reaction center of the electrophilic attack was the C(8) atom of the heterocyclic system, which agreed well with the experimental data.
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References
R. Taylor, Electrophilic Aromatic Substitution, Wiley, Chichester, 1990, 513 pp.
F. S. Carey, R. J. Sundberg, Adv. Org. Chem. Part A, Springer Science, Virginia, 2007, 1203 pp.
S. Caron, Practical Synthetic Organic Chemistry: Reactions, Principles, and Techniques, Wiley, New Jersey, 2011, 872 pp.
T. Yamato, K. Fujita, H. Kamimura, Tetrahedron, 1995, 51, 9851
R. Mundla, Tetrahedron Lett., 2000, 41, 4277
E. Yu. Chernova, G. A. Mokrushina, O. N. Chupakhin, S. K. Kotovskaya, V. I. Ilénko, O. T. Andreeva, E. I. Boreko, G. V. Vladyko, L. V. Korobchenko, A. D. Garagulya, V. M. Dukhovnaya, Pharm. Chem. J. (Engl. Transl.), 1991, 25, 44 [Khim.-Farm. Zh., 1991, 25, 50]
H. Suzuki, M. Sawaki, R. Sakimoto, J. Chem. Soc., 1971, 1509
J. S. Dewar, P. M. Maitlis, J. Chem. Soc., 1957, 2518
A. Kobe, H. Levin, Ind. Eng. Chem., 1950, 42, 352.
R. S. Begunov, A. A. Sokolov, V. O. Belova, A. N. Fakhrutdinov, A. S. Shashkov, I. V. Fedyanin, Tetrahedron Lett., 2015, 56, 5701.
N. S. Prostakov, A. V. Varlamov, D. L. S. Nende, A. P. Krapivko, A. A. Fomichev, N. I. Golovtsov, I. V. Shendrik, A. E. Aliev, B. B. Singkh, J. Org. Chem. USSR (Engl. Transl.), 1990, 26, 1351 [Zh. Org. Khim., 1990, 26, 1351]
H. Saunders, J. Chem. Soc., 1955, 3275.
P. Hohenberg, W. Kohn, Phys. Rev., 1964, 136, B864
W. Kohn, L. Sham, Phys. Rev., 1965, 140, A1133.
A. D. Becke, J. Chem. Phys., 1993, 98, 5648.
B. A. Miehlich, H. S. Savin, H. Preuss, Chem. Phys. Lett., 1989, 157, 200.
M. Mueller, Fundamentals of Quantum Chemistry. Molecular Spectroscopy and Modern Electronic Structure Computation, Kluwer Academic Publishers, New York, 2002.
A. A. Granovsky, Firefly version 8, http://classic.chem.msu.su/gran/firefly/index.html
W. Schmidt, K. K. Baldridge, J. A. Boatz, S. T. Elbert, M. S. Gordon, J. H. Jensen, S. Koseki, N. Matsunaga, K. A. Nguyen, S. Su, T. L. Windus, M. Dupuis, J. A. Montgomery, J. Comput. Chem., 1993, 14, 1347.
R. A. Abramovitch, J. G. Saha, Adv. Heterocycl. Chem., 1966, 6, 229.
K. Fukui, T. Yonezawa, Ch. Nagata, H. Shingu, J. Chem. Phys., 1954, 22, 1433.
M. Breza, V. Milata, ARKIVOC, 2005, 9, 80.
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Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 0644—0647, March, 2016.
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Begunov, R.S., Sokolov, A.A., Belova, V.O. et al. Quantum chemical study of regioselectivity of reactions of substituted pyrido[1,2-a]benzimidazoles with electrophiles. Russ Chem Bull 65, 644–647 (2016). https://doi.org/10.1007/s11172-016-1349-4
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DOI: https://doi.org/10.1007/s11172-016-1349-4