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Monosubstituted benzenes. Some features of the electron density distribution obtained byab initio calculations

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Abstract

A comparative analysis was made of the electron density distribution in monosubstituted benzenes by the nonempirical LCAO-MO SCF STO-3G method. It was shown that the effective charge that appears at the carbon atoms of the benzene ring as a result of introduction of the substituent is divided into π and σ components in the same proportions, irrespective of the position of the carbon atoms (ortho, meta, para). It was established that there are also linear relationships between the π charges of theortho, meta, andpara carbon atoms of monosubstituted benzenes. Thus, the changes in all the π and σ charges of theortho, meta, andpara carbon atoms during substitution in benzene are related linearly to each other. The obtained equations in the generalized form reflect the response of the benzene ring to substitution.

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Literature cited

  1. 1.

    R. T. C. Brownlee and R. W. Taft,J. Am. Chem. Soc. 92, No. 24, 7007 (1970).

  2. 2.

    W. J. Hehre, R. W. Taft, and R. D. Topsom,Progr. Phys. Org. Chem. 12, 159 (1976).

  3. 3.

    A. Hald,Mathematical Statistics with Technical Applications [Russian translation], IL, Moscow (1956).

  4. 4.

    W. J. Hehre, L. Radom, and J. A. Pople,J. Am. Chem. Soc. 94, No. 5, 1496 (1972).

  5. 5.

    W. F. Reynolds, P. G. Mezey, and G. K. Hamer,Can. J. Chem. 55, No. 3, 522 (1977).

  6. 6.

    V. A. Palm,Fundamentals of Quantitative Theory of Organic Reactions [in Russian], Khimiya, Leningrad (1977).

  7. 7.

    W. J. Hehre, M. Taagepera, R. W. Taft, and R. D. Topsom,J. Am. Chem. Soc. 103, No. 6, 1344 (1981).

  8. 8.

    G. Butt and R. D. Topsom,J. Mol. Struct. 164, 399 (1988).

  9. 9.

    T. Silvestro and R. D. Topsom,J. Mol. Struct. 206, 309 (1990).

  10. 10.

    A. Pross, L. Radom, and R. W. Taft,J. Org. Chem. 45, No. 5, 818 (1980).

  11. 11.

    P. J. Mezey and W. F. Reynolds,Can. J. Chem. 55, No. 5, 1567 (1977).

  12. 12.

    S. Bohm and J. Kulthan,Int. J. Quant. Chem. 26, No. 1, 21 (1984).

  13. 13.

    M. Taagepera, K. D. Summerhays, W. J. Hehre, and R. D. Topsom,J. Org. Chem. 46, No. 5, 891 (1981).

  14. 14.

    G. Butt, R. D. Topsom, and R. W. Taft,J. Mol. Struct. 153, 141 (1987).

  15. 15.

    S. Marriott and R. D. Topsom,Aust. J. Chem. 39, No. 7, 1157 (1986).

  16. 16.

    G. H. Penner, P. George, and C. W. Bock,J. Mol. Struct. 152, 201 (1987).

  17. 17.

    S. Marriott, A. Silvestro, and R. D. Topsom,J. Chem. Soc. Perkin Trans. 2, No. 4, 457 (1988).

  18. 18.

    S. Marriott, T. Silvestro, R. D. Topsom, and C. W. Bock,J. Mol. Struct. 151, 15 (1987).

  19. 19.

    N. A. Ogorodnikova, A. S. Peregudov, É. I. Fedin, and D. N. Kravtsov,Izv. Akad. Nauk, Ser. Khim., No. 10, 2219 (1989).

  20. 20.

    N. A. Ogorodnikova, A. A. Koridze, and S. P. Gubin,J. Organometal. Chem. 215, No. 3, 293 (1981).

  21. 21.

    R. W. Taft, E. Pross, I. R. Fox, et al.,J. Am. Chem. Soc. 85, No. 20, 3146 (1963).

  22. 22.

    N. A. Ogorodnikova, B. A. Kvasov, and D. N. Kravtsov,Izv. Akad. Nauk, Ser. Khim., No. 6, 1434 (1988).

  23. 23.

    A. Streitwieser, Jr., and E. R. Vorpagel,Collection Czech. Chem. Comm. 53, No. 9, 1961 (1988).

  24. 24.

    R. F. W. Bader,Acc. Chem. Res. 18, No. 1, 9 (1985).

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Additional information

A. N. Nesmeyanov Institute of Heteroorganic Compounds, Russian Academy of Sciences, 117813 Moscow. Translated fromIzvestiya Akademii Nauk, Seriya Khimicehskaya, No. 6, pp. 1345–1352, June, 1992.

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Ogorodnikova, N.A., Kvasov, B.A. Monosubstituted benzenes. Some features of the electron density distribution obtained byab initio calculations. Russ Chem Bull 41, 1049–1055 (1992). https://doi.org/10.1007/BF00866583

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Key words

  • Monosubstituted benzenes
  • electron density distribution