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Theoretical analysis of reactions of electrophilic iodination and chlorination of benzene and polycyclic arenes in density functional theory approximation

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Abstract

Quantum-chemical method DFT B3LYP/6-311G* was applied to stage by stage thermodynamic calculation of reactions of electrophilic iodination of benzene, naphthalene, phenanthrene, and anthracene with iodine and iodine monochloride, and comparison with chlorination reactions was performed. The main distinction of iodination process from chlorination was an enhanced reversibility owing to protodeiodination. The reversibility of iodination grows with the electron-donor properties of aromatic substrates. The calculations permit an assumption that the chlorination of anthracene and phenanthrene with iodine monochloride occurs most probably through stages of electrophilic iodination-dehydroiodination.

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References

  1. Merkushev, E.B., Usp. Khim., 1984, vol. 53, p. 583.

    CAS  Google Scholar 

  2. Cacchi, S., Fabrizi, G., Parisi, L.M., Heterocycles, 2002, vol. 58, p. 667.

    Article  CAS  Google Scholar 

  3. Negishi, E-J., J. Organometal. Chem., 1999, vol. 576, p. 179.

    Article  CAS  Google Scholar 

  4. Merkushev, E.B., Synthesis, 1988, p. 923.

  5. Cheprakov, A.V., Makhon’kov, D.I., and Beletskaya, I.P., Izv. Akad. Nauk SSSR, Ser. Khim., 1987, p. 11.

  6. Skulski, L., Molecules, 2000, vol. 5, p. 1331.

    CAS  Google Scholar 

  7. Turner, D.E., O’Malley, R.F., Sardella, D.J., Barinelli, K.S., and Kaul, P. J. Org. Chem., 1994, vol. 59, p. 7335.

    Article  CAS  Google Scholar 

  8. Chaikovskii, V.K. and Filimonov, V.D., Zh. Org. Khim., 2001, vol. 37, p. 1189.

    Google Scholar 

  9. Filimonov, V.D., Krasnokutskaya, E.A., Poleshchuk, O.Kh., and Lesina, Yu.A., Izv. Akad. Nauk, Ser. Khim., 2006, p. 1280.

  10. Kekule, A., Lieb. Ann. 1866, vol. 137, p. 129.

    Google Scholar 

  11. Graham, W.S., Nichol, R.J., and Ubbelohde, A.R., J. Chem. Soc., 1955, p. 115.

  12. Smith, W.B., J. Org. Chem., 1985, vol. 50, p. 3649.

    Article  CAS  Google Scholar 

  13. Nicolet, B.H., J. Am. Chem. Soc., 1921, vol. 43, p. 2081.

    Article  CAS  Google Scholar 

  14. Terent’ev, A.P., Belen’kii, L.I., and Yanovskaya, L.A., Zh. Obshch. Khim., 1954, vol. 24, p. 1265.

    CAS  Google Scholar 

  15. Meerwein, H., Hoffman, P., and Schill, F., J. Prakt. Chem., 1939, vol. 154, p. 266.

    Article  Google Scholar 

  16. Suzuki, H. and Goto, R., Bull. Chem. Soc. Jpn., 1963, vol. 36, p. 389.

    Article  CAS  Google Scholar 

  17. Mattern, D.L. and Chen, X., J. Org. Chem., 1991, vol. 56, p. 5903.

    Article  CAS  Google Scholar 

  18. Filimonov, V.D., Krasnokutskaya, E.A., and Lesina, Yu.A., Zh. Org. Khim., 2003, vol. 39, p. 924.

    Google Scholar 

  19. Tomasi, J. and Perisco, M., Chem. Rev., 1994, vol. 94, p. 2027.

    Article  CAS  Google Scholar 

  20. Frisch, M.J., Trucks, G.W., Schlegel, H.B., Gill, P.M.W., Johnson, B.G., Robb, M.A., Cheeseman, J.R., Keith, T., Petersson, G.A., Montgomery, J.A., Raghavachari, K., Al-Laham, M.A., Zakrzewski, V., Ortiz, J.V., Foresman, J.B., Closlowski, J., Stefanov, B.B., Nanayakkara, A., Challacombe, M., Peng, C.Y., Ayala, P.Y., Chen, W., Wong, M.W., Andress, J.L., Replogle, E.S., Gomperts, R., Martin, R.L., Fox, D.J., Binkley, J.S., Defress, D.J., Baker, J., Stewart, J.P., Head-Gordon, M., Gonzales, C., and Pople, J.A., Gaussian 98, Revision A., Pittsburg: Gaussian Inc:, 1998.

    Google Scholar 

  21. Becke, A.D., J. Chem. Phys., 1993, vol. 98, p. 5648.

    Article  CAS  Google Scholar 

  22. Lee, C., Yang, W., and Parr, R.G., Phys. Rev. B, 1988, vol. 37, p. 785.

    Article  CAS  Google Scholar 

  23. Glukhovtsev, M.N., Pross, A., McGrath, M.P., and Radom, L., J. Chem. Phys., 1995, vol. 103, p. 1878.

    Article  CAS  Google Scholar 

  24. Sakai, H., Maeda, Y., Ichiba, S., and Negita, H., J. Chem. Phys., 1980, vol. 72, p. 6192.

    Article  CAS  Google Scholar 

  25. Su, J.T. and Zewail, A.H., J. Phys. Chem. A, 1998, vol. 102, p. 4082.

    Article  CAS  Google Scholar 

  26. Tang, L-T., Wei, Y., Wang, Y., Hu, S.-W., Liu, X.-O., Chu, T.-W., and Wang, X.-Y., J. Mol. Struct. Theochem., 2004, vol. 686, p. 25.

    Article  CAS  Google Scholar 

  27. Drepaul, I., Fagundez, V., Guiterrez, F., Lau, E.H., and Joens, J.A., J. Org. Chem., 1996, vol. 61, p. 3571.

    Article  CAS  Google Scholar 

  28. Su, J.T. and Zewail, A.H., J. Phys. Chem. A, 1998, vol. 102, p. 4082.

    Article  CAS  Google Scholar 

  29. Tustin, G.C. and Rule, M., J. Catalys., 1994, vol. 147, p. 186.

    Article  CAS  Google Scholar 

  30. Duan, S., Turk, J., Spiegle, J., Corbin, J., Masnovi, J., and Baker, R.J., J. Org. Chem., 2000, vol. 65, p. 3005.

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Tomsk Polytechnical University, Tomsk, 634050, Russia

    V. D. Filimonov, E. A. Krasnokytskaya & Yu. A. Lesina

  2. Tomsk State Pedagogical University, Tomsk, Russia

    O. Kh. Poleshchuk

Authors
  1. V. D. Filimonov
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  2. E. A. Krasnokytskaya
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  3. O. Kh. Poleshchuk
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  4. Yu. A. Lesina
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Correspondence to V. D. Filimonov.

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Original Russian Text © V.D. Filimonov, E.A. Krasnokytskaya, O.Kh. Poleshchuk, Yu.A. Lesina, 2008, published in Zhurnal Organicheskoi Khimii, 2008, Vol. 44, No. 5, pp. 691–696.

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Filimonov, V.D., Krasnokytskaya, E.A., Poleshchuk, O.K. et al. Theoretical analysis of reactions of electrophilic iodination and chlorination of benzene and polycyclic arenes in density functional theory approximation. Russ J Org Chem 44, 681–687 (2008). https://doi.org/10.1134/S1070428008050072

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  • DOI: https://doi.org/10.1134/S1070428008050072

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