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Unusual Lability of Pentafluorophenoxy Group in Reactions of Potassium Aroxides with Pentafluoropyridine

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Abstract

The kinetics of the reactions of pentafluoropyridine with potassium aroxides, leading to formation of polyfluorinated aryl pyridyl ethers, conform to the Bro/nsted equation. The data obtained for potassium pentafluorophenoxide deviate from the general correlation because of readily occuring reverse reaction, replacement of the pentafluorophenoxy group by released fluoride ion. PM3 calculations of the electronic structure of the reagents, intermediate σ-complexes, and products showed that the replacement of fluorine in pentafluoropyridine is a charge-controlled process, whereas unusually easy replacement of the pentafluorophenoxy group in the corresponding aryl pyridyl ether by fluorine is explained by structural features of its lowest unoccupied molecular orbital.

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REFERENCES

  1. Aksenov, V.V., Vlasov, V.M., and Yakobson, G.G., J. Fluorine Chem. 1982, vol. 20, no. 4, pp. 439-458.

    Google Scholar 

  2. Vlasov, V.M. and Sheremet, O.P., Izv. Sib. Otd. Akad. Nauk SSSR, Ser. Khim. Nauk 1982, issue 2, no. 4, pp. 114-120.

  3. Chantooni, M.K. and Kolthoff, I.M., J. Phys. Chem. 1976, vol. 80, no. 12, pp. 1306-1310.

    Google Scholar 

  4. Koppel, I.A., Taft, R.W., Anvia, F., Zhu, S.-Z., Hu, L.-Q., Sung, K.-S., Des Marteau, D.D., Yagupolskii, L.M., Yagupolskii, Y.L., Ignat'ev, N.V., Kondratenko, N.V., Volkonskii, A.Yu., Vlasov, V.M., Notario, R., and Maria, P.C., J. Am. Chem. Soc. 1994, vol. 116, no. 7, pp. 3047-3057.

    Google Scholar 

  5. Rodionov, P.P. and Furin, G.G., J. Fluorine Chem. 1990, vol. 47, no. 3, pp. 361-434.

    Google Scholar 

  6. Bordwell, F.G. and Hughes, D.L., J. Am. Chem. Soc. 1986, vol. 108, no. 19, pp. 5991-5997.

    Google Scholar 

  7. Ritchie, C.D. and Sager, W.F., Progress in Physical Organic Chemistry Cohen, S.G., Streitwieser, A., Jr., and Taft, R.W., Eds., New York: Intersci., 1963, vols. 1, 2. Translated under the title Sovremennye problemy fizicheskoi organicheskoi khimii, Moscow: Mir, 1967, pp. 498-555.

    Google Scholar 

  8. Stewart, J.J.P., J. Comput. Chem. 1989, vol. 10, no. 2, pp. 209-220, 221-264; Stewart, J.J.P., QCPE-455.

    Google Scholar 

  9. Strassner, T., Can. J. Chem. 1997, vol. 75, no. 7, pp. 1011-1022.

    Google Scholar 

  10. Wallis, M.P., Spiers, I.D., Schwalbe, C.H., and Fraser, W., Tetrahedron Lett. 1995, vol. 36, no. 21, pp. 3759-3762; Schaefer, T., Penner, G.H., Takeuchi, G., and Tseki, P., Can. J. Chem. 1988, vol. 66, no. 7, pp. 1647-1650.

    Google Scholar 

  11. Lias, S.G., Bartmess, J.E., Liebman, J.F., Holmes, J.L., Levin, R.D., and Mallard, W.G., J. Phys. Chem., Ref. Data 1988, vol. 17, suppl. 1, p. 768.

    Google Scholar 

  12. Buncel, E. and Manderville, R.A., J. Phys. Org. Chem. 1993, vol. 6, no. 2, pp. 71-82.

    Google Scholar 

  13. Argile, A. and Ruasse, M.-F., Tetrahedron Lett. 1980, vol. 21, no. 14, pp. 1327-1330.

    Google Scholar 

  14. Renfrew, A.H.M., Rettura, D., Taylor, J.A., Whitmore, J.M.J., and Williams, A., J. Am. Chem. Soc. 1995, vol. 117, no. 20, pp. 5484-5491; Shakes, J., Raymond, C., Rettura, D., and Williams, A., J. Chem. Soc., Perkin Trans. 2 1996, no. 8, pp. 1553-1557.

    Google Scholar 

  15. Jarman, M. and McCague, R., J. Chem. Soc., Chem. Commun. 1984, no. 2, pp. 125-127.

  16. Schaftenaar, G., QCPE-619.

  17. Shteingarts, V.D., Osina, O.I., Yakobson, G.G., and Vorozhtsov, N.N., Jr., Zh. Vses. Khim. Obva. 1966, vol. 11, no. 1, pp. 115-116.

    Google Scholar 

  18. Gething, B., Patrick, C.R., and Tatlow, J.C., J. Chem. Soc. 1962, no. 11, pp. 186-190.

  19. Sintezy ftororganicheskikh soedinenii (Syntheses of Organofluorine Compounds), Knunyants, I.L. and Yakobson, G.G., Eds., Moscow: Khimiya, 1973, p. 312.

    Google Scholar 

  20. Hodgson, H.H. and Moore, F.H., J. Chem. Soc. 1925, vol. 127, pp. 1599-1604.

    Google Scholar 

  21. Gordon, A.J. and Ford, R.A., The Chemist's Companion New York: Wiley, 1972. Translated under the title Sputnik khimika, Moscow: Mir, 1976, pp. 437-444.

    Google Scholar 

  22. Fadeeva, V.P. and Moryakina, I.M., Izv. Sib. Otd. Akad. Nauk SSSR, Ser. Khim. Nauk 1985, issue 2, no. 5, pp. 85-88.

  23. Kobrina, L.S., Shteingarts, V.D., and Shchegoleva, L.N., Izv. Sib. Otd. Akad. Nauk SSSR, Ser. Khim. Nauk 1974, issue 1, no. 2, pp. 68-77.

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  1. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Division, Russian Academy of Sciences, pr. Akademika Lavrent'eva 9, Novosibirsk, 630090, Russia

    V. M. Vlasov, V. V. Aksenov, P. P. Rodionov, I. V. Beregovaya & L. N. Shchegoleva

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  1. V. M. Vlasov
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  2. V. V. Aksenov
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  3. P. P. Rodionov
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  4. I. V. Beregovaya
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  5. L. N. Shchegoleva
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Vlasov, V.M., Aksenov, V.V., Rodionov, P.P. et al. Unusual Lability of Pentafluorophenoxy Group in Reactions of Potassium Aroxides with Pentafluoropyridine. Russian Journal of Organic Chemistry 38, 115–125 (2002). https://doi.org/10.1023/A:1015371212613

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