Russian Chemical Bulletin

, Volume 56, Issue 11, pp 2239–2246 | Cite as

Selective mono-and diamination of polyfluorinated benzenes and pyridines with liquid ammonia

  • T. A. Vaganova
  • S. Z. Kusov
  • V. I. Rodionov
  • I. K. Shundrina
  • E. V. MalykhinEmail author


Amination of pentafluoropyridine, 2,3,5,6-tetrafluoropyridine, 4-chlorotetrafluoropyridine, 3,5-dichlorotrifluoropyridine, octafluorotoluene, α,α,α,2,3,5,6-heptafluorotoluene, decafluoro-m-xylene, decafluorobiphenyl, hexafluorobenzene, and pentafluorobenzene with liquid ammonia was investigated. Bis-aminodefluorination temperatures for the majority of substrates were shown to exceed significantly the corresponding temperatures of monoaminodefluorination. The optimal conditions for selective preparation of mono-and diaminopolyfluoro(het)arenes were elucidated. An efficient method for isolation of particular polyfluorophenylenediamines from product mixtures formed in nonselective reactions of pentafluorobenzene and hexafluorobenzene with aqueous ammonia based on complexation with a crown ether is proposed.

Key words

organofluorine compounds ammonia aminodefluorination polyfluorodiaminopyridines polyfluorophenylenediamines nucleophilic substitution 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    N. N. Vorozhtsov, G. G. Yakobson, and V. E. Platonov, USSR Pat. 166661; Byul. izobret., 1964, 23, 17; N. N. Vorozhtsov, G. G. Yakobson, and V. D. Shteingarts, USSR Pat. 162826; Byul. izobret., 1964, 11, 14 (in Russian).Google Scholar
  2. 2.
    G. G. Yakobson, T. D. Petrova, and L. S. Kobrina, Fluorine Chem. Rev., 1974, 7, 115; L. S. Kobrina, Fluorine Chem. Rev., 1974, 7, 1; G. G. Yakobson and V. M. Vlasov, Synthesis, 1976, 652; V. E. Platonov and G. G. Yakobson, Synthesis, 1976, 6, 374.Google Scholar
  3. 3.
    (a) Sintezy Ftororganicheskikh soedinenii [Syntheses of Organofluorine Compounds], Eds I. L. Knunyants and G. G. Yakobson, Khimiya, Moscow, 1973, 312 pp.; (b) 143; (c) 190; (d) 192; (e) 194; (f) 139; (g) 195.Google Scholar
  4. 4.
    Yu. N. Sazanov, Zh. Prikl. Khim., 2001, 74, 1217 [Russ. J. Appl. Chem., 2001, 74, 1253 (Engl. Transl.)]; S. Ando, T. Matsuura, and S. Sasaki, in Fluoropolymers 2: Properties, Ed. G. Hougham, Kluwer Academic-Plenum Publishers, New York, 1999, 277.Google Scholar
  5. 5.
    L. Revesz, F. E. Di Padova, T. Buhl, R. Feifel, H. Gram, P. Hiestand, U. Manning, R. Wolf, and A. G. Zimmerlin, Bioorg. Med. Chem. Lett., 2002, 12, 2109; GB Pat. 1161492; Chem. Abstr., 1969, 71, 91313; Organofluorine Compounds in Medicinal Chemistry and Biomedical Applications, Eds R. Filler, Y. Kobayashi, and L. M. Yagupolskii, Elsevier, Amsterdam, 1993, 386 pp.; D. J. McNamara and P. D. Cook, J. Med. Chem., 1987, 30, 340.CrossRefGoogle Scholar
  6. 6.
    G. A. Selivanova, L. M. Pokrovskii, V. D. Shteingarts, Zh. Org. Khim., 2001, 37, 429 [Russ. J. Org. Chem., 2001, 37, 404 (Engl. Transl.)].Google Scholar
  7. 7.
    G. A. Selivanova, T. V. Chuikova, A. A. Shtark, and V. D. Shteingarts, Zh. Org. Khim., 1988, 24, 2513 [J. Org. Chem. USSR, 1988, 24, 2267 (Engl. Transl.)].Google Scholar
  8. 8.
    E. V. Malykhin and V. D. Shteingarts, Ros. Khim. Zhurn., 1999, 43, 49 [Mendeleev Chem. J., 1999, 43, 37 (Engl. Transl.)].Google Scholar
  9. 9.
    Khimicheskaya entsiklopediya [Chemical Encyclopedia], Ed. I. L. Knunyants, Sovetskaya entsiklopediya, Moscow, 1988, 1, 149 (in Russian).Google Scholar
  10. 10.
    R. D. Chambers, J. Hutchinson, and W. K. R. Musgrave, J. Chem. Soc., 1964, 5634.Google Scholar
  11. 11.
    R. E. Banks, M. G. Barlow, J. C. Hornby, and M. Mamaghani, J. Chem. Soc., Perkin Trans. 1, 1980, 817.Google Scholar
  12. 12.
    R. D. Chambers, J. Hutchinson, and W. K. R. Musgrave, J. Chem. Soc., 1965, 5040.Google Scholar
  13. 13.
    R. D. Chambers, J. Hutchinson, and W. K. R. Musgrave, J. Chem. Soc. C, 1966, 220.Google Scholar
  14. 14.
    G. M. Brooke, J. Fluorine Chem., 1997, 86, 1.CrossRefGoogle Scholar
  15. 15.
    R. D. Chambers, J. S. Waterhouse, and D. L. H. Williams, J. Chem. Soc., Perkin Trans. 2, 1977, 585.Google Scholar
  16. 16.
    Sintezy ftororganicheskikh soedinenii [Syntheses of Organofluorine Compounds], CJSC Science and Production Association PiM-Invest, Moscow, 2005, 201 pp. (in Russian).Google Scholar
  17. 17.
    E. V. Aroskar, M. T. Chaudhry, R. Stephens, and J. C. Tatlow, J. Chem. Soc., 1964, 2975.Google Scholar
  18. 18.
    F. A. M. Ayanbadejo, Spectrochim. Acta A, 1969, 25, 1009.CrossRefGoogle Scholar
  19. 19.
    G. G. Yakobson, V. D. Shteingarts, A. I. Miroshnikov, N. N. Vorozhtsov, Dokl. Akad. Nauk SSSR, 1964, 159, 1109 [Dokl. Chem., 1964, 159, 1347 (Engl. Transl.)].Google Scholar
  20. 20.
    D. D. Callander, P. L. Coe, and J. C. Tatlow, Tetrahedron, 1966, 22, 419.CrossRefGoogle Scholar
  21. 21.
    G. M. Brooke and W. K. R. Musgrave, J. Chem. Soc., 1965, 1864.Google Scholar
  22. 22.
    E. J. Forbes, R. D. Richardson, and J. C. Tatlow, Chem. Ind. (London), 1958, 630.Google Scholar
  23. 23.
    G. M. Brooke, J. Burdon, M. Stacey, and J. C. Tatlow, J. Chem. Soc., 1960, 1768.Google Scholar
  24. 24.
    A. M. Doyle and A. E. Pedler, J. Chem. Soc. C, 1971, 282.Google Scholar
  25. 25.
    P. Robson, J. Roylans, R. Stephens, J. C. Tatlow, and R. E. Wortchington, J. Chem. Soc., 1964, 5748.Google Scholar
  26. 26.
    G. A. Selivanova, L. Yu. Gurskaya, L. M. Pokrovskii, V. F. Kollegov, and V. D. Shteingarts, J. Fluorine Chem., 2004, 125, 1829.CrossRefGoogle Scholar
  27. 27.
    F. Vögtle and W. M. Müller, Chem. Ber., 1981, 114, 3179.CrossRefGoogle Scholar
  28. 28.
    Host Guest Complex Chemistry Macrocycles, Eds F. Vogtle and E. Weber, Springer-Verlag, Berlin, 1985.Google Scholar
  29. 29.
    A. Gordon and R. Ford, The Chemist’s Companion, Wiley, New York, 1972.Google Scholar
  30. 30.
    S. Z. Kusov, E. G. Lubenets, V. A. Semikolenov, V. S. Kobrin, and A. G. Khmel’nitskii, Izv. Sib. Otd. Akad. Nauk SSSR. Ser. Khim. nauk, 1989, 62 [Izv. Sib. Otd. Akad. Nauk SSSR, Ser. Khim. Nauk, 1989 (Engl. Transl.)].Google Scholar
  31. 31.
    G. W. Gokel, D. J. Cram, C. L. Liotta, H. P. Harris, and F. L. Cook, J. Org. Chem., 1974, 39, 2445.CrossRefGoogle Scholar
  32. 32.
    C. Tamborski and E. J. Saloski, J. Org. Chem., 1966, 31, 746.CrossRefGoogle Scholar
  33. 33.
    R. D. Chambers, J. Hutchinson, and W. K. L. Musgrave, J. Chem. Soc., 1964, 3573.Google Scholar
  34. 34.
    GB Pat. 1367383; Chem. Abstr., 1974, 82, 31266.Google Scholar
  35. 35.
    A. Abo-Amer, N. Yu. Adonin, V. V. Bardin, P. Fritzen, H.-J. Frohn, and G. Steinberg, J. Fluorine Chem., 2004, 125, 1771.CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, Inc. 2007

Authors and Affiliations

  • T. A. Vaganova
    • 1
  • S. Z. Kusov
    • 1
  • V. I. Rodionov
    • 1
  • I. K. Shundrina
    • 1
  • E. V. Malykhin
    • 1
    • 2
    Email author
  1. 1.N. N. Vorozhtsov Novosibirsk Institute of Organic ChemistrySiberian Branch of the Russian Academy of SciencesNovosibirskRussian Federation
  2. 2.Novosibirsk State UniversityNovosibirskRussian Federation

Personalised recommendations