Chemistry of Heterocyclic Compounds

, Volume 43, Issue 5, pp 599–607 | Cite as

Reaction of diketene with cyanothioacetamide: A convenient and regioselective method for the preparation of new 4(1H)-pyridone derivatives

  • V. V. Dotsenko
  • S. G. Krivokolysko
  • B. P. Litvinov


The reaction of diketene with cyanothioacetamide in dry dioxane in the presence of triethylamine gives triethylammonium 3-cyano-6-methyl-4-oxo-1,4-dihydro-2-pyridinethiolate. The regioselective S-alkylation of this thiolate is a convenient method for the preparation of substituted 4(1H)-pyridones and also derivatives of thiazolo[3,2-a]pyridine and thieno[2,3-b]pyridine. The action of 2-amino-1,1,3-tricyanopropene on this thiolate leads to its transformation into a new heterocyclic system, namely, 5H-pyrido[2′,3′:4,5]thiopyrano[2,3-b]pyridine; treatment with iodine yields the oxidation product, namely, the corresponding bis(2-pyridyl) disulfide. The structure of isopropyl (3-cyano-6-methyl-4-oxo-1,4-dihydro-2-pyridinyl)thioacetate was confirmed by X-ray diffraction structural analysis.


diketene, 4(1H)-pyridones 5H-pyrido[2′,3′:4,5]thiopyrano[2,3-b]pyridines thiazolo-[3,2-a]pyridines thieno[2,3-b]pyridines cyanothioacetamide S-alkylation X-ray diffraction structural analysis Thorpe-Ziegler cyclization cyclocondensation 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    R. J. Clemens, Chem. Rev., 86, 241 (1986).CrossRefGoogle Scholar
  2. 2.
    R. N. Lacey, in: I. L. Knunyants (editor), Progress in Organic Chemistry [Russian translation], Vol. 2, Mir, Moscow (1964), p. 230.Google Scholar
  3. 3.
    P. V. Murphy, T. J. O’Sullivan, and N. W. A. Geraghty, J. Chem. Soc., Perkin Trans. 1, 2109 (2000).Google Scholar
  4. 4.
    P. V. Murphy, T. J. O’Sullivan, B. D. Kennedy, and N. W. A. Geraghty, J. Chem. Soc., Perkin Trans. 1, 2121 (2000).Google Scholar
  5. 5.
    K. N. Zelenin, S. V. Oleinik, A. A. Potekhin, V. V. Ovcharenko, J. Sinkkonen, and K. Pihlaja, ARKIVOC, iss. V, 94 (2003).Google Scholar
  6. 6.
    A. V. Kadushkin, D. B. Nilov, D. D. Nekrasov, N. P. Solov’eva, and V. G. Granik, Mendeleev Commun., 5, 193 (1995).CrossRefGoogle Scholar
  7. 7.
    B. X. Zhao and S. Eguchi, Heterocycl. Commun., 4, 113 (1998).Google Scholar
  8. 8.
    J. Häusler, Monatsh. Chem., 113, 1213 (1982).Google Scholar
  9. 9.
    Jahyo Kang, Yong Ha Kim, Min Park, Chul Hae Lee, and Wang-Joo Kim, Synth. Commun., 14, 265 (1984).CrossRefGoogle Scholar
  10. 10.
    T. Kato, Y. Kubota, M. Tanaka, H. Takahashi, and T. Chiba, Heterocycles, 9, 841 (1978).Google Scholar
  11. 11.
    T. Kato and T. Hozumi, Chem. Pharm. Bull., 20, 1574 (1972).Google Scholar
  12. 12.
    E. Suzuki, B. Katsuragawa, and S. Inoue, J. Chem. Soc., Perkin Trans. 1, 72 (1977).Google Scholar
  13. 13.
    E. Suzuki, H. Sekizaki, and S. Inoue, Synthesis, 652 (1975).Google Scholar
  14. 14.
    N. A. V. Reddy, S. N. Maiti, and R. G. Micetich, J. Chem. Res. Synops, 32 (1990).Google Scholar
  15. 15.
    E. G. Howard, US Patent No. 2,733,260 (1956); Chem. Abstr., 50, 12104 (1956).Google Scholar
  16. 16.
    E. G. Howard, A. Kotch, R. V. Lindsey, Jr., and R. E. Putnam, J. Am. Chem. Soc., 80, 3924 (1958).CrossRefGoogle Scholar
  17. 17.
    F. M. Abdel-Galil, S. M. Sherif, and M. H. Elnagdi, Heterocycles, 24, 2023 (1986).Google Scholar
  18. 18.
    Yu. A. Sharanin, V. K. Promonenkov, and V. P. Litvinov, in: Advances in Science and Technology. Organic Chemistry, Current Directions in Research and the Application of Chemical Means for Plant Protection [in Russian], Vol. 20, VINITI, Moscow (1991), Part 2, p. 73.Google Scholar
  19. 19.
    V. P. Litvinov, Usp. Khim., 68, 817 (1999).Google Scholar
  20. 20.
    V. V. Dotsenko, Chemical Sciences Candidate’s Dissertation, Moscow (2004).Google Scholar
  21. 21.
    V. V. Dotsenko, S. G. Krivokolysko, A. N. Chernega, and V. P. Litvinov, Izv. Akad. Nauk, Ser. Khim., 918 (2003).Google Scholar
  22. 22.
    V. P. Litvinov, V. V. Dotsenko, and S. G. Krivokolysko, Izv. Akad. Nauk, Ser. Khim., 847 (2005).Google Scholar
  23. 23.
    V. V. Dotsenko, S. G. Krivokolysko, A. N. Chernega, and V. P. Litvinov, Izv. Akad. Nauk, Ser. Khim., 1432 (2002).Google Scholar
  24. 24.
    F. H. Allen, O. Kennard, D. G. Watson, L. Brammer, A. G. Orpen, and R. Tailor, J. Chem. Soc., Perkin Trans. 2, Issue 12, S1 (1987).Google Scholar
  25. 25.
    L. N. Kuleshova and P. M. Zorkii, Acta Crystallogr., B37, 1363 (1976).Google Scholar
  26. 26.
    J. S. A. Brunskill, A. De, and D. F. Ewing, J. Chem. Soc., Perkin Trans. 1, 629 (1978).Google Scholar
  27. 27.
    M. Mittelbach, Monatsh. Chem., 116, 689 (1985).CrossRefGoogle Scholar
  28. 28.
    D. J. Watkin, C. K. Prout, J. R. Carruthers, and P. W. Betteridge, CRYSTALS, issue 10, Chemical Crystallography Laboratory, University of Oxford (1996)Google Scholar
  29. 29.
    J. R. Carruthers and D. J. Watkin, Acta Crystallogr., A35, 698 (1979).Google Scholar
  30. 30.
    A. C. T. North, D. C. Phillips, and F. S. Mathews, Acta Crystallogr., A24, 351 (1968).Google Scholar

Copyright information

© Springer Science+Business Media, Inc. 2007

Authors and Affiliations

  • V. V. Dotsenko
    • 1
  • S. G. Krivokolysko
    • 2
  • B. P. Litvinov
    • 3
  1. 1.“ChemEx” LaboratoryVladimir Dal East-Ukrainian National UniversityLuganskUkraine
  2. 2.N. D. Zelinsky Institute of Organic ChemistryRussian Academy of SciencesMoscowRussia
  3. 3.Institute of Organic ChemistryNational Academy of Sciences of UkraineKievUkraine

Personalised recommendations