Skip to main content
SpringerLink
Log in

Heterocyclization of compounds containing diazo and cyano groups. 6. Theoretical and experimental investigations of cyclization of 2-cyano-2-diazoacetamides to 5-hydroxy-1,2,3-triazole-4-carbonitriles

  • Published:
Chemistry of Heterocyclic Compounds Aims and scope

Abstract

A series of N-alkyl- and N-aryl-2-cyano-2-diazoacetamides was synthesized by the reaction of 2-amino-2-cyanoacetamides with sodium nitrite in hydrochloric acid. The mechanism of their heteroclectrocyclization to 5-hydroxy-1,2,3-triazoles was investigated kinetically and theoretically by the B3LYP/6-31+G* method. The conclusion was made on the basis of the determined activation energy of the cyclization process. reaction parameters ϖ, and kinetic isotope effects, that there is a difference between the mechanisms of cyclization of the N-alkyl and N-aryl derivatives of 2-cyano-2-diazoacetamide; cyclization of the N-alkyl derivatives takes place by a monorotatory mechanism, while cyclization of the N-aryl derivatives takes place by a mechanism where one of the stages is heteroelectrocyclization of 2-diazoacetimidates.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. M. Yu. Kolobov, V. A. Bakulev, V. S. Mokrushin, and A. T. Lebedev,Khim. Geterotsikl. Soedin., No. 11, 1503 (1987).

    Google Scholar 

  2. V. A. Bakulev, V. G. Kartsev, and V. S. Mokrushin,Khim. Geterotsikl. Soedin., No. 11, 1443 (1989).

    Google Scholar 

  3. A. Padwa, T. J. Blacklock, and R. Losa,J. Org. Chem.,47, 3712 (1982).

    Article  Google Scholar 

  4. V. A. Bakulev and I. P. Gloriozov,Khim. Geterotsikl. Soedin., No. 4, 504 (1989).

    Google Scholar 

  5. M. N. Nguyen, T. K. Ha, and R. A. M. O'FerrallJ. Org. Chem.,55, 3251 (1990).

    Article  Google Scholar 

  6. D. M. Birney,J. Org. Chem.,61, 243 (1996).

    Article  Google Scholar 

  7. W. M. F. Fabian, V. A. Bakulev, and C. O. Kappe,J. Org. Chem.,63, 5801 (1998).

    Article  PubMed  Google Scholar 

  8. R. Huisgen,Khim. Geterotsikl. Soedin., No. 5, 579 (1981).

    Google Scholar 

  9. O. Dimroth,Lieb. Ann. Chem.,335, 1 (1904).

    Google Scholar 

  10. D. Barton and W. D. Ollis (editors),General Organic Chemistry [Russian translation], Vol. 4. Khimiya, Moscow (1983), p. 728.

    Google Scholar 

  11. A. J. Gordon and R. A. Ford,The Chemist's Companion, Wiley-Interscience (1973), p. 541.

  12. J. Hine and M. Hine,J. Am. Chem. Soc.,74, 5266 (1952).

    Article  Google Scholar 

  13. C. L. Perrin and J. D. Thoburn,J. Org. Chem.,54, 764 (1989).

    Article  Google Scholar 

  14. V. A. Bakulev, Yu. Yu. Morzherin, A. T. Lebedev, E. F. Dankova, M. Yu. Kolobov, and Yu. M. Shafran,Bull. Soc. Chim. Belg.,102, 493 (1993).

    Google Scholar 

  15. E. N. Marvell,Thermal Electrocyclic Reaction, Wiley-Interscience, New York (1980), p. 422.

    Google Scholar 

  16. A. R. Katritzky and J. M. Lagowski, in:Comprechensive Heterocyclic Chemistry, II, Part 4A. Pergamon (1986), p. 4.

  17. S. Scheiner and L. Wang,J. Am. Chem. Soc.,115, 1958 (1993).

    Article  Google Scholar 

  18. I. E. Mikhailov, E. P. Ivashchenko, A. I. Shif, V. M. Feigel'man, and L. P. Olekhnovich,Zh. Org. Khim.,59, 1416 (1989).

    Google Scholar 

  19. A. D. Becke,Phys. Rev.,38, 3098 (1988).

    Article  Google Scholar 

  20. A. D. Becke,J. Chem. Phys.,98, 5648 (1993).

    Article  Google Scholar 

  21. B. G. Cox,Modern Liquid Phase Kinetics, Oxford University Press (1994), p. 83.

  22. C. L. Perrin, J. D. Thoburn, and A. J. Kresge,J. Am. Chem. Soc.,114, 8800 (1992).

    Article  Google Scholar 

  23. Yu. M. Shafran, V. A. Bakulev, V. S. Mokrushin and S. G. Alekseev,Khim. Geterotsikl. Soedin., No. 9, 1266 (1984).

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Ural State Technical University, Ekaterinburg, Russia

    Yu. Yu. Morzherin, M. Yu. Kolobov & V. S. Mokrushin

  2. Institut für Organische Chemie und Makromolekulare Chemie, Friedrich-Schiller-Universität, Jena, Germany

    M. Brauer, E. Anders & V. A. Bakulev

Authors
  1. Yu. Yu. Morzherin
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. M. Yu. Kolobov
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. V. S. Mokrushin
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. M. Brauer
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. E. Anders
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. V. A. Bakulev
    View author publications

    You can also search for this author in PubMed Google Scholar

Additional information

For Communication 5, see [1].

Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 26–41, January, 2000.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Morzherin, Y.Y., Kolobov, M.Y., Mokrushin, V.S. et al. Heterocyclization of compounds containing diazo and cyano groups. 6. Theoretical and experimental investigations of cyclization of 2-cyano-2-diazoacetamides to 5-hydroxy-1,2,3-triazole-4-carbonitriles. Chem Heterocycl Compd 36, 22–36 (2000). https://doi.org/10.1007/BF02256840

Download citation

  • Received:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF02256840

Keywords

Search

Navigation