Advertisement

Russian Chemical Bulletin

, Volume 66, Issue 11, pp 2095–2102 | Cite as

2,6-Disubstituted 4-azidopyrimidines: synthesis, kinetic and thermodynamic studies of azide-tetrazole rearrangement by NMR spectroscopy

  • N. V. Pleshkova
  • E. B. Nikolaenkova
  • V. P. Krivopalov
  • V. I. Mamatyuk
Full Article
  • 26 Downloads

Abstract

Thermodynamic and kinetic parameters of the tautomeric tetrazole-azide rearrangement for a series of 2,6-disubstituted 4-azidopyrimidines are determined by NOESY/EXSY and DNMR: ΔH = 15—28 kJ mol–1; ΔS = 47—65 J mol–1 К–1; Е a = 93—117 kJ mol–1; lgA = 15.1—18.9. They are dependent on electronic properties of the substituents and the polarity of solvent.

Key words

4-azidopyrimidine tetrazolo[c]pyrimidines azide-tetrazole equilibrium NMR NOESY/EXSY DNMR entropy enthalpy rate constant Arrhenius equation 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    S. V. Chapyshev, Molecules, 2015, 20, 19142.CrossRefGoogle Scholar
  2. 2.
    Organic Azides: Syntheses and Applications, Ed. S. Bräse, K. Banert, Wiley, Chichester, West Sussex, UK, 2010, 507 pp.Google Scholar
  3. 3.
    Nitrenes and Nitrenium Ions, Eds D. E. Falvey, A. D. Gudmunddottir, Wiley, Hoboken, New Jersey, 2013, 586 pp.Google Scholar
  4. 4.
    V. I. Minkin, A. D. Garnovskii, J. Elguero, A. R. Katritzky, O. V. Denisko, Advances in Heterocyclic Chemistry, Ed. A. R. Katritzky, Academic Press, San Diego, 2000, 76, 157.CrossRefGoogle Scholar
  5. 5.
    V. Ya. Pochinok, L. Ph. Avramenko, P. S. Grigorenko, V. N. Skopenko, Russ. Chem. Rev., 1975, 44, 481.CrossRefGoogle Scholar
  6. 6.
    M. Tisler, Synthesis, 1973, 123.Google Scholar
  7. 7.
    T. Sasaki, K. Kanematsu, M. Murata, Tetrahedron, 1971, 27, 5121.CrossRefGoogle Scholar
  8. 8.
    Jr. C. Temple, J. A. Montgomery, J. Org. Chem., 1965, 30, 826.CrossRefGoogle Scholar
  9. 9.
    V. P. Krivopalov, V. I. Mamatyuk, V. P. Mamaev, Chem. Heterocycl. Compd., 1990, 26, 1370.CrossRefGoogle Scholar
  10. 10.
    I. A. Khalymbadzha, T. S. Shestakova, S. L. Deev, V. L. Rusinov, O. N. Chupakhin, Z. O. Shenkarev, A. S. Arse-niev, Russ. Chem. Bull., 2013, 62, 521.CrossRefGoogle Scholar
  11. 11.
    T. S. Shestakova, Z. O. Shenkarev, S. L. Deev, O. N. Chupakhin, I. A. Khalymbadzha, V. L. Rusinov, A. S. Arseniev, J. Org. Chem., 2013, 78, 6975.CrossRefGoogle Scholar
  12. 12.
    S. N. Sirakanyan, D. Spinelli, A. Geronikaki, A. A. Hova-kimyan, A. S. Noravyan, Tetrahedron, 2014, 70, 8648.CrossRefGoogle Scholar
  13. 13.
    S. N. Sirakanyan, D. Spinelli, A. Geronikaki, V. G. Kartsev, H. A. Panosyan, A. G. Ayvazyan, R. A. Tamazyan, V. Frenna, A. A. Hovakimyan, Tetrahedron, 2016, 72, 1919.CrossRefGoogle Scholar
  14. 14.
    E. B. Gorbunov, R. K. Novikova, P. V. Plekhanov, P. A. Slepukhin, G. L. Rusinov, V. L. Rusinov, V. N. Charushin, O. N. Chupakhin, Chem. Heterocycl. Compd., 2013, 49, 766.CrossRefGoogle Scholar
  15. 15.
    A. Thomann, J. Zapp, M. Hutter, M. Empting, R. W. Hartmann, Org. Biomol. Chem., 2015, 13, 10620.CrossRefGoogle Scholar
  16. 16.
    I. Alkorta, F. Blanco, J. Elguero, R. M. Claramunt, Tetra-hedron, 2010, 66, 2863.CrossRefGoogle Scholar
  17. 17.
    I. Alkorta, F. Blanco, J. Elguero, Tetrahedron, 2010, 66, 5071.CrossRefGoogle Scholar
  18. 18.
    P. Cmoch, H. Korczak, L. Stefaniak, G. A. Webb, J. Phys. Org. Chem., 1999, 12, 470.CrossRefGoogle Scholar
  19. 19.
    A. Thomann, A. G. G. de Mello Martins, C. Brengel, M. Empting, R.W. Hartmann, ACS Chem. Biol., 2016, 11, 1279.CrossRefGoogle Scholar
  20. 20.
    A. Y. Denisov, V. P. Krivopalov, V. I. Mamatyuk, V. P. Mamaev, Magn. Reson. Chem, 1988, 26, 42.CrossRefGoogle Scholar
  21. 21.
    R. R. Ernst, G. Bodenhausen, A. Wokaun, Principle of Nuclear Magnetic Resonance in One and Two Dimensios, Claredon Press, 1990, pp. 610.Google Scholar
  22. 22.
    C. L. Perrin, T. J. Dwyer, Chem. Rev., 1990, 90, 935.CrossRefGoogle Scholar
  23. 23.
    http://nmr.nioch.nsc.ru/noekin/.Google Scholar
  24. 24.
    J. Sandstrom, Dynamic NMR Spectroscopy, Academic press, New York, 1982, 226 pp.Google Scholar
  25. 25.
    V. P. Krivopalov, E. B. Nikolaenkova, V. F. Sedova, V. P. Mamaev, Chem. Heterocycl. Compd., 1983, 19, 977.CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2017

Authors and Affiliations

  • N. V. Pleshkova
    • 1
  • E. B. Nikolaenkova
    • 1
  • V. P. Krivopalov
    • 1
  • V. I. Mamatyuk
    • 1
    • 2
  1. 1.N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry of Siberian BranchRussian Academy of SciencesNovosibirskRussian Federation
  2. 2.Novosibirsk State University (National Research University)NovosibirskRussian Federation

Personalised recommendations