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Chemistry of Heterocyclic Compounds

, Volume 27, Issue 1, pp 76–80 | Cite as

PMR spectroscopic study of the kinetics of H/D exchange in methyl groups in a series of heterocyclic azines

  • M. M. Markova
  • V. P. Lezina
  • S. B. Gashev
  • A. U. Stepanyantz
  • B. V. Mislavskii
  • L. D. Smirnov
Article
  • 32 Downloads

Abstract

The rate of H/D exchange among methyl group protons in a series of substituted 3-hydroxypyridines, 5-hydroxypyrimidines, and their N-oxides has been shown to increase with increasing acidity of the medium. The most reactive form of these molecules is the cationic form at pH<2. The rate of H/D exchange of CH3 group protons in 3-hydroxypyridine derivatives has also been found to be several orders of magnitude lower than the rates of exchange for methyl-substituted 5-hydroxypyrimidine and its N-oxide. Effective rate constants for methyl group proton exchange have been estimated. In the case of methyl-substituted 5-hydroxypyrimidine N-oxide derivatives it has been established that the rate of proton exchange is greater for an ortho-methyl group than for a methyl group in the para-position relative to the N-oxide site.

Keywords

Methyl Organic Chemistry Acidity Spectroscopic Study Effective Rate 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

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Literature Cited

  1. 1.
    V. P. Lezina, A. U. Stepanyants, L. D. Smirnov, and M. I. Vinnik,Izv. Akad. Nauk SSSR, Ser. Khim., No. 8, 317 (1978).Google Scholar
  2. 2.
    V. P. Lezina, L. V. Shirokova, A. U. Stepanyants, and L. D. Smirnov,Izv. Akad. Nauk SSSR, Ser. Khim., No. 9, 2001 (1981).Google Scholar
  3. 3.
    V. P. Lezina, M. M. Borunov, S. B. Gashev, and L. D. Smirnov,Izv. Akad. Nauk SSSR, Ser. Khim., No. 1, 40 (1983).Google Scholar
  4. 4.
    V. P. Lezina, S. B. Gashev, M. M. Borunov, L. D. Smirnov, and K. M. Dyumaev,Izv. Akad. Nauk SSSR, Ser. Khim., No. 12, 3697 (1984).Google Scholar
  5. 5.
    N. M. émanuel' and D. G. Knorre,Course in Chemical Kinetics [in Russian], Vysshaya Shkola, Moscow (1984), p. 248.Google Scholar
  6. 6.
    N. M. Rodigin and é. N. Rodigina,Sequential Chemical Reactions [in Russian], Izd. Akad. Nauk SSSR, Moscow (1960).Google Scholar
  7. 7.
    V. P. Lezina, M. M. Kozlova, S. B. Gashev, A. U. Stepanyants, and L. D. Smirnov,Khim. Geterotsikl. Soedin., No. 8, 1111 (1986).Google Scholar
  8. 8.
    Y. Goto, T. Niiya, N. Honjo, T. Sakamoto, H. Yoshizava, H. Yamanaka, and T. Kubota,Chem. Pharm. Bull., 30, 1126 (1982).Google Scholar
  9. 9.
    V. P. Lezina, M. M. Kozlova, S. B. Gashev, L. V. Gol'tsova, A. U. Stepanyants, and L. D. Smirnov,Khim. Geterotsikl. Soedin., No. 10, 1369 (1987).Google Scholar
  10. 10.
    C. D. Johnson, N. R. Katritzky, and S. A. Shapiro,J. Am. Chem. Soc.,91, 6654 (1969).Google Scholar
  11. 11.
    O. A. Reutov,Theoretical Principles of Organic Chemistry [in Russian], Moscow State University Press (1964).Google Scholar
  12. 12.
    J. H. Chesterfield and J. F. W. McOmie,J. Chem. Soc.,93, 1998 (1960).Google Scholar
  13. 13.
    S. B. Gashev, V. P. Lezina, and S. D. Smirnov,Khim. Geterotsikl. Soedin., No. 9, 1252 (1983).Google Scholar

Copyright information

© Plenum Publishing Corporation 1991

Authors and Affiliations

  • M. M. Markova
    • 1
    • 2
  • V. P. Lezina
    • 1
    • 2
  • S. B. Gashev
    • 1
    • 2
  • A. U. Stepanyantz
    • 1
    • 2
  • B. V. Mislavskii
    • 1
    • 2
  • L. D. Smirnov
    • 1
    • 2
  1. 1.Institute of Chemical PhysicsAcademy of Sciences of the USSRMoscow
  2. 2.Scientific-Research Institute of PharmacologyAcademy of Medical Sciences of the USSRMoscow

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