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DOI: 10.1039/A709002A (Paper) Reference Section for: J. Chem. Soc., Perkin Trans. 2, 1998, 1827-1832

Solvation and nucleophilic reactivity of 1,2,4-triazolate ion in acetonitrile–methanol mixtures

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Yasuhiko Kondo, Kouji Yano, Ossun Fang, Hiromi Saito and Tatsuya Takagi

Abstract

The 1,2,4-triazolate ion is a stronger hydrogen-bond accepting base than 5-substituted 1,2,3-benzotriazolate ions. Partly because of this characteristic, the transition-state anion of the 1,2,4-triazolate ion reaction with ethyl iodide indicates the most significant hydrogen-bond accepting basicity of a transition-state anion so far observed. The PM3 atomic charge on the nitrogen atom at the 4-position of the 1,2,4-triazolate ion and the average PM3 atomic charge on the nitrogen atom at the 1- and 3-positions of 5-substituted 1,2,3-benzotriazolate ions make the most significant contribution to the basicity of the relevant anion. The significant basicity for the transition-state anion has been rationalized through an empirical correlation between the specific interaction enthalpy, ΔtHSIAN→MeOH, and the PM3 atomic charge.

References

  1. H. Wamhoff, in Comprehensive Heterocyclic Chemistry, eds. A. R. Katritzky and C. W. Rees, Pergamon Press, Oxford, 1984, vol. 5, p. 669 Search PubMed.
  2. J. P. Poyla, in Comprehensive Heterocyclic Chemistry, eds. A. R. Katritzky and C. W. Rees, Pergamon Press, Oxford, 1984, vol. 5, p. 733 Search PubMed.
  3. A. R. Katritzky, H.-X. Chang and B. Yang, Synthesis, 1995, 503 CrossRef CAS.
  4. G. Schwarzenbach and K. Lutz, Helv. Chim. Acta, 1940, 28, 1162 CrossRef.
  5. Landolt Bornstein Tabellen, Springer-Verlag, Berlin, 1960, vol. 2, ch. 7 Search PubMed.
  6. Y. Kondo, T. Tsukamoto and C. Moriguchi, J. Chem. Soc., Perkin Trans. 2, 1996, 1699 RSC.
  7. Y. Kondo, T. Tsukamoto and N. Kimura, J. Chem. Soc., Perkin Trans. 2, 1997, 1765 RSC.
  8. Y. Kondo, M. Ittoh and S. Kusabayashi, J. Chem. Soc., Faraday Trans., 1982, 78, 2793 RSC.
  9. Y. Kondo, T. Fujiwara, A. Hayashi and S. Kusabayashi, J. Chem. Soc., Faraday Trans., 1989, 85, 2931 Search PubMed.
  10. Y. Kondo, T. Fujiwara, A. Hayashi, S. Kusabayashi and T. Takagi, J. Chem. Soc., Perkin Trans. 2, 1990, 741 RSC.
  11. F. G. Bordwell and D. L. Hughes, J. Am. Chem. Soc., 1984, 106, 3234 CrossRef CAS.
  12. C. D. Ritchie, Physical Organic Chemistry. The Fundamental Concepts, Marcell Dekker, New York, 2nd edn., 1990 Search PubMed.
  13. F. G. Bordwell, Acc. Chem. Res., 1988, 21, 456 CrossRef CAS.
  14. Y. Kondo, K. Kondo and S. Kusabayashi, J. Chem. Soc., Perkin Trans. 2, 1993, 1141 RSC.
  15. Y. Kondo, O. Nonaka, K. Iwasaki, T. Kuwamoto and T. Takagi, J. Chem. Soc., Perkin Trans. 2, 1994, 473 RSC.
  16. J. J. P. Stewart, J. Comput. Chem., 1989, 10, 209 CrossRef CAS MOPAC93 program package, Dr J. J. P. Stewart and Fujitsu Ltd., Tokyo, Japan.
  17. A. E. Tipping, P. Jimenez, E. Ballesteros, J.-L. M. Abboud, M. Yanez, M. Esseffar and J. Elguero, J. Org. Chem., 1994, 59, 1039 CrossRef CAS.
  18. Y. Kondo, W. Sugitani, M. Tokui and T. Takagi, J. Chem. Soc., Perkin Trans. 2, 1995, 1049 RSC.
  19. Y. Kondo, S. Kusabayashi and T. Mitsuhashi, J. Chem. Soc., Perkin Trans. 2, 1988, 1799 RSC.
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