Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
권호 표지
DOI QR코드

DOI QR Code

Mechanism for the Reaction of Substututed Phenacyl Arenesulfonates with Substituted Pyridines under High Pressures

  • Published : 1997.11.20
Download PDF
⟨ Previous Next ⟩

Abstract

The rates for the reaction of (Z)-phenacyl (X)-benzenesulfonates with (Y)-pyridines in acetone were measured by an electrical conductivity method at 1-2000 bars and 45 ℃. The magnitudes of the Hammett reaction constants, ρX, ρY and ρZ, represent the degree of Nu-C bond formation and that of C-L bond breaking. The magnitude of correlation interaction term ρij can be used to determine the structure of the transition state (TS) for the SN reaction. As the pressure is increased, the Hammett reaction constants, ρX, |ρY| and ρZ are increased, but correlation interaction coefficient, |ρXZ| and ρYZ, are decreased. The results indicate that the reaction of (Z)-phenacyl (X)-benzenesulfonates with (Y)-pyridines probably moves from an associative SN2 to late-type SN2 mechanism by increasing pressure.

Keywords

References

  1. Dokl. Akad. Nauk. USSR v.122 Gonikberg, M. G.;Kitairgorodsky, A. L.
  2. J. Chem.Educ. v.44 Le Noble, W. J.
  3. Bull. Chem. Soc. Jpn. v.46 Tamura, K.;Ogo, T.;Imoto, T.
  4. J. Am. Chem. Soc. v.97 Okamoto, T.;Lee, K. I.
  5. J. Chem. Soc., Perkin Trans. Ⅱ Yoh, S. D.;Kim, S. H.;Park, J. H.
  6. Tetrahedron Letters v.29 Yoh, S. D.;Lee, O. S.
  7. Advances in Linear Free Energy Relationships Charpman, N. B.;Shorter, J.
  8. Correlation Analysis in Chemistry Charpman, N. B.;Shorter, J.
  9. Mechanism and Theory in Organic Chemistry(3rd Ed.) Lowry, T. H.;Richardson, K. S.
  10. The Hammett Equation Johnson, C. D.
  11. Chem. Rev. v.53 Jaff$\'{e}$, H. H.
  12. J. Phys. Org. Chem. v.8 Yoh, S. D.;Cheong, D. Y.
  13. J. Phys. Org. Chem. v.9 Yoh, S. D.;Cheong, D. Y.
  14. J. Korean Chem. Soc. v.24 Hwang, J. U.;You, S. D.;Jee, J. G.
  15. Proc. R. Soc. London, Ser. A v.15 Gibson, R. O.;Fawcett, E. W.;Perren, M. W.
  16. Bull. Korean Chem. Soc. v.4 Hwang, J. U.;Chung, J. J.;Yoh, S. D.;Jee, J. G.
  17. Bull. Korean Chem. Soc. v.6 Lee, O. S.;Yoh, S. D.