Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Kinetics and Mechanism of Aminolysis of Phenyl Benzoates in Acetonitrile

  • Published : 1995.09.20
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Abstract

The kinetics and mechanism of the reactions of phenyl benzoates with benzylamines and pyrrolidine are investigated in acetonitrile. The variations of ρX (ρXY>0) and ρZ (ρYZ<0) with respect to the substituent in the substrate (σY) indicate that the reactions proceed through a tetrahedral intermediate, T±, with its breakdown in the rate determining step. The large magnitudes of ρZ, ρXY and ρYZ as well as the effects of secondary kinetic isotope effects involving deuterated nucleophiles are also in line with the proposed mechanism.

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References

  1. J. Chem. Soc., Perkin Trans. 2 Bond, P. M.;Castro, E. A.;Moodie, R. B.
  2. J. Am. Chem. Soc. v.99 Gresser, M. J.;Jencks, W. P.
  3. J. Org. Chem. v.45 Castro, E. A.;Freudenberg, M.
  4. J. Org. Chem. v.46 Castro, C.;Castro, E. A.
  5. J. Chem. Soc., Perkin Trans. 2 Castro, E. A.;Steinfort, G. B.
  6. J. Org. Chem. v.50 Castro, E. A.;Santander, C. L.
  7. J. Org. Chem. v.54 Castro, E. A.;Ureta, C. J.
  8. J. Org. Chem. v.55 Castro, E. A.;Ureta, C. J.
  9. J. Chem. Soc., Perkin Trans. 2 v.55 Castro, E. A.;Ureta, C. J.
  10. J. Chem. Res. Castro, E. A.;Ibanez, F.;Saitua, A. M.;Santos, J. G.
  11. J. Chem. Res. Castro, E. A.;Ibanez, F.;Saitua, A. M.;Santos, J. G.
  12. J. Am. Chem. Soc. v.115 Stefanidis, D.;Cho, S.;Dhe-Paganon, S.;Jencks, W. P.
  13. Chem. Soc. Rev. v.23 Williams, A.
  14. J. Am. Chem. Soc. v.94 Menger, F. M.;Smith, J. H.
  15. J. Chem. Soc., Perkin Trans. 2 Jedrzejczak, M.;Motie, R. E.;Satchell, D. P. N.;Satchell, R. S.;Wassef, W. N.
  16. Adv. Phys. Org. Chem. v.27 Lee, I.
  17. Bull. Korean Chem. Soc. v.15 Lee, I.
  18. J. Chem. Soc., Perkin Trans. 2 Oh, H. K.;Shin, C. H.;Lee, I.
  19. J. Chem. Soc., Perkin Trans. 2 Koh, H. J.;Lee, H. W.;Lee, I.
  20. Adv. Phys. Org. Chem. v.14 Pross, A.
  21. Chem. Rev. v.75 Johnson, C. D.
  22. Tetrahedron v.34 McLennan, D. J.
  23. J. Chem. Educ. v.64 Buncel, E.;Wilson, H.
  24. J. Phys. Org. Chem. v.5 Lee, I.
  25. J. Chem. Res. Lee, I.;Koh, H. J.;Lee, H. W.
  26. J. Chem. Res. Lee, I.;Koh, H. J.;Lee, H. W.
  27. J. Chem. Soc., Perkin Trans. 2 Lee, I.;Koh, H. J.;Lee, B. S.;Sohn, D. S.;Lee, B. C.
  28. Bull. Korean Chem. Soc. v.11 Lee, I.;Koh, H. J.;Lee, B-S.;Lee. H. W.
  29. J. Chem. Soc., Perkin Trans. 2 Heo, C. K. M.;Bunting, J. W.
  30. J. Chem. Soc., Perkin Trans. 2 Bunting, J. W.;Mason, J. M.;Heo, C. K. M.
  31. Bull. Soc. Chim. Belg. v.94 Nagy, O. B.;Reuliaux, V.;Bertrand, N.;van der Mensbrugghe, A.;Leseul, J.;Nagy, J. B.
  32. Chemical Computations and Errors Grunpler, T. B.;Yoh, J. H.
  33. Phil. Mag. v.2 Guggenheim, E. A.