Bulletin of the Korean Chemical Society

  • 제20권7호
  • /
  • Pages.805-808
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  • 1999
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  • 0253-2964(pISSN)
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  • 1229-5949(eISSN)
대한화학회 (Korean Chemical Society)
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Kinetics and Mechanism for the Reaction of 4-Nitrophenyl 2-Furoate with Secondary Alicyclic Amines

  • 발행 : 1999.07.20
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초록

Second-order-rate constants (kN) have been measured spectrophotometrically for the reactions of 4-nitrophenyl 2-furoate (1) with a series of secondary alicyclic amines in H2O containing 20 mole % DMSO at 25.0℃. 1 is about 5-8 times more reactive than 4-nitrophenyl benzoate (2), although 1 is expected to be less reactive than 2 based on MO calculations and 13 C NMR study. The Brфnsted-type plots for the aminolysis reactions of 1 and 2 are linear with βnuc values of 0.78 and 0.85, respectively. The replacement of the CH=CH group by an O atom in the acyl moiety (2->1) does not cause any mechanism change. The reaction of piperidine with a series of substituted phenyl 2-furoates gives a linear Hammett plot with a large ρ- value (ρ- = 2.88) when σ- constants are used. The linear Brфnsted and Hammett plots with a large ρ- value suggest that the aminolysis reaction of 1 proceeds via rate-determining break-down of the addition intermediate to the porducts.

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참고문헌

  1. Catalysis in Chemistry and Enzymology Jencks, W. P.;Catalysis in Chemistry and Enzymology
  2. J. Am. Chem. Soc. v.99 Hupe, D. J.;Jencks, W. P.
  3. J. Am. Chem. Soc. v.104 Jencks, W. P.;Brant, S. R.;Gandler, J. R.;Fendrich, G.;Nakamura, C.
  4. J. Am. Chem. Soc. v.115 Stefanidis, D.;Cho, S.;Dhe-Paganon, S.;Jencks, W. P.
  5. J. Org. Chem. v.62 Oh, H. K.;Woo, S. Y.;Shin, C. H.;Park, Y. S.;Lee, I.
  6. New J. Chem. v.21 Koh, H. J.;Lee, J. W.;Lee, H. W.:Lee, I.
  7. J. Chem. Soc., Perkin Trans. v.2 Koh, H. J.;Kim, S. I.;Lee, B. C.;Lee, I.
  8. J. Chem. Soc., Perkin Trans. v.2 Oh, H. K.;Shin, C. H.;Lee, I.
  9. J. Org. Chem. v.61 Castro, E. A.;Pizzaro, M I.;Santos, J. G.
  10. J. Org. Chem. v.58 Castro, E. A.;Ibanez, F.;Santos, AJ. G.;Ureta, C.
  11. J. Org. Chem. v.61 Castro, E.A.;Cubillos, M.Santos, J. G.
  12. J. Org. Chem. v.62 Castro, E. A.;Araneda, C. A.
  13. Chem. Soc. Rev. v.23 Williams, A.
  14. J. Am. Chem. Soc. v.111 BaSaif, S.;Luthra, A. K.;Williams, A.
  15. J. Am. Chem. Soc. v.104 Detar, D. F.
  16. Bull. Chem. Soc. Japn. v.69 Okuyama, T.;Takano, H.;Senda, K.
  17. Advances in Linear Free Energy Relationships Champan, N. B.;Shorter, J.
  18. Techniques of Organic Chemistry(4th ed.) v.6 Bernasconi, C. F.(ed.)
  19. Bull. Korean Chem. Soc. v.11 Um, I. H.;Choi, K. E.;Kwon, D. S.
  20. Bull. Korean Chem. Soc. v.18 Um, I. H.;Yeom, E. S.;Kwon, H. J.;Kown, D. S.
  21. Bull. Korean Chem. Soc. v.18 Um, I. H.;Kim, M. J.;Min, J. S.;Kown, D. S.
  22. Can J. Chem. v.76 Um, I. H.;Chung, E. K.;Lee, S. M.;
  23. Tetrahedton Lett. v.38 Um, I. H.;Chung, E. K.;Kwon, D. S.
  24. Tetrahedron v.53 Um, I. H.;Hong, Y. J.;Kown, D. S.
  25. J. Am. Chem. Soc. v.94 Menger, F. M.;Smith, J. A.
  26. J. Chem. Soc., Perkin Trans. v.2 Colthurst, M. J.;Williams, A.
  27. J. Chem. Soc., Perkin Trans. Castro, E. A.;Steinfort, G. B.
  28. J. Org. Chem. v.50 Castro, E. A.;Santander, C. L.
  29. J. Org. Chem. v.51 Castro, E. A.;Valdiva, J. L.
  30. J. Org. Chem. v.33 Kirsch, J. F.;Clewell, W.;Simon, A.
  31. Biochemistry v.1 Caplow, M.;Jencks, W. P.
  32. J. Phys. Org. Chem. v.4 Correia, V. R.;Cuccovia, I. M.;Chaimovich, H.
  33. Practical Organic Chemistry Vogel, A. I.
  34. Bull. Korean Chem. Soc. v.17 Um, I. H.;Nahm, J. H.;Lee, Y. J.;Kown, D. S.
  35. Int. J. Chem. Kinet. v.30 Oh, H. K.;Woo, S. Y.;Shin, C. H.;Lee, I.
  36. J. Am. Chem. Soc. v.111 Jencks, W. P.
  37. Can. J. Chem. Um, I. H.;Min, J. S.;Lee, H. W.
  38. J. Chem. Res. (s) Um, I. H.;Kwon, H. J.;Kwon, D. S.;Park, J. Y.
  39. J. Chem. Res. (M) Um, I. H.;Kown, H. I.;Kwon, D. S.;Park, J. Y.
  40. Adv. Phys. Org. Chem. v.14 Pross, A.
  41. J. Org. Chem. v.45 Buncel, E.;Chuaqui, C.
  42. J. Chem. Educ. v.64 Buncel, E.;Wilson, H.
  43. Bull. Korean Chem. Soc. v.11 Kown, D. S.;Lee, G. J.;Um, I. H.
  44. J. Am. Chem. Soc. v.111 Buncel, E.;Um, I. H.;Hoz, S.
  45. Physical and Mechanistic Organic Chemistry(2nd ed.) Jones, R. A. Y.