Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
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Kinetic Study on the Reaction of para-substitued Benzylbromide with Isoquinoline under High Pressure

고압하에서의 이소퀴놀린과 브롬화 벤질류의 반응에 관한 속도론적인 연구

  • Published : 19980400
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Abstract

Kinetic studies on the reaction of isoquinoline with para-substituted benzylbromides were conducted under various pressures (1 ~1000 bar) in acetonitrile. From the rate constants obtained, the activation parameters such as$\DeltaV^{\neq}, \Delta\beta^{\neq}, \DeltaH^{\neq}, \DeltaS^{\neq}, \DeltaG^{\neq}$ and Ea were evaluated. Reaction rate increasing the pressure and temperature. The activation compressibility coefficient and the activation entropy showed negative values. From the substituent effect and the results, it was found that the reaction proceeds through $S_N2$ mechanism, but the structure of transition state was slightly changed with substituents and pressure.

Acetonitrile 용매내에서 isoquinoline과 치한된 benzylbromide의 반응을 압력변화(1~1000bar)에 따라 반응속도론적으로 연구하였다. 속도상수로부터 활성화파라미터들을 TEX>$\(DeltaV^{\neq}, \Delta\beta^{\neq}, \DeltaH^{\neq}, \DeltaS^{\neq}, \DeltaG^{\neq},Ea)$구하였다. 온도가 증가함에 따라 속도상수는 증가 하고, TEX>$\DeltaV^{\neq}, \Delta\beta^{\neq},및 \DeltaS^{\neq}$는 모두 음의 값으로 나타내었다. 치환기효과와 실험 결과로 부터 반응메카니즘을 고찰한 결과 전체적인 반응은 $S_{N}2$반응 메카니즘으로 진행되나, 치환체와 압력변화에 따라 전이상태 구조에 약간의 변화가 있었다.

Keywords

References

  1. The Physics of High Pressure Bell London Bridgman P. W.
  2. Chemical Reactions at High Pressures Spon K. Weale
  3. Adv. Phy. Org. Chem. v.2 Whalley, E.
  4. Prog. Reaction Kinetics v.5 Kohnstam, G.
  5. Rep. Prog. Phys. Chem. v.23 Eckert, C.
  6. Angew, Chem. Int. Ed. v.14 Jenner, G.
  7. J. Chem. Rev. Asano T.;LeNoble, W.
  8. Kinetics in Solutions Moelyn-Hughes
  9. J. Am. Chem. Soc. v.88 Hyne, J. B.
  10. Trans. Faraday Soc. v.31 Evans, M. G.;Polanyi M.
  11. Bull Chem. Soc. v.45 Kondo, Y.;Tojima, H.;Tokura N.
  12. Phys. Chem. v.5 Menschutkin, N.Z.
  13. Phil. Mag. v.2 Guggenheim, E. A.
  14. Advances in Physical Organic Chemistry(2nd Ed.) Whalley, E.
  15. Physical Chemistry of Electrolytic Solution(3rd Ed.) Harned, H. S.;Owen, B. B.
  16. Physical Organic Chemystry(1st Ed.) Isaacs, N. S.
  17. Chem. Comm. Kevillc, D.N.
  18. J. Chem. Soc. Archer, B. L.;Hudson, R. F.
  19. Rate and Equilibria of Org. Leffler, J. E.;Grunwald, E.
  20. J. Org. Chem. v.20 Leffler, J.E.
  21. J. Org. Chem. v.31 Leffler, J. E.
  22. J. Chem. Soc(B) Rogne, O.
  23. Chem. Revs. v.53 Jeffe, H. H.
  24. Tetrahedron Lett. v.23 Lee, I.;Kim, N. I.;Sohn, S. C.