Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
권호 표지

A Study for the Reaction of ${\beta}$-Picoline with p-Substituted Benzoyl Chlorides by Pressure

압력변화에 따른 ${\beta}$-피콜린과 염화벤조일류의 반응에 대한 연구

  • 김영철 (한양대학교 자연과학대학 화학과) ;
  • 김세경 (한양대학교 자연과학대학 화학과)
  • Published : 1992.08.20
Download PDF
⟨ Previous Next ⟩

Abstract

The reaction of ${\beta}$-picoline with substituted benzoyl chlorides has been studied by means of conductometry under various pressures in acetonitrile. From the values of pseudo-first order and second order rate constants, the activation parameters (${\Delta}V{\neq}$, ${\Delta}{\beta}{\neq}$, ${\Delta}H{\neq}$, ${\Delta}S{\neq}$ and ${\Delta}G{\neq}$) and the pressure dependence of Hammett ${\rho}$ value were studied. The activation volume, the activation compressibility coefficient and the activation entropy were all negative. By increasing pressure the rate constant and Hammett ${\rho}$ value were increased, and the reaction mechanism was proceed in bond formation favored.

10$^{\circ}C$와 20$^{\circ}C$에서 ${\beta}$-피콜린과 치환된 벤조일클로라이드류의 반응을 압력변화에 따라 아세토니트릴용매내에서 전기전도도법으로 연구하였다. 유사 1차속도상수와 2차속도상수로부터 여러 가지 활성화파라미터들(${\Delta}V{\neq}$, ${\Delta}{\beta}{\neq}$, ${\Delta}H{\neq}$, ${\Delta}S{\neq}$ and ${\Delta}G{\neq}$)을 구하고, Hammett ${\rho}$값의 압력의존성을 설명하였다. ${\Delta}V{\neq}$, ${\Delta}{\beta}{\neq}$ 및 ${\Delta}S{\neq}$ 는 모두 음의 값을 나타내었고, 압력증가에 따라 속도상수와 Hammett ${\rho}$값은 증가하며, 결합형성이 더욱 촉진된 반응메카니즘으로 진행됨을 알 수 있었다.

Keywords

References

  1. Can. J. Chem. v.48 B. T. Baliga;E. Whalley
  2. Can. J. Chem. v.53 M. L. Tonnet;E. Whalley
  3. Progr. Phys. Org. Chem. v.11 M. H. Abraham
  4. J. Am. Chem. Soc. v.104 J. W. Viers;J. C. Schug
  5. Can. J. Chem. v.49 S. J. Dickson;J. B. Hyne
  6. Trans. Faraday Soc. v.31 M. G. Evans;M. Polanyi
  7. Bull. Korean Chem. Soc. v.6 O. C. Kwun;J. B. Kyung
  8. Bull. Chem. Soc. Jpn. v.45 Yasuhiko Kondo;Masaru Ohnishi;Niichiro Tokura
  9. J. Org. Chem. v.36 P. Haberfield;Abraham Nudelman;Allen Bloom;Richard Romm;Henry Ginsberg
  10. J. Am. Chem. Soc. v.102 E. M. Arnett;R. Reich
  11. J. Chem. Soc. H. C. Brown
  12. J. Korean Chem. Soc. v.35 Y. C. Kim;D. J. Koo
  13. Z. Physik. Chem. v.5 N. Menschutkin
  14. Phill. Mag. v.2 E. A. Guggenheim
  15. Bull. Chem. Soc. Jpn. v.46 K. Tamura;Y. Ogo
  16. High Pressure Chemistry H. Kelm
  17. Advances in Physical Organic Chemistry v.2 E. Whalley
  18. Rate and Equilibria of Org. Reaction J. E. Leffler;E. Grunwald
  19. J. Chem. Soc. v.B O. Rogne
  20. Chem. Revs. v.53 H. H. Jaffe
  21. J. Chem. Phys. v.31 A. J. Ellis;W. S. Fyfe;R. I. Rutherford