Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
권호 표지

Kinetic Studies on Solvolyses of Substituted Cinnamoyl Chlorides in Alcohol-Water Mixture

알코올-물 혼합 용매계에서 치환된 염화신남오일의 가용매분해반응에 관한 속도론적 연구

  • Koo, In Sun (Department of Chemical Education, Gyeongsang National University) ;
  • Kim, Jung Soon (Department of Chemical Education, Gyeongsang National University) ;
  • An, Sun Kyoung (Department of Chemical Education, Gyeongsang National University) ;
  • Yang, Kyu Il (Department of Chemical Education, Gyeongsang National University) ;
  • Lee, Ic Hoon (Department of Chemistry, Inha University)
  • 구인선 (경상대학교 과학교육학부 화학전공) ;
  • 김정순 (경상대학교 과학교육학부 화학전공) ;
  • 안선경 (경상대학교 과학교육학부 화학전공) ;
  • 양기열 (경상대학교 과학교육학부 화학전공) ;
  • 이익춘 (인하대학교 화학과)
  • Published : 19991000
Download PDF
⟨ Previous Next ⟩

Abstract

Solvolyses of para-substituted cinnamoyl chlorides in aqueous binary mixtures of acetone, ethanol, methanol were investigated at 25.0$^{\circ}C$. These data were interpreted using the Grunwald-Winstein relationship, Hammett equation, and quantum mechanical model. Grunwald-Winstein plots of the first-order rate constants for para-substituted cinnamoyl chlorides with $Y_{CI}$ showed marked dispersions into three separate curves for the three aqueous mixtures with a large m vaIue for aqueous alcohol solvents. This study has shown that the potential energy surface and quanturm mechanical model predict transition state variation correctly for $S_N1$ like $S_N2$ reaction mechanism of para-substituted cinnamoyl chlorides.

아세톤, 에탄올, 메탄올 이성분 혼합수용액에서 파라치환된 cinnamoyl chloride의 가용매분해반응을 25$^{\circ}C$에서 수행하였다. 이들 속도자료로부터 Grunwald-Winstein관계식, Hammett 식, PES 모형과 QM모형을 이용하여 해석 하였다. 파라 치환된 cinnamoyl chloride의 일차반응속도상수를 이용하여 Grunwald-Winstein 도시를 한 결과 세 개의 분리된 곡선으로 분산 현상을 보였으며 알코올 수용액에서 큰 m 값을 나타내었다. PES 모형과 QM 모형에 의한 전이상태 변화에 대한 예측으로부터 본 연구에서의 반응은 결합 이탈이 많이 진전된 $S_N1$형 $S_N2$ 반응으로 진행되고 있음을 알 수 있었다.

Keywords

References

  1. Adv. Phys. Org. Chem. v.14 Bentley, T. W.;Schleyer, P. von R.
  2. Adv. Phys. Org. Chem. v.17 Bentley, T. W.;Llewelleyn, G.
  3. J. Am., Chem. Soc. v.70 Grunwald, E.;Winstein, S.
  4. J. Chem. Soc., Perkin Trans. 2 Bentley, T. W.;Carter, G. E.;Harris, H. C.
  5. J. Chem. Soc., Perkin Trans. 2 Bentley, T. W.;Harris, H. C.
  6. J. Chem. Soc., Perkin Trans. 2 v.53 Bentley, T. W.;Freeman, A. E.
  7. J. Chem. Soc., Perkin Trans. 2 Bentley, T. W.;Harris, H. C.;Koo, I. S.
  8. J. Chem. Soc., Chem. Commun. Bentley, T. W.;Koo, I. S.
  9. J. Chem. Soc., Perkin Trans. 2 Bentley, T. W.;Koo, I. S.
  10. J. Chem. Soc., Perkin Trans. 2 Bentley, T. W.;Harris, H. C.
  11. J. Org. Chem. v.53 Bentley, T. W.;Harris, H. C.
  12. J. Am. Chem. Soc. v.83 Jencks, W. P.
  13. Acta Chem. Scand. v.17 Euranto, E. K.;Cleve, N. J.
  14. J. Am. Chem. Soc. v.102 Holterman, H. A. J.;Engberts, J. B. F. N.
  15. J. Am. Chem. Soc. v.115 Stefanidis, D.;Jencks, W. P.
  16. J. Am. Chem. Soc. v.108 Blokzijl, W.;Engberts, J. B. N.;Blander, M. J.
  17. Adv. Phys. Org. Chem. v.5 Review Johnson, S. L.
  18. J. Am. Chem. Soc. v.91 Kevil, D. N.;Foss, F. D.
  19. J. Chem. Soc., Perkins Trans. 2 Kevil, D. N.;Knauss, D. C.
  20. Chem. Rev. v.75 Williams, A.;Douglas, K. T.
  21. The Chemistry of Acyl Halides Kivinen, A.;S. Patai(Ed.)
  22. Comprehensive Chemical Kinetics v.10 R. J. E. Tallbot;Bamford, C. H.(Ed.);Tipper. C. H.(Ed.)
  23. Chimia v.15 Hudson, R. F.
  24. J. Chem. Soc. Hudson, R. F.;Moss, G. E.
  25. J. Chem. Soc., Perkin Trans. 2 Miller, J.;Ying, O. L.
  26. J. Am. Chem. Soc. v.109 Ba-Saif, S.;Luthra, A. K.;Williams, A.
  27. Bull. Soc. Chim. Fr. Kevil, D. N.;Kim, C. B.
  28. J. Chem. Soc., Perkin Trans. 2 Kevil, D. N.;Kim, C. B.
  29. J. Chem. Soc., Perkin Trans. 2 Bentley, T. W.;Cater, G. E.;Harris, H. C.
  30. J. Chem. Soc., Perkin Trans. 2 Bentley, T. W.;Harris, H. C.
  31. J. Chem. Soc., Chemical Communication Bentley, T. W.;Koo, I. S.
  32. J. Chem. Soc., Perkin Trans. 2 Kim, T. H.;Huh, C.;Lee, I.
  33. J. Am. Chem. Soc. v.77 Hammond, G. S.
  34. J. Am. Chem. Soc. v.89 Thornton, E. R.
  35. J. Am. Chem. Soc. v.101 Harris, J. M.;Shafer, S. G.;Moffatt, J. R.;Becker, A. R.
  36. J. Chem. Soc. More O'Ferrall, R. A.
  37. J. Am. Chem. Soc. v.103 Pross, A.;Shaik, S. B.
  38. J. Chem. Soc., Perkin Trans. 2 Koo, I. S.lYang, K.;Kang, K.;Lee, I.;Bentley, T. W.
  39. Bull. Korean. Chem. Soc. v.18 Koo, I. S.;Yang, K.;Koo, J. C.;Park, J. K.;Lee, I.
  40. Bull. Korean Chem. Soc. v.15 Yang K. Y.;Koo, I. S.;Lee, I.;Jo, D. S.
  41. Chem. Soc. Perkin Trans. 2 Bentley, T. W.;Harris, H. C.
  42. J. Org. Chem. v.50 Bentley, T. W.;Robert, K.
  43. J. Org. Chem. v.46 Bentley, T. W.;Bowen, C. T.;Brown, H. C.;Chloupek, F. J.
  44. J. Org. Chem. v.53 Bentley, T. W.;Harris, H. C.
  45. J. Chem. Soc., Perkin Trans. 2 Koo, I. S.;Bentley, T. W.;Kang, D. H.;Lee, I.
  46. J. Chem. Soc., Perkin Trans. 2 Bentley, T. W.;Jones, R. O.
  47. J. Org. Chem. v.59 Kevil, D. N.;Ismail, N. Hj. H.;D'souza, M. J.
  48. J. Am. Chem. Soc. v.73 Winstein, S.;Grunwald, E.;Jones, H. W.
  49. Physical Organic Chemistry Hammett, L. P.