Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
권호 표지

Linear Relationships between Thermodynamic Parameters (Part V) Critical Evaluation and Mechanistic Significances of the Relationship

熱力學函數間의 直線關係 (第 5 報) 關係式의 評價와 反應機構上의 意義

  • Lee, Ik-Choon (Chemistry Division, Atomic Energy Research Institute)
  • 이익춘 (原子力硏究所 化學硏究室)
  • Published : 19650300
Download PDF
⟨ Previous Next ⟩

Abstract

Justifications for the use of ${\sigma}$ and Y as independent potential energy variables in the general equation have been reviewed and some mechanistic significances of the relationship discussed. Analysis of the activation parameters for the solvolysis of benzyl chlorides in ethanol-water mixture showed that there are two distinct series of substrate constants ${\alpha}'$, which can be correlated linearly within a series with the substituent constants ${\sigma}$ conforming to the generally accepted concept of change in mechanism from $S_N1$ to $S_N2$.

一般式中의 potential energy 變數로서 ${\sigma}$ Y를 使用할 수 있음을 밝혔고 또 關係式의 反應機構上의 意義를 論하였다. Benzyl chlorides의 solvolysis反應 data를 適用함으서 物質常數 ${\alpha}'$는 2個의 뚜렷한 系列을 形成하며 置換基常數 ${\sigma}$와는 各系列마다 別途로 直線關係를 가지며 이로서 $S_N1$으로부터 $S_N2$로의 反應機構의 變化를 알 수가 있었다.

Keywords

References

  1. Journal of the Korean Chemical Society v.7 Ikchoon Lee
  2. Journal of the Korean Chemical Society v.7 Ikchoon Lee;Y.J. Park
  3. Journal of the Korean Chemical Society v.7 Ikchoon Lee
  4. Physical Organic Chemistry L.P. Hammett
  5. J. Am. Chem. Soc. v.70 E. Grunwald;S. Winstein
  6. Rates and Equilibria of Organic Reactions J.E. Leffler;E. Grunwald
  7. Journal of the Korean Chemical Society v.7 Ikchoon Lee
  8. Journal of the Korean Chemical Society v.7 Ikchoon Lee;Y.J. Park
  9. Journal of the Korean Chemical Society v.7 Ikchoon Lee
  10. Rates and Equilibria of Organic Reactions J.E.Leffler;E.Grunwald
  11. J.Am. Chem. Soc. v.82 R.D.Campbell;H.M.Gilow
  12. J.Am. Chem. Soc. v.85 L.G. Hepler
  13. J.Am. Chem. Soc. v.86 H.C.Ko;W.F. O'Hara;T. Hu;L.G. Hepler
  14. J.Am. Chem. Soc. v.59 R.J.Hartman;A.M.Borders
  15. J.Am. Chem. Soc. v.62 R.J.Hartman;A.G.Gassman
  16. J. Chem. Soc. J.D.Dickinson;C.Eaborn
  17. J. Am. Chem. Soc. v.83 R.M. Laird;R. E. Parker
  18. J. Am. Chem. Soc. v.73 C.G.Swain;W.P.Langsdorf, Jr.
  19. Helv. Chim. Acta v.XLIV G.Klopman;R.F. Hudson
  20. J. Chem. Soc. G.Klopman;R.F.Hudson
  21. J. Am. Chem. Soc. v.73 S.Winstein;E.Grunwald;H.W. Jones
  22. J. Am. Chem. Soc. v.84 J.W. Hill;A.Fry
  23. J. Am. Chem. Soc. v.84 J.B.Hyne;R.Wills;R.E.Wonkka
  24. J. Am. Chem. Soc. v.85 J.B.Hyne;R.Wills
  25. The Reactions in Solution E. A. Moelwyn-Hughes
  26. J.Am.Chem.Soc. v.73 E.Grunwald;B.J.Berkowitz
  27. J.Am.Chem.Soc. v.75 B.Gutbezahl;E.Grunwald
  28. Rates and Equilibria of Organic Reactions J.E.Leffler;E.Grunwald
  29. J.Am.Chem. Soc. v.80 E.M.Kosower
  30. J.Am.Chem. Soc. v.85 E.M.Arnett(et al.)
  31. J.Am.Chem. Soc. v.83 A. G. Harrison;P. Kebarle;F. P. Lossing
  32. J.Am.Chem. Soc. v.80 H.C. Brown;Y. Okamoto
  33. Steric Effects in Organic Chemistry R. W. Taft, Jr.;M. S. Newman(ed.)
  34. Physical Organic Chemistry J. Hine
  35. S. Winstein
  36. Progress in Physical Organic Chemistry v.I A.Streitwieser, Jr.
  37. Chem.Revs. v.56 A.Streitwieser, Jr.
  38. J.Am.Chem. Soc. v.82 J.B.Hyne