대한화학회지 (Journal of the Korean Chemical Society)

  • 제30권2호
  • /
  • Pages.172-180
  • /
  • 1986
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  • 1017-2548(pISSN)
  • /
  • 2234-8530(eISSN)
대한화학회 (Korean Chemical Society)
권호 표지

Hammett 치환기 상수에 대한 분자궤도론적 해석 (I)

Molecular Orbital Analyses on Hammett Substituent Constant (I)

  • 박병각 (영남대학교 이과대학 화학과) ;
  • 이갑룡 (효성여자대학교 사범대학 화학과)
  • Byung-Kak Park (Department of Chemistry, Yeungnam University) ;
  • Gab-Yong Lee (Department of Chemistry, Hyosung Womens's University)
  • 발행 : 1986.04.20
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초록

치환-벤조산, -베젠 및 -나프탈렌의 세 계열에 대해 LCAO MO법으로 Hammett치환기 상수를 해석하였다. Hammett ${\sigma}$값은 이론적으로 유도효과와 공명효과의 독립적인 기여의 합으로 취급됨을 알았다. 즉, 유도효과를 정적유도효과(static inductive effect, Is)와 동적유도효과 (dynamic inductive effect, Id)로 나누어 각각 net charge 및 근사자기편극률 지수로 취하고 공명효과로서 치환 분자와 비치환분자의 HOMO에너지 차$({\Delta}E^{HOMO})$로 취하였으며 계산결과 Hammett ${\sigma}$값은 정적유도효과, 동적유도효과 및 ${\Delta}E^{HOMO}$의 합에 의존됨을 알았다.

The Hammett's substituent constants were analyzed for the substituted-benzoic acid, -benzene and -naphthalene by LCAO MO method. Hammett's ${\sigma}$-values have been theoretically proved to treat as the sum of independent contribution of inductive effect and resonance effect. That is, Is (static inductive effect) and Id (dynamic inductive effect) corresponding to inductive effect are chosen as net charge and approximate self atom polarizability indices respectively, and ${\Delta}E^{HOMO}$ which is the difference in HOMO energy level between substituted molecule and unsubstituted molecule as resonance effect. In conclusion, it has been found that the observed ${\sigma}$-values depend on the sum of Id, Is and ${\Delta}E^{HOMO}$.

키워드

참고문헌

  1. Physical Organic Chemistry L.P. Hammett
  2. An Instroduction to Physical Organic Chemistry E.M. Kosower
  3. Reaction Kinetics v.2 K.J. Laidler
  4. Chem. Revs. v.53 H.H. Jaffe
  5. J. Am. Chem. Soc. v.80 H.C. Brown;Y. Okamoto
  6. Bull. Chem. Soc., Jpn. v.45 Y. Yukawa;Y. Tsuno;M. Suwada
  7. J. Am. Chem. Soc. v.95 A.J. Hoefnagel;B.M. Wepster
  8. Prog. Phys. Org. Chem. v.10 S. Ehrenson;R.T.C. Brownlee;R.W. Taft
  9. J. Am. Chem. Soc. v.75 C.G. Swain;C.B. Scott
  10. J. Chem. Phys. v.20 H.H. Jaffe
  11. J. Chem. Phys. v.21 H.H. Jaffe
  12. Tetrahedron v.26 K. Imafuku;S. Nakama;H. Matsumura
  13. Z. Chem. v.8 J. Kuthan;V. Skala
  14. Chem. Abst. v.70 J. Kuthan;V. Skala
  15. J. Chem. Ed. v.55 O.H. Rousseau;F. Texier
  16. J. Org. Chem. v.45 G. Kemister;A. Pross;L. Radom;R.W. Taft
  17. Rec. Trav. Chim. v.72 F.L.J. Sixma
  18. J. Am. Chem. Soc. v.84 M.J.S. Dewar;P.J. Grisdale
  19. J. Org. Chem. v.44 S.K. Knudson;J.P. Idoux
  20. J. Am. Chem. Soc. v.103 E.R. Vorpagel;A. Streitwieser, Jr.;S.D. Alexandratos
  21. J. Am. Chem. Soc. v.104 D.L. Grier;A. Streitwieser, Jr.
  22. Steric Effects in Organic Chemistry R.W. Taft;M.S. Newman(ed.)
  23. Correlation Analysis in Chemistry J. Shorter
  24. Molecular Orbital Theory for Organic Chemists M.J.S. Dewer
  25. The HMO Model and its Application, ed. E. Heilbronner;H. Bock
  26. J. Chem. Phys. v.20 K. Fukui;T. Yonezawa;H. Shingu
  27. Structure and Mechanism in Organic chemistry C.K. Ingold
  28. Introduction to Quantum Chemistry T. Yonezawa(et al.)
  29. Introduction to Quantum Chemistry T. Yonezawa(et al.)
  30. 分子軌道法入門 廣田穰
  31. Molecular Orbital Theory for Organic Chemists, ed. A. Streitwieser, Jr.
  32. 有機量子化學入門 飛田滿彦
  33. 分子構造論入門 兒島邦夫