MO Studies on the Reaction of t-Butoxyl, t-Butyl Radical with Substituted-Toluenes

t-Butoxyl, t-Butyl 라디칼에 의한 치환체-톨루엔의 수소 추출반응에 대한 분자궤도론적 연구

  • 전용구 (대전기계창) ;
  • 황미숙 (원광대학교 문리과대학 화학과) ;
  • 이익춘 (인하대학교 이과대학 화학과)
  • Published : 1983.12.20

Abstract

The reaction for the hydrogen abstraction from substituted-toluenes by t-butoxyl and t-butyl radical have been studied MO theoretically using CNDO/2 method. The reaction for the abstraction from substituted-toluenes by t-butoxyl radical showed the negative ${\rho}$ values from Hammett equation, since t-butoxyl radial is electrophilic, relatively low energy SOMO, which can interact with HOMO energy of substituted-toluens. On the other hand, t-butyl radical is nucleophilic, relatively high energy SOMO, which can interact with LUMO energy of substituted-toluenes. And so the reaction of abstraction from substituted-toluenes by t-butyl radical exhibited positive ${\rho}$ values.

Keywords

References

  1. Table of Interatomic Distance and Configuration in Molecules and Ions I. E. Sutton
  2. J. Amer. Chem. Soc. v.70 C. Walling;E. R. Briggs;K. B. Wolfstirn;F. T. Mayo
  3. Free Radicals in Solution C. Walling
  4. Free Radicals v.1 G. A. Russell;J. K. Kochi(ed.)
  5. J. Amer. Chem. Soc. v.89 H. Sakurai;A. Hosomi
  6. J. Amer. Chem. Soc. v.82 C. Walling;B. B. Jacknow
  7. J. Amer. Chem. Soc. v.87 R. D. Gilliom;B. F. Ward, Jr.
  8. J. Amer. Chem. Soc. v.94 A. A. Zavitas;J. A. Pinto
  9. J. Amer. Chem. Soc. v.94 A. A. Zavitas
  10. J. Amer. Chem. Soc. v.99 W. H. Davis, Jr.;W. A. Pryor
  11. J. Amer. Chem. Soc. v.96 W. A. Pryor;W. H. Davis Jr.;J. P. Stainley
  12. J. Amer. Chem. Soc. v.101 D. D. Tanner;P. W. Samal;T. C. S. Ruo;R. I. Henriques
  13. J. Amer. Chem. Soc. v.104 W. A. Pryor;F. Y. Tang;R. H. Tang;D. F. Church
  14. J. Amer. Chem. Soc. v.6 G. A. Russell;R. C. Williamson
  15. J. Chem. Soc. Perkin Ⅱ R. J. Elliot;W. G. Richards
  16. J. Amer. Chem. Soc. v.96 W. A. Pryor;W. H. Davis Jr.
  17. J. Amer. Chem. Soc. v.97 R. W. Henderson
  18. Free-Radicals W. A. Pryor
  19. Chemical Reactivity and Reaction Paths G. Klopman
  20. J. Chem. Edu. v.55 Olivier Henri-Rousseau;Fernand Texier
  21. Bull. Chem. Soc. v.27 K. Fukui;T. Yonezawa;C. Nagata
  22. J. Amer. Chem. Soc. v.96 R. W. Henderson;R. D. Ward Jr.
  23. J. Amer. Chem. Soc. v.91 E. I. Heiba;R. M. Dessau;W. J. Koehi Jr.
  24. Chem. Tech. A. A. Zavitas
  25. J. Amer. Chem. Soc. v.87 C. Walling;M. T. Gibian