Determination of Reactivities by Molecular Orbital Theory (VII). SCF-IMO Studies on the Diels-Alder Reactions between Cyclopentadiene and 2-Substituted Acrylonitriles

화학반응성의 분자궤도론적 연구 (제7보). 시클로펜타디엔과 아크릴로니트릴 치환체간의 Diels-Alder 반응에 대한 SCF-IMO 연구

  • 이익춘 (인하대학교 이과대학 화학과) ;
  • 최은화 (인하대학교 이과대학 화학과)
  • Published : 1975.08.30


The ground state SCF IMO theory was applied to the Diels-Alder reactions of cyclopentadiene with 2-substituted acrylonitriles. The CNDO/2 MO of the separate systems, including both $\sigma$ and $\pi$ electrons, was used as starting point. The qualitative prediction of the relative reactivity was made with the calculated primary interaction energies. Here the calculated activation energies appeared to be realistic. The stereoselectivity determined by the calculated secondary interaction energies represented the endo-selectivity for all the substituents. The reason for the slightly unsymmetrical ring closure at the transition state was discussed in terms of valence inactive electron densities of the reacting atoms.



  1. Diels-Alder Reactions A. Wasseerman
  2. Chem. Soc. Spec. Publ. no.21 M.J.S. Dewar
  3. J. Amer. Chem. Soc. v.90 L. Salem
  4. Theor. Chim. Acta v.8 E. Klopman;R.F. Hudson
  5. J. Amer. Chem. Soc. v.91 A. Devaquet;L. Salem
  6. Molecular Phys. v.18 A. Devaquet
  7. J. Chem. Phys. v.43 J. A. Pople;D.P. Santry;G.A. Segal
  8. The Chem. Soc. no.18 Interatomic Distances L.E. Sutton
  9. J. Chem. Phys. v.17 R. S. Mulliken;C. A. Rieke;D. Orloff;H. Orloff
  10. Chem. Rev. v.72 W.C. Herndon
  11. Tetrahedron v.5 R.B. Woodward;T. Katz.
  12. J. Amer. Chem. Soc. v.93 I. Lee;M.H. Whnagbo
  13. J.C.S. Perkin II J.M. Mellor;C.F. Webb
  14. J. Chem. Phys. v.23 R.S. Mulliken(et al.)
  15. Bull. Chem. Soc. Japan v.42 K. Fukui(et al.)
  16. Approximate Molecular Orbital Theory J.A. Pople;P.L. Beveridge