Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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AM1 Studies on the Gas-Phase Pyrolysis of Iminoethers, 2-Alkoxypyridines, 2-N-Alkylated Pyridones and N-Alkylated Acetamides

  • Bon-Su Lee (Department of Chemistry, Inha University) ;
  • Chang Kon Kim (Department of Chemistry, Inha University) ;
  • Ikchoon Lee (Department of Chemistry, Inha University)
  • Published : 1991.10.20
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Abstract

The gas-phase pyrolysis reactions of iminoethers (Ⅱ), 2-alkoxypyridines (Ⅲ), 2-N-alkylated pyridones (Ⅳ) and N-alkylated acetamides (Ⅴ) have been studied MO theoretically with the AM1 method. The decomposition of these compounds proceeds by a concerted retro-ene process through a six-membered cyclic transition state. The reactivity decreases in the order (Ⅱ) > (Ⅲ) > (Ⅳ) > (Ⅴ), with a greater reactivity for the imine series, (Ⅱ) and (Ⅲ), compared to the amide series, (Ⅳ) and (Ⅴ), and a difference in basicity between the N and O atoms. Within a given series, however, the reactivity is dictated mainly by the aromaticity in the transition state. The reactivity order with respect to side alkyl chain of a species was found to increase as the steric crowding effect increases. The AM1 reactivity in this work agree well with the experimental results.

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References

  1. Bull. Korean Chem. Soc. Determination of Reactivity by MO Theory C. K. Kim;I. Lee;H. W. Lee;B. -S. Lee
  2. The Chemistry of the Functional Groups, Supplementary Volume B. Acid Derivatives R. Taylor;S. Patai(ed.)
  3. J. Chem. Soc. Perkin Trans. v.2 R. Taylor
  4. J. Chem. Soc., Perkin Trans. v.2 R. Taylor;M. P. Thorne
  5. J. Chem. Soc., Perkin Trans. v.2 S. de B. Norfolk;R. Taylor
  6. J. Chem. Soc., Perkin Trans. v.2 N. Al-Awadi;R. F. Al-Bashir;O. M. E. El-Dosouqui
  7. J. Phys. Chem. v.94 I. Lee;O. J. Cha;B. -S. Lee
  8. J. Phys. Org. Chem. v.3 I. Lee;O. J. Cha;B. -S. Lee
  9. Bull. Korean Chem. Soc. v.12 I. Lee;O. J. Cha;B. -S. Lee
  10. J. Am. Chem. Soc. v.107 M. J. S. Dewar;E. G. Zoebisch;E. F. Healy;J. J. P. Stewart
  11. J. Chem. Soc. Perkin Trans. v.2 R. Taylor
  12. Bull. Korean Chem. Soc. v.11 I. Lee;O. J. Cha;B. -S. Lee
  13. AMPAC: Austin Model 1 Package(QCPE No. 506) M. J. S. Dewar
  14. Theory and Practice of MO Calculations on Organic Molecules I. G. Csizmadia
  15. J. Am. Chem. Soc. v.93 M. J. S. Dewar;S. Kirschner
  16. J. Am. Chem. Soc. v.94 J. W. Mclver;A. Komornicki
  17. J. Chem. Soc., Perkin Trans. v.2 N. Al-Awadi;J. Ballam;P. R. Hemblade;R. Taylor
  18. Acta Chem. Scand. v.B40 R. Virtanen
  19. Acta Chem. Scand. v.B41 R. Kimmelma;E. Taskinen
  20. Acta Chem. Scand. v.B42 R. Kimmelma
  21. Tetrashedron v.31 F. Bernardi;I. Csizmadia;N. D. Epiotis
  22. Chem. Rev. v.60 C. H. Depuy;R. W. King
  23. Frontier Orbitals and Organic Chemical Reactions I. Fleming
  24. Angew. Chem. Int. Ed. Engl. v.8 H. M. R. Hoffmann
  25. J. Korean Chem. Soc. v.28 J. K. Cho;I. Lee;H. K. Oh;I. H. Cho
  26. The PMO Theory of Organic Chemistry M. J. S. Dewar;R. C. Dougherty
  27. J. Am. Chem. Soc. v.90 L. Salem
  28. Physical Organic Chemistry N. S. Isaacs
  29. J. Chem. Soc. A. Maccoll