Bulletin of the Korean Chemical Society

  • 제8권3호
  • /
  • Pages.193-196
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  • 1987
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  • 0253-2964(pISSN)
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  • 1229-5949(eISSN)
대한화학회 (Korean Chemical Society)
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Determination of Reactivity by MO Theory (Part 50). MO Studies on the Gas Phase Pyrolysis of Esters

  • 발행 : 1987.06.20
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초록

The gas phase pyrolyses of eight esters have been studied by MNDO-MO method. In the ethylformate pyrolysis, ${\alpha}$-methylation had a steric releasing effect whereas ${\beta}$-methylation had a steric crowding in the transition state; the latter, however, is over-compensated by a greater electronic repulsion resulting in a net steric releasing effect. Considerations of formal charges and geometrical changes involved in the activation led us to propose a pyrolysis mechanism in which a preequilibrium of acidic proton transfer is followed by the rate-limiting bond polarization of $C_{\alpha}$-O bond in a cyclic transition state.

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참고문헌

  1. Organic Reactions and Orbital Symmetry(2nd ed.) T. L. Gilchrist;R. S. Storr
  2. J. Am. Chem. Soc. v.84 R. Taylor;G. G. Smith;W. H. Wetzel
  3. J. Chem. Soc., Perkin 2 R. Taylor
  4. J. Chem. Soc., Perkin 2 G. Chuchani;I. Martin;A. Maccoll
  5. J. Chem. Soc., Perkin 2 H. B. Amin;R. Taylor
  6. J. Chem. Soc., Perkin 2 R. Taylor
  7. J. Chem. Soc., Perkin 2 R. Taylor;M. P. Thorne
  8. J. Chem. Soc., Perkin 2 S. deB. Narfolk;R. Taylor
  9. J. Chem. Soc., Perkin 2 H. B. Amin;R. Taylor
  10. J. Chem. Soc., Perkin 2 H. B. Amin;R. Taylor
  11. J. Chem. Soc., Perkin 2 R. Taylor
  12. J. Phys. Chem. v.84 I. Martin;G. Chuchani;I. Avlla;A. Rotinov;R. Olmas
  13. J. Phys. Chem. v.84 G. Chuchani;I. Martin;J. A. Hernandez A.;A. Rotinov;G. Fralle;D. B. Bigley
  14. J. Am. Chem Soc. v.99 M. J. S. Dewar;W. Thiel
  15. Theory and Practice of MO Calculations on Organic Molecules I. G. Csizmadia
  16. J. Am. Chem. Soc. v.97 N. D. Epiotis;R. L. Yates;F. Bernardi
  17. J. Am. Chem. Soc. v.101 T. K. Brunck;F. Weinlrold
  18. J. Am. Chem. Soc. v.106 J. E. Dubois;M. F. Ruasse;A. Argile
  19. Chem. Rev. v.85 W. P. Jencks
  20. J. Chem. Soc. Chem. Commun. I. Lee;S. S. Sohn
  21. Tetrahedron Lett. I. Lee;H. K. Kang
  22. I. Lee;H. Y. Kim;H. K. Kang
  23. Chemical Structure and Bonding R. L. Dekock;H. B. Gray
  24. J. Am. Chem. Soc. v.100 J. R. Larson;N. D. Epiotis;F. Bernardi
  25. The Molecular Orbital Theory of Organic Chemistry M. J. S. Dewar
  26. J. Am. Chem. Soc. v.77 G. S. Hammond
  27. Mechanism and Theory in Organic Chemistry(2nd ed.) T. H. Lowry;K. S. Richardson

피인용 문헌

  1. A quantum chemical investigation of pyrolysis reactions of glyoxylic acid ethylester : PYROLYSIS REACTIONS OF GLYOXYLIC ACID ETHYLESTER vol.40, pp.4, 1987, https://doi.org/10.1002/qua.560400405
  2. From Sulfoxide Precursors to Model Oligomers of Conducting Polymers vol.124, pp.25, 1987, https://doi.org/10.1021/ja012700p