DOI QR코드

DOI QR Code

Theoretical Studies on the Gas-Phase Pyrolysis of Carbonate Esters, Hydroxy-Esters and -Ketones

  • Published : 1991.02.20

Abstract

Gas-phase pyrolyses of carbonate esters, ${\alpha}$- and ${\beta}$-hydroxy esters and ${\beta}$-hydroxy ketones have been studied theoretically by the AM1 MO method. Carbonate esters were found to decompose by two types of processes; in the reaction pathway involving an intermediate, the decomposition of the intermediate was rate-limiting, but direct pyrolyses were also possible via a six-membered cyclic transition state in which the methoxy oxygen attacks a hydrogen atom on the ${\beta}$-carbon. The hydroxy esters and ketones were found to decompose in a concerted process involving a six-membered cyclic transition state. Successive methylation on the ${\alpha}$- and ${\gamma}$-carbon led to an increase in the reactivity in agreement with experiments.

Keywords

References

  1. Determination of Reactivity by MO Theory I. Lee;J. K. Cho;C. K. Kim
  2. J. Phys. Chem. v.94 I. Lee;O. J. Cha;B. -S. Lee
  3. J. Phys. Org. Chem. v.3 I. Lee;O. J. Cha;B. -S. Lee
  4. Bull. Korean Chem. Soc. v.11 I. Lee;O. J. Cha;B. -S. Lee
  5. Bull. Korean Chem. Soc. v.8 I. Lee;Y. S. Park;B. -S. Lee
  6. Angew. Chem. Int. Ed. Engl. v.8 H. M. R. Hoffmann
  7. Angew. Chem. Int. Ed. Engl. v.17 W. Oppolzer;V. Snieckus
  8. J. Chem. Phys. v.20 K. Fukui;T. Yonezawa;H. Shingu
  9. J. Am. Chem. Soc. v.97 K. Fukui;S. Inagaki
  10. J. Am. Chem. Soc. v.98 S. Inagakai;H. Fujimoto;K. Fukui
  11. J. Am. Chem. Soc. v.98 S. Inagaki;H. Fujimoto;K. Fukui
  12. Theory of Orientation and Stereoselection K. Fukui
  13. J. Chem. Soc., Perkin Trans. 2 R. Taylor
  14. J. Chem. Soc., Perkin Trans. 2 R. Taylor
  15. J. Chem. Soc., Perkin Trans. 2 R. Taylor;M. P. Thorne
  16. J. Chem. Soc., Perkin Trans. 2 S. de B. Norfolk;R. Taylor
  17. J. Chem. Soc., Perkin Trans. 2 D. B. Bigley;R. E. Gabbott
  18. J. Chem. Soc., Perkin Trans. 2 D. B. Bigley;R. E. Gabbott
  19. J. Chem. Soc., Perkin Trans. 2 N. Al-Awadi;D. B. Bigley;R. E. Gabbott
  20. J. Phys. Chem. v.84 G. Chuchani;I. Martin;J. A. Hernandez;A. Rotinov;G. Fraile;D. B. Bigley
  21. Chem. Riv. v.60 C. H. Depuy;R. W. King
  22. J. Chem. Soc., Perkin Trans. 2 A. Maccoll
  23. J. Chem. Soc., Perkin Trans. 2 N. A. Al-Awadi;R. F. Al-Bashir;O. M. E. El-Dusouqui
  24. The Chemistry of the Functional Groups, Supplementary Volume B. Acid Derivatives R. Taylor;S. Patai(ed.)
  25. J. Am. Chem. Soc. v.107 M. J. S. Dewar;D. M. Storch
  26. J. Am. Chem. Soc. v.107 M. J. S. Dewar;E. G. Zoebisch;E. F. Healy;J. J. P. Stewart
  27. Angew. Chem. Int. Ed. Engl. v.19 K. Muller
  28. J. Phys. Chem. v.80 S. Bell;J. S. Crighton
  29. J. Phys. Chem. v.74 K. Fukui
  30. J. Am. Chem. Soc. v.94 J. W. McIver;A. Komornicki
  31. J. Chem. Soc. Perkin 2 R. August;I. McEwen;R. Taylor
  32. J. Chem. Soc. Perkin 2 R. Taylor
  33. J. Chem. Soc. Perkin 2 R. Taylor

Cited by

  1. Theoretical studies on the gas-phase smiles rearrangement vol.4, pp.5, 1991, https://doi.org/10.1002/poc.610040509
  2. Theoretical studies of substituent effects on thermal eliminations of aryl ethyl carbonates andS-arylO-ethyl thiocarbonates vol.6, pp.4, 1991, https://doi.org/10.1002/poc.610060404
  3. Theoretical studies of substituent effects on thermal eliminations of aryl ethyl carbonates andS-arylO-ethyl thiocarbonates vol.6, pp.4, 1991, https://doi.org/10.1002/poc.610060404
  4. The Effect of Medium on Rate and Mechanism: Aminolysis ofO-4-Nitrophenyl Thionobenzoate in MeCN and H2O vol.68, pp.20, 2003, https://doi.org/10.1021/jo034637n
  5. Theoretical study of the mechanism of thermal decomposition of carbonate esters in the gas phase vol.18, pp.2, 1991, https://doi.org/10.1002/poc.866
  6. Aminolyses of 4-Nitrophenyl Phenyl Carbonate and Thionocarbonate: Effect of Modification of Electrophilic Center from C&dbd;O to C&dbd;S on Reactivity and Mechanism vol.71, pp.6, 1991, https://doi.org/10.1021/jo052417z
  7. Pyrolysis of (thio)carbonates via computation analysis vol.17, pp.6, 1991, https://doi.org/10.1142/s0219633618500414
  8. A theoretical study towards thermolysis process of thionesters and thiolesters vol.17, pp.2, 2018, https://doi.org/10.1142/s0219633618500141
  9. Theoretical Computations on the Pyrolysis of Alkyl (dithio)acetates vol.17, pp.3, 1991, https://doi.org/10.2174/1570178616666190717123039