Bulletin of the Korean Chemical Society

  • 제12권1호
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  • Pages.97-101
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  • 1991
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  • 0253-2964(pISSN)
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  • 1229-5949(eISSN)
대한화학회 (Korean Chemical Society)
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Theoretical Studies on the Gas-Phase Pyrolysis of Carbonate Esters, Hydroxy-Esters and -Ketones

  • 발행 : 1991.02.20
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초록

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.

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참고문헌

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피인용 문헌

  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