Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Determination of Reactivity by MO Theory (Part 50). MO Studies on the Gas Phase Pyrolysis of Esters

  • Published : 1987.06.20
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Abstract

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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  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