Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Kinetics and Mechanism of the Pyridinolysis of Aryl Cyclopropanecarboxylates in Acetonitrile

  • Koh, Han-Joong (Department of Science Education, Chonju National University of Education) ;
  • Kang, Suk-Jin (Department of Science Education, Chonju National University of Education) ;
  • Kim, Cheol-Ju (Department of Chemistry, Chonbuk National University) ;
  • Lee, Hai-Whang (Department of Chemistry, Inha University) ;
  • Lee, Ik-Choon (Department of Chemistry, Inha University)
  • Published : 2003.07.20
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Abstract

Kinetic studies of the reaction of Z-aryl cyclopropanecarboxylates with X-pyridines in acetonitrile at 55.0 ℃ have been carried out. The reaction proceeds by a stepwise mechanism in which the rate-determining step is the breakdown of the zwitterionic tetrahedral intermediate, $T^{\pm}$. These mechanistic conclusions are drawn base on (i) the large magnitude of ρx and ρz, (ii) the positive sign of ρxz and the larger magnitude of ρxz than normal $S_N2$ processes, (iii) a small positive enthalpy of activation, Δ$H^≠$, and a large negative, Δ$S^≠$, and lastly (iv) adherence to the reactivity-selectivity principle (RSP) in all cases.

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References

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