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http://dx.doi.org/10.5012/bkcs.2003.24.7.925

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)
Publication Information
Bulletin of the Korean Chemical Society / v.24, no.7, 2003 , pp. 925-930 More about this Journal
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.
Keywords
Aryl cyclopropanecarboxylates; Stepwise mechanism; Zwitterionic tetrahedral intermediate; Cross interaction constant; Reactivity-selectivity principle;
Citations & Related Records
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