Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Kinetics and Mechanism of the Aminolysis of O-Methyl-S-Phenylthiocarbonates in Methanol

  • Song, Ho-Bong (Department of Chemistry, Kyung-Gi University) ;
  • Choi, Moon-Ho (Department of Chemistry, Kyung-Gi University) ;
  • Koo, In-Sun (Department of Chemistry Education and Research Institute of Natural Sciences,Gyeongsang National University) ;
  • Oh, Hyuck-Keun (Department of Chemistry, Chonbuk National University) ;
  • Lee, Ik-choon (Department of Chemistry, Inha University)
  • Published : 2003.01.20
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Abstract

Kinetic studies of the reaction of O-methyl-S-phenylthiocarbonates with benzylamines in methanol at 45.0 ℃ 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, $T^{\pm}$, with a hydrogen-bonded four-center type transition state (TS). These mechanistic conclusions are drawn based on (ⅰ) the large magnitude of ${\rho}_X\;and\;{\rho}_Z$, (ⅱ) the normal kinetic isotope effects $(k_H/k_D\;>\;1.0)$ involving deuterated benzylamine nucleophiles, (ⅲ) the positive sign of ${\rho}_{XZ}$ and the larger magnitude of ${\rho}_{XZ}$ than that for normal $S_N2$ processes, and lastly (ⅳ) adherence to the reactivity-selectivity principle (RSP) in all cases.

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References

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