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http://dx.doi.org/10.5012/bkcs.2003.24.1.091

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)
Publication Information
Bulletin of the Korean Chemical Society / v.24, no.1, 2003 , pp. 91-94 More about this Journal
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.
Keywords
O-Methyl-S-phenylthiocarbonates; Stepwise mechanism; Zwitterionic tetrahedral intermediate; Cross-interaction constant;
Citations & Related Records
Times Cited By KSCI : 1  (Citation Analysis)
Times Cited By Web Of Science : 19  (Related Records In Web of Science)
Times Cited By SCOPUS : 20
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