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http://dx.doi.org/10.5012/bkcs.2004.25.7.1041

Kinetic Studies on the Structure-Reactivity of Aryl Dithiomethylacetates  

Oh, Hyuck-Keun (Department of Chemistry, Chonbuk National University)
Park, Jie-Eun (Department of Chemistry, Chonbuk National University)
Lee, Hai-Whang (Department of Chemistry, Inha University)
Publication Information
Bulletin of the Korean Chemical Society / v.25, no.7, 2004 , pp. 1041-1045 More about this Journal
Abstract
Kinetic studies of the pyridinolysis $(XC_5H_4N)$ of aryl dithiomethylacetates $(CH_3CH_2C(=S)SC_6H_4Z,\;1)$ are carried out in acetonitrile at $60.0^{\circ}C$. A biphasic Bronsted plot is obtained with a change in slope from a large $({\beta}X\;{\cong}\;0.8)$ to a small $({\beta}X\;{\cong}\;0.2)$ value at $pK_a^{\circ}$ = 5.2, which is attributed to a change in the rate limiting step from breakdown to formation of a zwitterionic tetrahedral intermediate, $T^{\pm}$, in reaction path as the basicity of the pyridine nucleophile increases. This mechanism is supported by the change of the cross-interaction constant ${\rho}xz$ from a large positive ( ${\rho}xz$ = +1.36) for the weakly basic pyridines to a small negative ( ${\rho}_xz$ = -0.22) value for the strongly basic pyridines. The magnitudes of ${\rho}z$ and activation parameters are also consistent with the proposed mechanism.
Keywords
Nucleophilic substitution reaction; Pyridinolysis; Cross-interaction constant; Zwitterionic tetrahedral intermediate; Stepwise mechanism;
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