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http://dx.doi.org/10.5012/bkcs.2011.32.5.1539

Kinetics and Mechanism of the Aminolysis of O-Methyl S-Aryl Thiocarbonates in Acetonitrile  

Oh, Hyuck-Keun (Department of Chemistry, Research Institute of Physics and Chemistry, Chonbuk National University)
Publication Information
Bulletin of the Korean Chemical Society / v.32, no.5, 2011 , pp. 1539-1542 More about this Journal
Abstract
The aminolysis of O-methyl S-aryl thiocarbonates with benzylamines are studied in acetonitrile at -45.0$^{\circ}C$. The ${\beta}_X$(${\beta}_{nuc}$) values are in the range 0.62-0.80 with a negative cross-interaction constant, ${\rho}_{XZ}$ = -0.42, which are interpreted to indicate a concerted mechanism. The kinetic isotope effects involving deuterated benzylamine nucleophiles ($XC_6H_4CH_2ND_2$) are large, $k_H/k_D$ = 1.29-1.75, suggesting that the N-H(D) bond is partially broken in the transition state by forming a hydrogen-bonded four-center cyclic structure. The concerted mechanism is enforced by the strong push provided by the MeO group which enhances the nucleofugalities of both benzylamine and arenethiolate from the putative zwitterionic tetrahedral intermediate.
Keywords
Nucleophilic substitution reaction; Concerted mechanism; Cross-interaction constant; Kinetic isotope effects; Four-center cyclic transition state;
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