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http://dx.doi.org/10.5012/bkcs.2004.25.4.557

Kinetics and Mechanism of the Aminolysis of Anilino Thioethers with Benzylamines in Acetonitrile  

Oh, Hyuck-Keun (Department of Chemistry, Chonbuk National University)
Lee, Jae-Myun (Department of Chemistry, Chonbuk National University)
Sung, Dae-Dong (Department of Chemistry, Dong-A University)
Lee, Ik-Choon (Department of Chemistry, Inha University)
Publication Information
Bulletin of the Korean Chemical Society / v.25, no.4, 2004 , pp. 557-559 More about this Journal
Abstract
The aminolyses of anilinothioethers $(C_6H_5N(CH_3)CH_2SC_6H_4Z)$ in acetonitrile with benzylamines $(XC_6H_4CH_2NH_2)$ have been investigated. The rates are much lower in acetonitrile than in methanol (with aniline). The Bronsted ${\beta}_X$ values are similar but ${\beta}_Z$ values are smaller compared to those for the reactions in MeOH with anilines. The large negative ${\rho}_{XZ}({\cong}-0.8$, after correction for fall-off) value is interpreted to indicate a frontside attack $S_N2$ mechanism, in which the two oppositely changed reaction centers in the TS, $-N^{{\delta}+}{\cdots}S^{{\delta}-}-$, are in close vicinity increasing the interaction between nucleophile and leaving group. The inverse secondary kinetic isotope effects ($k_H/k_D$ < 1.0) are observed with deuterated benzylamines $(XC_6H_4CH_2ND_2)$.
Keywords
Anilinothioether; Frontside-attack; $S_N2$; Inverse secondary isotope effect;
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