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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 25, Number 4
BKCSDE 25(4)
April 20, 2004 

Kinetics and Mechanism of the Aminolysis of Anilino Thioethers with Benzylamines in Acetonitrile
Hyuck Keun Oh, Jae Myun Lee, Dae Dong Sung, Ikchoon Lee*
Anilinothioether, Frontside-attack, SN2, Inverse secondary isotope effect
The aminolyses of anilinothioethers (C6H5N(CH3)CH2SC6H4Z) in acetonitrile with benzylamines (XC6H4CH2NH2) have been investigated. The rates are much lower in acetonitrile than in methanol (with aniline). The Bronsted βX values are similar but βZ values are smaller compared to those for the reactions in MeOH with anilines. The large negative ρXZ (≡ -0.8, after correction for fall-off) value is interpreted to indicate a frontside attack SN2 mechanism, in which the two oppositely changed reaction centers in the TS, -Nδ+ ...Sδ--, are in close vicinity increasing the interaction between nucleophile and leaving group. The inverse secondary kinetic isotope effects (kH/kD < 1.0) are observed with deuterated benzylamines (XC6H4CH2ND2).
557 - 559
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