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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 22, Number 10
BKCSDE 22(10)
October 20, 2001 

Kinetics and Mechanism of the Aminolysis of Thiophenyl 2-Thiopheneacetates in Acetonitrile
Hyuck Keun Oh, Juri Jeong
Aminolysis, Acyl transfer reaction, Stepwise mechanism.
Kinetic studies of the reaction of Z-thiophenyl 2-thiopheneacetates with X-benzylamines in acetonitrile 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±, with a hydrogen-bonded four-center type transition state (TS). These mechanistic conclusions are drawn base on (i) the large magnitude of ρX and ρZ, (ⅱ) the normal kinetic isotope effects (kH/kD > 1.0) involving deuterated benzylamine nucleophiles, (ⅲ) the positive sign of ρXZ and the larger magnitude of ρXZ than that for normal SN2 processes, and lastly (iv) adherence to the reactivity-selectivity principle (RSP) in all cases.
1123 - 1126
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