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Kinetics and mechanism of the aminolysis of O-ethyl S-aryl thiocarbonates in acetonitrile

✍ Scribed by Hyuk Keun Oh; Yun Ho Lee; Ikchoon Lee

Publisher
John Wiley and Sons
Year
2000
Tongue
English
Weight
51 KB
Volume
32
Category
Article
ISSN
0538-8066

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✦ Synopsis

The kinetics and mechanism of the reactions of O-ethyl S-(Z)aryl thiocarbonates with (X)benzylamines in acetonitrile at 45.0ЊC are studied. Relatively small values of ␀ X (␀ nuc ) Ο­ 0.6 Ο³ 0.8 and ␀ Z (␀ lg ) Ο­ Οͺ0.5 Ο³ Οͺ0.7 together with a negative cross-interaction constant XZ (Ο­ Οͺ0.47) and failure of the reactivity-selectivity principle (RSP) are interpreted to indicate a concerted mechanism. The normal kinetic isotope effects (k H /k D Ο­ 1.3 Ο³ 1.8) involving deuterated benzylamine nucleophiles suggest a hydrogen-bonded, four-center-type transition state.

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