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Kinetics and mechanism of the aminolysis of O ‐ethyl S ‐aryl thiocarbonates in acetonitrile
Author(s) -
Oh Hyuk Keun,
Lee Yun Ho,
Lee Ikchoon
Publication year - 2000
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/(sici)1097-4601(2000)32:3<131::aid-kin2>3.0.co;2-c
Subject(s) - chemistry , aminolysis , kinetic isotope effect , benzylamine , acetonitrile , deuterium , kinetics , reactivity (psychology) , nucleophile , aryl , selectivity , medicinal chemistry , computational chemistry , stereochemistry , organic chemistry , catalysis , physics , alkyl , quantum mechanics , medicine , alternative medicine , pathology
The kinetics and mechanism of the reactions of O ‐ethyl S ‐( Z )aryl thiocarbonates with (X)benzylamines in acetonitrile at 45.0°C are studied. Relatively small values of β X (β nuc ) = 0.6 ∼ 0.8 and β Z (β lg ) = −0.5 ∼ −0.7 together with a negative cross‐interaction constant ρ XZ (= −0.47) and failure of the reactivity–selectivity principle (RSP) are interpreted to indicate a concerted mechanism. The normal kinetic isotope effects ( k H / k D = 1.3 ∼ 1.8) involving deuterated benzylamine nucleophiles suggest a hydrogen‐bonded, four‐center‐type transition state. © 2000 John Wiley & Sons, Inc. Int J Chem Kinet 32: 131–135, 2000