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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 35, Number 9
BKCSDE 35(9)
September 20, 2014 

Kinetics and Mechanism of Anilinolyses of Aryl Methyl and Aryl Propyl Chlorothiophosphates in Acetonitrile
Hasi Rani Barai, Hai Whang Lee*
Thiophosphoryl transfer reaction, Anilinolysis, Y-Aryl methyl and Y-aryl propyl chlorothiophosphates, Deuterium kinetic isotope effect, Cross-interaction constant
Nucleophilic substitution reactions of Y-aryl methyl (8) and Y-aryl propyl (10) chlorothiophosphates with substituted anilines and deuterated anilines are investigated kinetically in acetonitrile at 55.0 oC. A concerted mechanism is proposed for 8 based on the negative ρXY (= –0.23) value, while a stepwise mechanism with a rate-limiting leaving group departure from the intermediate is proposed for 10 based on the positive ρXY (= +0.68) value. The deuterium kinetic isotope effects (DKIEs; kH/kD) are 0.89-1.28 and 0.62-1.20 with 8 and 10, respectively. Primary normal and secondary inverse DKIEs are rationalized by a frontside attack involving hydrogen bonded, four-center-type transition state and backside attack involving in-line-type transition state, respectively.
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