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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 32, Number 7
BKCSDE 32(7)
July 20, 2011

Title	Kinetics and Mechanism of the Anilinolysis of Diethyl Thiophosphinic Chloride in Acetonitrile
Author	Md. Ehtesham Ul Hoque, Hai Whang Lee *
Keywords	Phosphoryl transfer reaction, Anilinolysis, Diethyl thiophosphinic chloride, Deuterium kinetic isotope effect
Abstract	The nucleophilic substitution reactions of diethyl thiophosphinic chloride with substituted anilines (XC6H4NH2) and deuterated anilines (XC6H4ND2) are investigated kinetically in acetonitrile at 55.0 oC. The values of deuterium kinetic isotope effects (DKIEs; kH/kD) invariably increase from secondary inverse (kH/kD < 1) to primary normal (kH/kD > 1) as the nucleophiles change from the strongly basic to weakly basic anilines. The secondary inverse with the strongly basic anilines and primary normal DKIEs with the weakly basic anilines are rationalized by the gradual transition state (TS) variation from a predominant backside attack, via invariably increasing the fraction of a frontside attack, to a predominant frontside attack, in which the reaction mechanism is a concerted SN2 pathway. A frontside attack involving a hydrogen bonded, four-center-type TS is substantiated by the primary normal DKIEs.
Page	2306 - 2310
Full Text	PDF / Supporting Information

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