Current time in Korea 04:40 Oct 01 (Thu) Year 2020 KCS KCS Publications
KCS Publications
My Journal  Log In  Register
HOME > Search > Browsing(BKCS) > Archives

Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 32, Number 9
BKCSDE 32(9)
September 20, 2011 

 
Title
Kinetics and Mechanism of the Anilinolysis of Diisopropyl Chlorophosphate in Acetonitrile
Author
Md. Ehtesham Ul Hoque, Hai Whang Lee *
Keywords
Phosphoryl transfer reaction, Anilinolysis, Diisopropyl chlorophosphate, Deuterium kinetic isotope effect
Abstract
The nucleophilic substitution reactions of diisopropyl chlorophosphate (3) with substituted anilines (XC6H4NH2) and deuterated anilines (XC6H4ND2) are investigated kinetically in acetonitrile at 55.0 oC. The anilinolysis rate of 3 is rather slow to be rationalized by the conventional stereoelectronic effects. The obtained deuterium kinetic isotope effects (DKIEs; kH/kD) are secondary inverse (kH/kD = 0.71-0.95) with maximum magnitude at X = H. A concerted mechanism involving predominant backside nucleophilic attack is proposed on the basis of the secondary inverse DKIEs.
Page
3245 - 3250
Full Text
PDF / Supporting Information