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http://dx.doi.org/10.5012/bkcs.2012.33.2.663

Kinetics and Mechanism of the Anilinolysis of Dibutyl Chlorophosphate in Acetonitrile  

Hoque, Md. Ehtesham Ul (Department of Chemistry, Inha University)
Lee, Hai-Whang (Department of Chemistry, Inha University)
Publication Information
Bulletin of the Korean Chemical Society / v.33, no.2, 2012 , pp. 663-669 More about this Journal
Abstract
The nucleophilic substitution reactions of dibutyl chlorophosphate (3) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $55.0^{\circ}C$. The obtained deuterium kinetic isotope effects (DKIEs; kH/kD) are secondary inverse ($k_H/k_D$ = 0.86-0.97) with the strongly basic anilines while primary normal ($k_H/k_D$ = 1.04-1.10) with the weakly basic anilines. The DKIEs, steric effects of the two ligands, activation parameters, cross-interaction constants, variation trends of the kH/kD values with X, and mechanism are discussed for the anilinolyses of the nine ($R_1O$)($R_2O$)P(=O)Cl-type chlorophosphates. A concerted mechanism is proposed with a backside nucleophilic attack transition state for the strongly basic anilines and with a frontside attack involving a hydrogen-bonded four-center-type transition state for the weakly basic anilines on the basis of the magnitudes, secondary inverse and primary normal, and variation trends of the $k_H/k_D$ values with X.
Keywords
Phosphoryl transfer reaction; Anilinolysis; Dibutyl chlorophosphate; Deuterium kinetic isotope effect;
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