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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 32, Number 12
BKCSDE 32(12)
December 20, 2011 

Kinetics and Mechanism of the Anilinolysis of Bis(N,N-dimethylamino) Phosphinic Chloride in Acetonitrile
Hasi Rani Barai, Hai Whang Lee *
Phosphoryl transfer reaction, Anilinolysis, Bis(N,N-dimethylamino) phosphinic chloride, Deuterium kinetic isotope effect
The nucleophilic substitution reactions of bis(N,N-dimethylamino) phosphinic chloride (3) with substituted anilines (XC6H4NH2) and deuterated anilines (XC6H4ND2) are investigated kinetically in acetonitrile at 65.0 oC. The anilinolysis rate of 3 is rather slow to be rationalized by the conventional stereoelectronic effects. The magnitudes of ρX (= –6.42) and βX (= 2.27) values are exceptionally great. The deuterium kinetic isotope effects (DKIEs; kH/kD) are secondary inverse (kH/kD = 0.69-0.96). A concerted SN2 mechanism involving a backside attack is proposed on the basis of secondary inverse DKIEs and the variation trend of the kH/kD values with X. The anilinolyses of six phosphinic chlorides in MeCN are briefly reviewed by means of DKIEs, steric effects of the two ligands, positive charge of the reaction center phosphorus atom, and selectivity parameters to obtain systematic information on phosphoryl transfer reaction mechanism.
4361 - 4365
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