Kinetics and Mechanism of the Anilinolysis of Bis(N,N-dimethylamino) Phosphinic Chloride in Acetonitrile 


Vol. 32,  No. 12, pp. 4361-4365, Dec.  2011
10.5012/bkcs.2011.32.12.4361


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  Abstract

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.

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  Cite this article

[IEEE Style]

H. R. Barai and H. W. Lee, "Kinetics and Mechanism of the Anilinolysis of Bis(N,N-dimethylamino) Phosphinic Chloride in Acetonitrile," Bulletin of the Korean Chemical Society, vol. 32, no. 12, pp. 4361-4365, 2011. DOI: 10.5012/bkcs.2011.32.12.4361.

[ACM Style]

Hasi Rani Barai and Hai Whang Lee. 2011. Kinetics and Mechanism of the Anilinolysis of Bis(N,N-dimethylamino) Phosphinic Chloride in Acetonitrile. Bulletin of the Korean Chemical Society, 32, 12, (2011), 4361-4365. DOI: 10.5012/bkcs.2011.32.12.4361.

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ISSN(Print) 0253-2964
ISSN(Online) 1229-5949