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http://dx.doi.org/10.5012/bkcs.2007.28.6.936

Kinetics and Mechanism of the Aminolysis of Diphenyl Phosphinic Chloride with Anilines  

Ul Hoque, Md.Ehtesham (Department of Chemistry, Inha University)
Lee, Hai-Whang (Department of Chemistry, Inha University)
Publication Information
Bulletin of the Korean Chemical Society / v.28, no.6, 2007 , pp. 936-940 More about this Journal
Abstract
The aminolyses of diphenyl phosphinic chloride (1) with substituted anilines in acetonitrile at 55.0 oC are investigated kinetically. Large Hammett ρ X (ρnuc = ?4.78) and Bronsted β X (βnuc = 1.69) values suggest extensive bond formation in the transition state. The primary normal kinetic isotope effects (kH/kD = 1.42-1.82) involving deuterated aniline (XC6H4ND2) nucleophiles indicate that hydrogen bonding results in partial deprotonation of the aniline nucleophile in the rate-limiting step. The faster rate of diphenyl phosphinic chloride (1) than diphenyl chlorophosphate (2) is rationalized by the large proportion of a frontside attack in the reaction of 1. These results are consistent with a concerted mechanism involving a partial frontside nucleophilic attack through a hydrogen-bonded, four-center type transition state.
Keywords
Anilinolysis of diphenyl phosphinic chloride; Frontside nucleophilic attack; Deuterium kinetic isotope effect;
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Times Cited By Web Of Science : 57  (Related Records In Web of Science)
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