Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Kinetics and Mechanism of the Anilinolysis of Diisopropyl Chlorophosphate in Acetonitrile

  • Received : 2011.07.13
  • Accepted : 2011.07.16
  • Published : 2011.09.20
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Abstract

The nucleophilic substitution reactions of diisopropyl 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 anilinolysis rate of 3 is rather slow to be rationalized by the conventional stereoelectronic effects. The obtained deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are secondary inverse ($k_H/k_D$ = 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.

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References

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