Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Kinetics and Mechanism of the Anilinolysis of Dipropyl Chlorothiophosphate in Acetonitrile

  • Received : 2011.09.25
  • Accepted : 2011.10.06
  • Published : 2011.12.20
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Abstract

The nucleophilic substitution reactions of dipropyl chlorothiophosphate (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; $k_H/k_D$) are primary normal ($k_H/k_D$ = 1.11-1.35). A concerted mechanism involving predominant frontside nucleophilic attack is proposed on the basis of the primary normal DKIEs and selectivity parameters. Hydrogen bonded, four-center-type transition state is proposed. The steric effects of the two ligands on the anilinolysis rates of various substrates are discussed.

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References

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