Bulletin of the Korean Chemical Society

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Kinetics and Mechanism of the Anilinolysis of O-Ethyl Phenyl Phosphonochloridothioate in Acetonitrile

  • Received : 2012.04.01
  • Accepted : 2012.05.23
  • Published : 2012.08.20
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Abstract

The nucleophilic substitution reactions of O-ethyl phenyl phosphonochloridothioate with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are kinetically investigated in acetonitrile at $55.0^{\circ}C$. The deuterium kinetic isotope effects (DKIEs) invariably increase from a secondary inverse DKIE ($k_H/k_D$ = 0.93) to a primary normal DKIE ($k_H/k_D$ = 1.28) as the substituent of nucleophile (X) changes from electron-donating to electron-withdrawing. These can be rationalized by the gradual transition state (TS) variation from a backside to frontside attack. A concerted $S_N2$ mechanism is proposed. A trigonal bipyramidal TS is proposed for a backside attack while a hydrogen-bonded, four-center-type TS is proposed for a frontside attack.

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References

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