Kinetics and Catalysis

, Volume 46, Issue 1, pp 21–28 | Cite as

Mechanism of the hydrolysis of N-aryliminotriphenylphosphoranes

  • S.-Y. Pyun
  • Y.-H. Lee
  • T.-R. Kim


Hydrolysis reactions of N-aryliminotriphenylphosphoranes (I) at varying pH have been investigated kinetically. The reactions produced aniline derivatives and triphenylphosphine oxide as the products. The reactions are first-order, and the Hammett ρ values are -0.29 and -0.63 at pH 3.0 and 8.0, respectively. The reaction rate increased linearly with acetate ion concentration at [AcO] < 0.05 M and approached a limiting value at higher base concentration. The plot of logkt versus pH shows that there are two different regions in the rate profile; one part in which logkt increases with hydronium ion concentration and the other where kt is a constant regardless of pH. On the basis of these results, a plausible hydrolysis mechanism is proposed. At pH < 8.0, the reaction proceeds by protonation of the iminophosphorane nitrogen atom, followed by the addition of a water molecule. At pH > 8.0, the proton transfer from water to α-nitrogen of the iminophosphorane becomes the rate limiting step.


Hydrolysis Nitrogen Atom Aniline Proton Transfer Hydrolysis Reaction 
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© MAIK “Nauka/Interperiodica” 2005

Authors and Affiliations

  • S.-Y. Pyun
    • 1
  • Y.-H. Lee
    • 2
  • T.-R. Kim
    • 3
  1. 1.Department of ChemistryPukyong National UniversityKorea
  2. 2.Department of ChemistryWonkwang UniversityChunbukKorea
  3. 3.Department of ChemistryKorea UniversityKorea

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