Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Leaving-Group Substituent Controls Reactivity and Reaction Mechanism in Aminolysis of Phenyl Y-Substituted-Phenyl Carbonates

  • Kang, Ji-Sun (Department of Chemistry and Nano Science, Ewha Womans University) ;
  • Song, Yoon-Ju (Department of Chemistry, Duksung Women's University) ;
  • Um, Ik-Hwan (Department of Chemistry and Nano Science, Ewha Womans University)
  • Received : 2013.04.01
  • Accepted : 2013.04.09
  • Published : 2013.07.20
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Abstract

A kinetic study is reported for the nucleophilic substitution reactions of phenyl Y-substituted-phenyl carbonates (5a-5k) with piperidine in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The plots of $k_{obsd}$ vs. [piperidine] for the reactions of substrates possessing a strong electron-withdrawing group (EWG) in the leaving group (i.e., 5a-5i) are linear and pass through the origin. In contrast, the plots for the reactions of substrates bearing a weak EWG or no substituent (i.e., 5j or 5k) curve upward, indicating that the electronic nature of the substituent Y in the leaving group governs the reaction mechanism. Thus, it has been suggested that the reactions of 5a-5i proceed through a stepwise mechanism with a zwitterionic tetrahedral intermediate (i.e., $T^{\pm}$) while those of 5j and 5k proceed through a stepwise mechanism with two intermediates (i.e., $T^{\pm}$ and its deprotonated form $T^-$). The slope of the Br${\o}$nsted-type plot for the second-order rate constants (i.e., $k_N$ or $Kk_2$) changes from -0.41 to -1.89 as the leaving-group basicity increases, indicating that a change in the rate-determining step (RDS) occurs. The reactions of 5a-5k with piperidine result in larger $k_1$ values than the corresponding reactions with ethylamine.

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References

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