Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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A Kinetic Study on Michael-type Reactions of 1-(X-Substituted Phenyl)-2-propyn-1-ones with Amines: Effect of Amine Nature on Reactivity and Mechanism

  • Um, Ik-Hwan (Division of Nano Sciences and Department of Chemistry, Ewha Womans University) ;
  • Hwang, So-Jeong (Division of Nano Sciences and Department of Chemistry, Ewha Womans University) ;
  • Lee, Eun-Ju (Division of Nano Sciences and Department of Chemistry, Ewha Womans University)
  • Published : 2008.04.20
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Abstract

Second-order rate constants have been measured spectrophotometrically for the Michael-type reaction of 1-(Xsubstituted phenyl)-2-propyn-1-ones (2a-f) with amines in $H_2O$ at 25.0 ${\pm}$ 0.1 ${^{\circ}C}$. A linear Brønsted-type plot is obtained with ${\beta}_{nuc}$ = 0.25 ${\pm}$ 0.02, a typical $\beta_{nuc}$ value for reactions which proceed through a stepwise mechanism with attack of amine on the electrophilic center being the rate-determining step. Secondary alicyclic amines are found to be more reactive than isobasic primary amines. The Hammett plot for the reactions of 2a-f with morpholine is not linear, i.e., the substrate with a strong electron-donating group (e.g., 4-MeO) exhibits a negative deviation from the Hammett plot. However, the Yukawa-Tsuno plot for the same reactions exhibits an excellent linear correlation with ρ = 0.62 and r = 0.82. Thus, it has been proposed that the nonlinear Hammett plot is not due to a change in the ra te-determining step but due to ground-state stabilization through resonance interactions.

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References

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