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http://dx.doi.org/10.5012/bkcs.2008.29.10.1911

Kinetic Study on Michael-type Reactions of 1-Phenyl-2-propyn-1-one with Alicyclic Secondary Amines: Effect of Medium on Reactivity and Mechanism  

Hwang, So-Jeong (Department of Chemistry and Nano Science, Ewha Womans University)
Park, Youn-Min (Department of Chemistry and Nano Science, Ewha Womans University)
Um, Ik-Hwan (Department of Chemistry and Nano Science, Ewha Womans University)
Publication Information
Bulletin of the Korean Chemical Society / v.29, no.10, 2008 , pp. 1911-1914 More about this Journal
Abstract
Second-order rate constants (kN) have been measured for Michael-type addition reactions of a series of alicyclic secondary amines to 1-phenyl-2-propyn-1-one (2) in MeCN at 25.0 ${\pm}$ 0.1 ${^{\circ}C}$. All the amines studied are less reactive in MeCN than in $H_2O$ although they are more basic in the aprotic solvent by 7-9 p$K_a$ units. The Bronsted-type plot is linear with $\beta_{nuc}$ = 0.40, which is slightly larger than that reported previously for the corresponding reactions in $H_2O$ ($\beta_{nuc}$ = 0.27). Product analysis has shown that only E-isomer is produced. Kinetic isotope effect is absent for the reactions of 2 with morpholine and deuterated morpholine (i.e., $k^H/k^D$ = 1.0). Thus, the reaction has been concluded to proceed through a stepwise mechanism, in which proton transfer occurs after the rate-determining step. The reaction has been suggested to proceed through a tighter transition state in MeCN than in H2O on the basis of the larger $\beta_{nuc}$ in the aprotic solvent. The nature of the transition state has been proposed to be responsible for the decreased reactivity in the aprotic solvent.
Keywords
Michael-type reaction; Concerted mechanism; Stepwise mechanism; Brønsted-type plot; Medium effect
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