Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Kinetics and Mechanism of the Addition of Benzylamines to α-Cyano-β-phenylacrylamides in Acetonitrile

  • Oh, Hyuck-Keun (Department of Chemistry, Research Center of Bioactive Materials, Chonbuk National University) ;
  • Ku, Myoung-Hwa (Department of Chemistry, Research Center of Bioactive Materials, Chonbuk National University) ;
  • Lee, Hai-Whang (Department of Chemistry, Inha University)
  • Published : 2005.06.20
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Abstract

Nucleophilic addition reactions of benzylamines (BA; $XC_6H_4CH_2NH_2$) to $\alpha-cyano-\beta$-phenylacrylamides (CPA; $YC_6H_4CH=C(CN)CONH_2$) have been investigated in acetonitrile at 25.0 ${^{\circ}C}$. The rate is first order with respect to BA and CPA and no base catalysis is observed. The addition of BA to CPA occurs in a single step in which the addition of BA to $C_{\beta}$ of CPA and proton transfer from BA to $C_{\alpha}$ of CPA take place concurrently with a four-membered cyclic transition state structure. The magnitude of the Hammett ($\rho_X$) and Bronsted ($\beta_X$) coefficients are rather small suggesting an early tansition state (TS). The sign and magnitude of the crossinteraction constant, $\rho_XY$ (= −D0.26), is comparable to those found in the normal bond formation processes in the $S_N2$ and addition reactions. The normal kinetic isotope effect ($k_H/k_D\;{\gt}$ 1.0) and relatively low ${\Delta}H^{\neq}$ and large negative ${\Delta}S^{\neq}$ values are also consistent with the mechanism proposed.

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References

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