Bulletin of the Korean Chemical Society

  • 제27권5호
  • /
  • Pages.733-738
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  • 2006
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  • 0253-2964(pISSN)
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  • 1229-5949(eISSN)
대한화학회 (Korean Chemical Society)
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Kinetic and Mechanism of the Addition of Benzylamines to α-Phenyl-β-thiophenylacrylonitriles in Acetonitrile

  • Hwang, Jae-young (Department of Chemistry, Gyeongsang National University) ;
  • Yang, Ki-yull (Department of Chemistry Education and the Research Institute of Natural Science, Gyeongsang National University) ;
  • Koo, In-Sun (Department of Chemistry Education and the Research Institute of Natural Science, Gyeongsang National University) ;
  • Sung, Dae-Dong (Department of Chemistry, Dong-A University) ;
  • Lee, Ik-choon (Department of Chemistry, Inha University)
  • 발행 : 2006.05.20
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초록

Nucleophilic addition reactions of p-substitutedbenzylamines $(XC _6H_4CH _2NH _2)$ to $\alpha$-phenyl-$\beta$-thiophenyl-acrylonitriles ($YC _4SH _2CH=C(CN)C_6H_4$Y') have been studied in acetonitrile at 25.0, 30.0, and 35.0 ${^{\circ}C}$. The reactions take place in single step in which the $C_\beta$ -N bond formation and proton transfer to $C_\alpha$ of $\alpha$-phenyl-$\beta$-thiophenylacrylonitriles occur concurrently with four-membered cyclic transition structure. These mechanistic conclusions are drawn based on (i) the large negative $\rho$x and large positive $\rho$Y' values and also large magnitude of $\rho$X, (ii) the negative sign and large magnitude of the cross-interaction constants ($\rho$XY), (iii) the normal kinetic isotope effects ($k_H/k_D$ > 1.0), and (iv) relatively low $\Delta H ^\neq$ and large negative $\Delta S ^\neq$ values.

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참고문헌

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