Bulletin of the Korean Chemical Society

  • 제26권4호
  • /
  • Pages.641-644
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  • 2005
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  • 0253-2964(pISSN)
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  • 1229-5949(eISSN)
대한화학회 (Korean Chemical Society)
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Kinetics and Mechanism of the Addition of Benzylamines to β-Cyanostilbenes in Acetonitrile

  • Oh, Hyuck-Keun (Department of Chemistry, Research Center of Bioactive Materials, Chonbuk National University) ;
  • Kim, In-Kon (Department of Chemistry, Research Center of Bioactive Materials, Chonbuk National University) ;
  • Sung, Dae-Dong (Department of Chemistry, Dong-A University) ;
  • Lee, Ik-Choon (Department of Chemistry, Dong-A University)
  • 발행 : 2005.04.20
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초록

Nucleophilic addition reactions of benzylamines $(XC_6H_4CH_2NH_2)\;to\;{\beta}$-cyanostilbenes ($YC_6H_4CH=C(CN)C_6H_4$Y’) have been studied in acetonitrile at 30.0 oC. A greater degree of N-$C_{\alpha}$ bond formation (larger ${\beta}_X$) is obtained with a stronger electron-withdrawing substituent in either ${\alpha}-\;(\delta\sigma_Y\;{\gt}\;0)\;or\;{\beta}-ring\;(\delta\sigma_{Y'}\;{\gt}$ 0). A stronger charge development is observed in the TS on $C_{\beta}\;(\rho_{Y'}$= 1.06 for X=Y=H) rather than on $C_{\alpha}\;(\rho_{Y}$ = 0.62 for X=Y’H) indicating the lag in the resonance development into the activating group (CN) on $C_{\beta}$ in the transition state. Similarly, the magnitude of $\rho$$_{XY'}$(−0.72) is greater than $\rho_{XY}$ (−0.66) due to a stronger interaction of the nucleophile with $\beta$-ring than $\alpha$-ring. The positive sign of $\rho_{YY'}$correctly reflects $\pi$ bond cleavage between the two rings in the TS. Relatively large kinetic isotope effects ($k_H/k_D\;{\geq}$ 2.0) involving deuterated nucleophiles ($XC_6H_4CH_2ND_2$) suggest a four-membered cyclic TS in which concurrent N-C$_{\alpha}$ and H(D)-C$_{\beta}$ bond formation occurs.

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피인용 문헌

  1. Effects of substituents on activation parameter changes in the Michael-type reactions of nucleophilic addition to activated alkenes and alkynes in solution vol.147, pp.2, 2016, https://doi.org/10.1007/s00706-015-1622-5