Bulletin of the Korean Chemical Society

  • 제25권4호
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  • Pages.557-559
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  • 2004
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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 Aminolysis of Anilino Thioethers with Benzylamines in Acetonitrile

  • 발행 : 2004.04.20
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초록

The aminolyses of anilinothioethers $(C_6H_5N(CH_3)CH_2SC_6H_4Z)$ in acetonitrile with benzylamines $(XC_6H_4CH_2NH_2)$ have been investigated. The rates are much lower in acetonitrile than in methanol (with aniline). The Bronsted ${\beta}_X$ values are similar but ${\beta}_Z$ values are smaller compared to those for the reactions in MeOH with anilines. The large negative ${\rho}_{XZ}({\cong}-0.8$, after correction for fall-off) value is interpreted to indicate a frontside attack $S_N2$ mechanism, in which the two oppositely changed reaction centers in the TS, $-N^{{\delta}+}{\cdots}S^{{\delta}-}-$, are in close vicinity increasing the interaction between nucleophile and leaving group. The inverse secondary kinetic isotope effects ($k_H/k_D$ < 1.0) are observed with deuterated benzylamines $(XC_6H_4CH_2ND_2)$.

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피인용 문헌

  1. Kinetics and Mechanism of the Addition of Benzylamines to β-Cyanostilbenes in Acetonitrile vol.26, pp.4, 2004, https://doi.org/10.5012/bkcs.2005.26.4.641
  2. Kinetics and Mechanism of the Addition of Benzylamines to β-Cyanostilbenes in Acetonitrile vol.26, pp.4, 2004, https://doi.org/10.5012/bkcs.2005.26.4.641
  3. Kinetics and Mechanism of the Addition of Benzylamines to α-Cyano-β-phenylacrylamides in Acetonitrile vol.26, pp.6, 2004, https://doi.org/10.5012/bkcs.2005.26.6.935
  4. Base-Promoted, Ketene-Forming Elimination Reactions. Mechanistic Borderline between E2 and E1cb Mechanisms vol.26, pp.7, 2004, https://doi.org/10.5012/bkcs.2005.26.7.1017
  5. Aminolysis of 2,4-Dinitrophenyl X-Substituted Benzoates and Y-Substituted Phenyl Benzoates in MeCN: Effect of the Reaction Medium on Rate and Mechanism vol.12, pp.4, 2004, https://doi.org/10.1002/chem.200500647
  6. Physical Chemistry Research Articles Published in the Bulletin of the Korean Chemical Society: 2003-2007 vol.29, pp.2, 2008, https://doi.org/10.5012/bkcs.2008.29.2.450