Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Kinetics and Mechanism of Nucleophilic Substitution Reaction of 4-Substituted-2,6-dinitrochlorobenzene with Benzylamines in MeOH-MeCN Mixtures

  • Kim, Young-Sun (Department of Chemistry Education and Education Research Institute, Gyeongsang National University) ;
  • Choi, Ho-June (Department of Chemistry Education and Education Research Institute, Gyeongsang National University) ;
  • Yang, Ki-Yull (Department of Chemistry Education and Education Research Institute, Gyeongsang National University) ;
  • Park, Jong-Keun (Department of Chemistry Education and Education Research Institute, Gyeongsang National University) ;
  • Koo, In-Sun (Department of Chemistry Education and Education Research Institute, Gyeongsang National University)
  • Received : 2010.08.25
  • Accepted : 2010.09.14
  • Published : 2010.11.20
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Abstract

The reaction rates of 4-X-2,6-dinitrochlorobenzenes (X = $NO_2$, CN, $CF_3$) with Y-substituted benzylamines (Y = p-$OCH_3$, p-$CH_3$, H, p-Cl) in MeOH-MeCN mixtures were measured by conductometry at $25^{\circ}C$. It was observed that the rate constant increased in the order of X = $NO_2$ > CN > $CF_3$ and in the order of Y = p-$OCH_3$ > p-$CH_3$ > H > p-Cl. When the solvent composition was varied, the rate constant increased in the order of 100% MeOH < 50% (v/v) MeOH-MeCN < 100% MeCN. These results may be ascribed to the formation of hydrogen bonds between the alcoholic hydrogen and nitrogen of benzylamines in groud state (GS). We conclude that the reaction takes place via $S_NAr$ base on the transition state parameters ${\rho}x$, ${\rho}Y$, $\beta_{nuc}$, and solvent effects.

Keywords

References

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