Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
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Kinetic Studies on the Reaction of Benzyl m-Nitrobenzenesulfonate with N,N-Dimethylanilines

벤질 m-술폰산니트로벤젠과 N,N-디메틸아닐린類와의 反應에 關한 反應速度論的 硏究

  • Yoh Soo-Dong (Department of Chemistry, Teacher's College, Kyungpook National University) ;
  • Lee Mu-Sang (Department of Chemistry, Teacher's College, Kyungpook National University)
  • 여수동 (慶北大學校 師範大學 化學科) ;
  • 이무상 (慶北大學校 師範大學 化學科)
  • Published : 1979.02.28
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Abstract

The kinetics of the reaction of benzyl m-nitrobenzenesulfonate with m-and p-substituted N,N-dimethylanilines in acetone have been investigated by an electric conductivity method. The effects of substituents on the reactivity of N,N-dimethylaniline and the existence of linear free energy relationship were discussed. The rate constants k were in the range 2.55∼487 $10^{-4}l{\cdot}mol^{-l}{\cdot}sec^{-1} (35^{\circ}C)$ and increased with the electron donating ability of substituents. In the present reaction, the Hammett plot was correlated with ${\sigma}$ substituent constant, especially using the new ${\sigma}$ value of 0.35 in p-MeO and it's ${\rho}$ value was found to be -1.37. r value for the reaction was very large than the value obtained in the reaction of benzyl bromide. $Br{\"{o}}nsted$ linear relationship was shown between rate constant and basicites except for p-MeO resulted from solvent effect. From the Bronsted plot, this reaction was suggested that the cleavage of the C${\cdot}{\cdot}{\cdot}$O bond in the $S_N2$ transition state proceed the bond formation.

Benzyl m-nitrobenzenesulfonate와 N,N-dimethylaniline類와의 反應速度를 아세톤 溶媒에서 電氣傳導度法으로 測定하였다. N,N-디메틸아닐린의 反應性에 關한 置換基效果와 直線 自由에너지 關係를 考察하였다. 反應速度常數 k는 2.55∼487 $10^{-4}l{\cdot}mol^{-l}{\cdot}sec^{-1} (35^{\circ}C)$였으며 置換基가 電子를 주는 能力이 클수록 反應은 빨랐다. Hammett 도시에서 置換基常數 ${\sigma}$와 ${\sigma}p$-MeO = -0.35의 새로운 값을 使用했을때 ${\rho}$ = -1.37의 좋은 直線이 얻어졌다. 本反應의 경우 r값은 브롬화벤질에 比해 큰 값을 가졌다. Bronsted 圖示에서 溶媒效果에 基因된 p-MeO基를 除外하고는 좋은 直線이 얻어졌으며 C${\cdot}{\cdot}{\cdot}$O 結合의 쪼개짐이 結合 形成보다 優先的인 $S_N2$ 轉移狀態를 갖는다고 推定된다.

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References

  1. J. Korean Chem. Soc. v.19 Soo-Dong Yoh
  2. J. Korean Chem. Soc. v.19 Soo-Dong Yoh
  3. J. Korean Chem. Soc. v.19 Soo-Dong Yoh
  4. Research Review of Kyungpook National Univ. v.22 Soo-Dong Yoh
  5. Nippon Kagaku Kaishi M. Tsuruta(et al.)
  6. Organic Functional Group Preparations S. R. Sandler;Wolf Karo
  7. J. Amer. Chem. Soc. v.85 B. B. P. Tice;Ikchoon Lee(et al.)
  8. J. Amer. Chem. Soc. v.82 A. C. Cope(et al.)
  9. J. Amer. Chem. Soc. v.68 D. D. Thomas(et al.)
  10. J. Amer. Chem. Soc. v.78 F. G. Bordwell;P. J. Boutan
  11. J. Org. Chem. v.26 L. Friedman;H. Shechter
  12. Ann. v.384 H. Staudinger;N. Kon.
  13. Bull. Chem. Soc. Japan. v.45 Y. Tsuno;M. Fujio;Y. Takai;Y. Yukawa