The Kinetics and Mechanism of Nucleophilic Addition of Mercaptan to ${\beta}$-Nitrostyrene in Acid Media Part IV. The Reactions of n-Amyl, n-Hexyl, n-Octyl, and n-Decyl Mercaptan with ${\beta}$-Nitrostyrene

酸性溶媒 속에서의 ${\beta}$-Nitrostyrene에 대한 Mercaptan의 親核性 添加反應에 관한 연구 [IV] n-Amyl-, n-Hexyl-, n-Octyl-, n-Decyl-Mercaptan과의 반응

  • Kim, Tae-Rin (Department of Chemistry, College of Engineering and Science, Korea University) ;
  • Choi, Young-Sang (Department of Chemistry, College of Engineering and Science, Korea University)
  • Published : 19690900

Abstract

The nucleophilic addition rate constants of n-amyl-, n-hexyl-, n-octyl-and n-decyl mercaptide ion to 3,4-methylenedioxy-${\beta}$-nitrostyrene were determined and found to be 2.82 ${\times}10^8$ $M^{-2} .sec^{-1}$, 1.00 ${\times}10^8$ $M^{-2}.sec^{-1}$, 2.23 ${\times}10^8$ $M^{-2} .sec^{-1}$ and 1.77 ${\times}10^8$ $M^{-2}.sec^{-1}$ respectively. At low pH, for n-amyl-, n-hexyl-, n-octyl-and n-decyl mercaptan the values determined are 2.82 ${\times}10^{-2}$ $M^{-1} . sec^{-1}$, 1.95 ${\times}10^{-2}$ $M^{-1} . sec^{-1}$, 7.08 ${\times}10^{-2}$ $M^{-1} . sec^{-1}$ and 5.63 ${\times}10^{-2}$ $M^{-1} . sec^{-1}$ respectively. The rate equations which can fully explain the addition mechanism over wide pH range were also be obtained.

Nucleophile의 親核性 添加反應性을 정량적으로 연구하고자 전보에 이어 3,4-methylenedioxy-${\beta}$-nitrostyrene에 대한 n-amyl, n-hexyl, n-Octyl, n-decylamercaptanㅓ의 添加反應速度常數를 측정한 결과 n-amylmercaptide, n-hexylmercaptide, n-octylmercaptide, n-decylmercaptide ino에 대해 각각 2.82${\times}10^8$, 100${\times}10^8$, 2.23${\times}10^8$과 1.77${\times}10^8$ $M^{-2} .sec^{-1}$를 얻었고, n-amyl, n-hexyl, n-Octyl, n-decylmercaptan분자에 대해서는 각각 2.82${\times}10^{-2}$, 1.95${\times}10^{-2}$, 7.08${\times}10^{-2}$과 5.63${\times}10^{-2}$$M^{-1} . sec^{-1}$를 얻었으며, 염기성뿐만 아니라 산성용매 속에서도 그의 반응메카니즘을 잘 설명할 수 있는 반응속도 식도 구하였다.

Keywords

References

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  3. 本誌 v.12 朴玉鉉;金泰麟
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