대한화학회지 (Journal of the Korean Chemical Society)

  • 제17권5호
  • /
  • Pages.363-370
  • /
  • 1973
  • /
  • 1017-2548(pISSN)
  • /
  • 2234-8530(eISSN)
대한화학회 (Korean Chemical Society)
권호 표지

$\alpha$-Cyano-$\beta$-piperonylacrylic Acid에 대한 n-Propylmercaptan의 친핵성 첨가반응에 관한 연구

The Kinetics and Mechanism of Nucleophilic Addition of n-Propylmercaptan to $\alpha$-Cyano-$\beta$-piperonylacrylic Acid

  • 김태린 (고려대학교 이공대학 화학과) ;
  • 허태성 (고려대학교 이공대학 화학과)
  • Kim, Tae-Rin (Department of Chemistry, College of Science and Engineering Korea University) ;
  • Huh, Tae-Seong (Department of Chemistry, College of Science and Engineering Korea University)
  • 발행 : 1973.10.30
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초록

$\alpha$-Cyano-$\beta$-piperonylacrylic acid에 대한 n-Propylmercaptan의 친핵성 첨가반응 속도 상수를 측정하여 넓은 pH 범위에서 잘 맞는 반응속도식을 구하였다. 이 식에 의하면 넓은 pH 범위에서 일어나는 복잡한 반응메카니즘을 정량적으로 잘 설명할 수 있었다. 즉 pH4.5이하에서는 $\alpha$-Cyano-$\beta$-piperonylacrylic acid에 mercaptan이 직접 첨가되며 pH 4.5∼6.5 사이에서는 주로 $\alpha$-Cyano-$\beta$-piperonylacrylic ion에 mercaptan 분자가 첨가되고 pH 7.5 부터는 $\alpha$-Cyano-$\beta$-piperonylacrylic ion에 mercaptan 분자와 mercaptide ion의 첨가가 경쟁적으로 일어나며 pH 10이상에서는 $\alpha$-Cyano-$\beta$-piperonylacrylic anion에 mercaptide ion의 첨가만이 일어남을 알 수 있었다.

The rate constants of the nucleophilic addition of n-propyl-mercaptan to $\alpha$-cyano-$\beta$-piperonylacrylic acid were determined at various pH and a rate equation which can be applied over wide pH range is obtained. The rate equation reveals that below pH 4.5 the reaction is initiated by the attack of n-propylmercaptan to $\alpha$-cyano-$\beta$-piperonylacrylic acid. At pH 4.5~6.5, however, n-propylmercaptan is added to $\alpha$-cyano-$\beta$-piperonylacrylate ion; at pH 7.04~9.5 the competitive reaction between n-propylmercaptan and n-propylmercaptide ion is anticipated to occur. Above pH 10 the addendum is n-propylmercaptide ion and the acceptor is $\alpha$-cyano-$\beta$-piperonylacrylate ion.

키워드

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