Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
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The Kinetics and Mechanism of Nucleophilic Addition of n-Propylmercaptan to $\alpha$-Cyano-$\beta$-piperonylacrylic Acid

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

  • 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)
  • 김태린 (고려대학교 이공대학 화학과) ;
  • 허태성 (고려대학교 이공대학 화학과)
  • Published : 1973.10.30
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Abstract

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.

$\alpha$-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.

Keywords

References

  1. The Chemistry of Alkene S. Patai
  2. Advances in Physical Organic Chemistry v.7 Z. Rappoport
  3. J.Chem. Soc. (B) Y. Ogata;A Kowusaki;I.K. Zhi
  4. Canad. J. Chem. v.47 J.A. Murkiss;J. D. Gettler
  5. J. Chem. Soc. (B) Z. Rappoport;R. Ta-Shama
  6. J. Amer. Chem. Soc. v.78 M.J. Kamlet;D. J. Glover
  7. J. Chem. Soc.(B) M.P. Naan;C.P. Hall
  8. J. Org. Chem. v.13 M. Kharash;C. Fuch
  9. J. Amer. Chem. Soc. v.69 C. D. Hurd;L.L. Geishbein
  10. J. Amer. Chem. Soc. v.74 R. Stewart
  11. J. Chem. Soc. E.A. Walker;J.R. Young
  12. J. Amer. Chem. Soc. v.77 D.S. Noyece;W.A. Pryor;A.H. Bottini
  13. J. Chem. Soc.(B) S. Patai;Z. Rappoport
  14. J. Chem. Soc.(B) S. Patai;Z. Rappoport
  15. J. Chem. Soc.(B) S. Patai;Z. Rappoport
  16. J. Amer. Chem. Soc. v.77 M.J. Kamlet
  17. J. Amer. Chem. Soc. v.83 T.I. Crowell;A.W. Francis Jr.
  18. Doctorial Dissertation, University of Virginia T.I. Crowell;T.R. Kim
  19. J. Amer. Chem. Soc. v.81 W.E. Truce;D.L. Goldhamer
  20. J. Amer. Chem. Soc. v.86 B. Dmuchovsky;B. P. Vinegard;F. B. Zienty
  21. Z. Physik.Chem. v.41 K.L. Mallik;M.N. Das
  22. J. Korean Chem. Soc. v.13 T.R. Kim;Y.S. Choi
  23. J. Korean Chem. Soc. v.13 K.S. Kwon;T.R. Kim
  24. J. Chem. Soc. v.105 W.J. Jones
  25. Progress in Physical Organic Chemistry v.1 E.M. Arvett