Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
권호 표지

Phase Transfer Catalytic Effects for Thiocyanate Displacement on Benzyl Chloride

티오시안산 염에 의한 염화벤질의 치환반응에 미치는 상이동 촉매효과

  • Seung Hyun Chang (Department of Chemistry, Taegu University) ;
  • Mu Hong Yoon (Department of Chemistry, Taegu University) ;
  • Chang Su Kim (Department of Chemistry Education, Taegu University) ;
  • Kwang Bo Chung (Department of Chemical Engineering, Dongguk University) ;
  • Jae Hu Shim (Department of Chemical Engineering, Dongguk University)
  • 장승현 (대구대학교 자연과학대학 화학과) ;
  • 윤무홍 (대구대학교 자연과학대학 화학과) ;
  • 김창수 (대구대학교 사범대학 화학교육과) ;
  • 정광보 (동국대학교 공과대학 화학공학과) ;
  • 심재후 (동국대학교 공과대학 화학공학과)
  • Published : 1989.12.20
Download PDF
⟨ Previous Next ⟩

Abstract

The catalytic effects of several phase-transfer catalysts (PTC) on the liquid-liquid heterogeneous nucleophilic displacement reaction of thiocyanate on benzyl chloride have been determined. Reactions followed a pseudo-first order dependency on the benzyl chloride concentration and the observed rate constant $(k_{obsd})$ were linearly related to the concentration of catalyst and varied with variables such as reaction temperature and solvent. The sequences of catalytic activity of the displacement were $NH_4Cl$ < BTMAC < 18-crown-6 < BTEAC < PEG < TBAC < CTMAB. Enthalpies and entropies of activation associated with the displacement were 15∼20 Kcal$mo^{l-1}$, -12∼-29 eu. respectively and the reaction occurs in the interphase comprising of microemulsion.

액-액 불균일계에서 염화벤질의 KSCN에 의한 친핵치환반응에 미치는 상이동 촉매 효능을 검토하였다. 반응은 염화벤질의 농도에 의존하는 유사일차 반응이었고, 반응속도 상수$(k_{obsd})$는 촉매농도에 비례하였으며, 반응온도 및 용매 등에 영향을 받았다. 본 치환반응에 대한 상이동 촉매능의 순위는 $NH_4Cl$ < BTMAC < 18-crown-6 < BTEAC < PEG < TBAC < CTMAB 이었다. 반응의 활성화 엔탈피 및 엔트로피는 각각 15∼20 Kcal${\cdot}mo^{l-1}$, -12∼-29 eu.이었으며, 반응은 미세한 유탁액으로 이루어지는 중간상인 interphase에서 일어남을 알 수 있었다.

Keywords

References

  1. Phase Transfer Catalysis in Organic Synthesis W. P. Weber;G. W. Gokel
  2. Chem. Technol. v.5 E. V. Dehmlow
  3. Angew. Chem. v.89 E. V. Dehmlow
  4. New Synth. Methods v.1
  5. J. Am. Chem. Soc. v.93 C. M. Starks
  6. J. Am. Chem. Soc. v.98 S. L. Regen
  7. J. Org. Chem. v.42 S. L. Regen
  8. J. Am. Chem. Soc. v.101 H. Molinari;F. Montanari;S. Quici;P. Tundo
  9. J. Am. Chem. Soc. v.101 P. Tundo;P. Venturello
  10. Synthesis no.2 M. Kodomari;T. Kuzuoda;S. Yoshitomi
  11. J. Am. Chem. Soc. v.95 C. L. Liotta;H. P. Harris
  12. J. Org. Chem. v.39 F. L. Cook;C. W. Bowers;C. L. Liotta
  13. J. Org. Chem. v.47 J. H. Harris;N. H. Hundley;T. G. Shannon;E. C. Struck
  14. J. Chem. Soc. Chem. Commun. D. Landini;A. M. Maia;F. Montanari
  15. J. Am. Chem. Soc. v.95 C. M. Starks;R. M. Owens
  16. J. Am. Chem. Soc. v.97 A. W. Herriot;D. Picker
  17. Tetrahedron Letters v.23 C. A. Martin;P. M. McCrann;G. H. Angelos;D. A. Taeger
  18. Bull. Chem. Soc. Jpn. v.54 T. Hideshima;M. Morinaga;H. Kimizuka
  19. J. Am. Chem. Soc. v.94 J. H. Fendler;E. J. Fendler;R. T. Medary;V. A. Woods
  20. J. Chem. Soc. Chem. Commun. J. H. Fendler
  21. The Condenced Chemical Dictionary G. G. Hawley
  22. Phase-Transfer Catalysis, Principle and Techniques C. M. Starks;C. Liotta
  23. J. Chem.Soc. Chem. Commn. J. M. Brown;J. A. Jenkins
  24. J. Am. Chem. Soc. v.95 C. J. O'Connor;E. J. Fendler;J. H. Fendler
  25. Macromolecules v.14 N. Ohtani;C. A. Wilkie;A. Nigam;S. L. Regen