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

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

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