Asymmetric Hydrogenation of Ethyl Pyruvate over Bimetallic Rh-Pt/Al2O3 Catalysts Modified with Dihydrocinchonidine

Dihydrocinchonidine으로 개질된 Rh-Pt/Al2O3 이원금속 촉매를 이용한 Ethyl Pyruvate의 비대칭 수소화

  • Cho, Hong-Baek (Division of Material and Chemical Engineering, Hanyang University) ;
  • Kang, Joon-seok (Division of Material and Chemical Engineering, Hanyang University) ;
  • Park, Yeung-Ho (Division of Material and Chemical Engineering, Hanyang University)
  • 조홍백 (한양대학교 재료화학공학부) ;
  • 강준석 (한양대학교 재료화학공학부) ;
  • 박융호 (한양대학교 재료화학공학부)
  • Received : 2006.03.09
  • Accepted : 2006.06.07
  • Published : 2006.08.10

Abstract

$Rh-Pt/Al_{2}O_{3}$ catalysts were used for the first time to study its reaction characteristics in the asymmetric hydrogenation of ethyl pyruvate. The catalysts were prepared either by impregnation of Rh on a commercial $Pt/Al_{2}O_{3}$ or by sequential impregnation of Rh followed by impregnation of Pt on $Al_{2}O_{3}$. Reaction rate and enantiomeric excess (ee%) were compared according to the preparation method, Rh contents, and the reduction temperature of the catalyst. The physical characteristics of the catalysts were analyzed using XRD and TEM. Bimetallic $Rh-Pt/Al_{2}O_{3}$ catalysts showed an improved reaction rate and optical purity (63.6 ee%) with increasing the reduction temperature. The variation of the Rh contents as well as the preparation method elicited a big difference on the reaction rate, while enantiomeric excess (ee%) was lower (56~60%) with all bimetallic catalysts than with monometallic $Pt/Al_{2}O_{3}$ catalyst.

Ethyl pyruvate의 비대칭 수소화 반응에 $Rh-Pt/Al_{2}O_{3}$ 이원금속 촉매를 처음으로 적용하고 그 반응특성을 조사하였다. $Rh-Pt/Al_{2}O_{3}$ 촉매는 상용 $Pt/Al_{2}O_{3}$에 Rh을 담지하거나 $Al_{2}O_{3}$에 Pt와 Rh을 연속적으로 함침시켜 제조하여, 촉매제법, Rh 함량 및 환원온도에 따라 반응속도, 광학선택도(ee%)가 변화하는 경향을 비교하였으며, XRD, TEM을 통하여 촉매의 물리적 특성을 분석하였다. $Rh-Pt/Al_{2}O_{3}$ 이원금속 촉매는 환원온도가 증가함에 따라 반응속도와 광학순도가 향상되었다(63.6 ee%). 또한 Rh의 함량에 따라서도 촉매 반응속도의 큰 변화를 보여주었는데, 그 변화 경향은 촉매 제조과정에 따라 달랐으나 광학선택도는 모든 이원촉매가 단일촉매에 비해 떨어지는 결과(56~60 ee%)를 나타내었다.

Keywords

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