공업화학 (Applied Chemistry for Engineering)

  • 제25권5호
  • /
  • Pages.503-509
  • /
  • 2014
  • /
  • 1225-0112(pISSN)
  • /
  • 2288-4505(eISSN)
한국공업화학회 (The Korean Society of Industrial and Engineering Chemistry)
권호 표지
DOI QR코드

DOI QR Code

카본/메조세공 실리카 복합 막을 응용한 키랄 에폭사이드의 가수분해반응과 동시 분리

Mesoporous Silica-Carbon Composite Membranes for Simultaneous Hydrolysis and Separation of Chiral Epoxide

  • Choi, Seong Dae (Department of Chemical Engineering, College of Engineering, Inha University) ;
  • Jeon, Sang Kwon (Department of Chemical Engineering, College of Engineering, Inha University) ;
  • Park, Geun Woo (Department of Chemical Engineering, College of Engineering, Inha University) ;
  • Yang, Jin Young (Department of Chemical Engineering, College of Engineering, Inha University) ;
  • Kim, Geon-Joong (Department of Chemical Engineering, College of Engineering, Inha University)
  • Received : 2014.07.09
  • Accepted : 2014.08.28
  • Published : 2014.10.10
PDF 다운로드
⟨ 이전 논문 다음 논문 ⟩

Abstract

탄소와 다공성 실리카로 구성된 복합막을 용이한 방법으로 제작하고 이들 막을 활용하여, 키랄 에폭사이드와 키랄디올 화합물의 친수성/소수성 특성차이를 기초로 한 동시 합성 및 분리과정에 응용하였다. 막반응기에 도입한 키랄 Co(III)-$BF_3$형 살렌촉매는 ECH, 1,2-EB와 SO 등의 에폭사이드 가수분해반응에 대하여 높은 활성을 나타내었고 여러 차례의 재사용이 가능하였다. 광학순도가 높은 키랄 에폭사이드 생성물은 가수분해반응이 진행된 후에 촉매와 함께 유기용액상에서 취득되었다. 물에 용해되는 친수성의 1,2-디올은 키랄 살렌의 촉매작용에 의하여 가수분해됨으로써 생성되는데, 이들은 반응이 진행되는 동안 SBA-16 또는 NaY/SBA-16 실리카층을 통해 물층으로 확산되었다. 물은 막반응계에서 반응물이면서 동시에 용매로서 거동하였다. 연속흐름형의 막반응기를 적용함으로써, 고순도, 고수율의 광학이성체를 생성물로서 얻을 수 있었으며, 촉매는 큰 활성저하를 나타내지 않아 여러 차례 재사용이 가능하였다.

The carbon/porous silica composite membrane was fabricated in a simple manner, which could be successfully for the simultaneous separation and production of chiral epoxides and 1,2-diols, based on their differences in hydrophilic/hydrophobic natures. The chiral Co(III)-$BF_3$ salen catalyst adopted in the membrane reactor system has given the very high enantioselectivity and recyclability in hydrolysis of terminal epoxides such as ECH, 1,2-EB, and SO. The optically pure epoxide and the chiral catalyst were collected in the organic phase after hydrolysis reaction. The hydrophilic water-soluble 1,2-diol product hydrolyzed by chiral salen diffused into the aqueous phase through the SBA-16 or NaY/SBA-16 silica composite layer during the reaction. The water acted simultaneously as a reactant and a solvent in the membrane system. One optical isomer was obtained with high purity and yield, and furthermore the catalysts could be recycled without observable loss in their activity in the continuous flow-type membrane reactor.

Keywords

References

  1. J. P. Collman, Z. Wang, A. Straumanis, A. M. Quelquejeu, and E. Rose, An efficient catalyst for asymmetric epoxidation of terminal olefins, J. Am. Chem. Soc., 121, 460 (1999). https://doi.org/10.1021/ja9818699
  2. R. M. Hanson, Highly diastereoselective reaction of a chiral, non-racemic amide enolate with (S)-glycidyl tosylate, Chem. Rev., 91, 437 (1991). https://doi.org/10.1021/cr00004a001
  3. M. Tokunaga, J. F. Larrow, F. Kakiuchi, and E. N. Jacobsen, Asymmetric catalysis with water: Efficient kinetic resolution of terminal epoxides by means of catalytic hydrolysis, Science, 277, 936 (1997). https://doi.org/10.1126/science.277.5328.936
  4. L. P. C. Nielson, C. P. Stevenson, D. G. Backmond, and E. N. Jacobsen, Highly reactive and enantioselective kinetic resolution of terminal epoxides with $H_2O$ and HCl catalyzed by new chiral (salen) Co complex linked with Al, J. Am. Chem. Soc., 126, 1360 (2004). https://doi.org/10.1021/ja038590z
  5. B. D. Brandes and E. N. Jacobson, Highly selective hydrolytic kinetic resolution of terminal epoxides catalyzed by chiral (salen) Co (III) complexes; Practical synthesis of enantioenriched terminal epoxides and 1,2-Diols, Tetrahedron: Asymmetry, 8, 3927 (1997). https://doi.org/10.1016/S0957-4166(97)00568-5
  6. P. S. Savle, M. J. Lamoreaux, J. F. Berry, and R.D. Gandour, New chiral cobalt salen complexes containing Lewis acid $BF_3$; A highly reactive and enantioselective catalyst for the hydrolytic kinetic resolution of epoxides, Tetrahedron: Asymmetry, 9, 1842 (1998).
  7. S. E. Schaus, B. D. Brandes, J. F. Larrow, M. Tokunaga, K. B. Hansen, A. E. Gould, M. E. Furrow, and E. N. Jacobson, Synthesis of polymeric salen complexes and application in the enantioselective hydrolytic kinetic resolution of epoxides as catalysts, J. Am. Chem. Soc., 124, 1307 (2002). https://doi.org/10.1021/ja016737l
  8. G-J Kim and J. H. Shin, The catalytic activity of new chiral salen complexes immobilized on MCM-41 by multi-step grafting in the asymmetric epoxidation, Tetrahedron Letters, 40, 6827 (1999). https://doi.org/10.1016/S0040-4039(99)01407-0
  9. D. Pini, A. Mandoli, S. Orlandi, and P. Salvadori, First example of a silica gel-supported optically active Mn(III)-salen complex as a heterogeneous asymmetric catalyst in the epoxidation of olefins, Tetrahedron: Asymmetry, 10, 3883 (1999). https://doi.org/10.1016/S0957-4166(99)00426-7
  10. S. B. Ogunwumi and T. Bein, Intrazeolite assembly of a chiral manganese salen epoxidation catalyst, Chem. Commun., 901 (1997).
  11. F. Minutolo, D. Pini, and P. Salvadori, Polymer-bound chiral (salen) Mn (III) complex as heterogeneous catalyst in rapid and clean enantioselective epoxidation of unfunctionalised olefins, Tetrahedron Letters, 37, 3375 (1996). https://doi.org/10.1016/0040-4039(96)00550-3
  12. T. Sano, Y. Kiyozumi, M. Kawamura, F. Mizukami, H. Takaya, T. Mouri, W. Inaoka, Y. Toida, M. Watanabe, and K. Toyoda, Preparation and characterization of ZSM-5 zeolite film, Zeolites, 11, 842 (1991). https://doi.org/10.1016/S0144-2449(05)80066-1
  13. T. Sano, Y. Kiyozumi, F. Mizukami, H. Takaya, T. Mouri, and M. Watanabe, Steaming of ZSM-5 zeolite film, Zeolites, 12, 131 (1992). https://doi.org/10.1016/0144-2449(92)90071-V
  14. Y. Kiyozumi, F. Mizukami, K. Maeda, T. Kodzasa, M. Toba, and S. Niwa, Synthesis of oriented zeolite film on mercury, Stud. Surf. Sci. and Catal., 105, 2225 (1997). https://doi.org/10.1016/S0167-2991(97)80694-5
  15. Y. Kiyozumi, F. Mizukami, K. Maeda, M. Toba, and S. Niwa, Synthesis of a zeolite film on a mercury surface, Adv. Mater., 8, 517 (1996). https://doi.org/10.1002/adma.19960080615
  16. S. Shimizu, Y. Kiyozumi, and F. Mizukami, Catalytic activity of a zeolite disc synthesized through solid-state reactions, Chem. Lett., 403 (1996).
  17. L.P. Szabo, E. H. Lipai, P. Hadik, E. Nagy, F. Mizukami, S. Shimizu, I. Kiricsi, and J. Bodnar, DL-lactic acid separation on enantiomodified zeolite membrane, J. Ind. Chem., 26, 147 (1998).
  18. S.-D. Choi and G-J Kim, Enantioselective hydrolytic kinetic resolution of epoxides catalyzed by chiral Co(III) salen complexes immobilized in the membrane reactor, Catal. Lett., 92, 35 (2004). https://doi.org/10.1023/B:CATL.0000011083.91015.a6