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Postsynthetic Modification Of Metal-organic Framework Cr-MIL-101 And Synthesis Of Chiral Pharmaceutical Intermediates Application

Posted on:2016-07-08Degree:MasterType:Thesis
Country:ChinaCandidate:P P WangFull Text:PDF
GTID:2191330470466788Subject:Analytical Chemistry
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Metal-organic frameworks(MOFs) are periodic network structure materials that composed of metal ions and multidentate organic ligands by self-assembleing. The characteristic of large surface areas, tunability pores and so on make MOFs widely used in molecular sensing, fluorescence and other fields. The Postsynthetic modification(PSM) has expanded the application of MOFs to a great extend. This thesis introducd small chrial molecule into the porous of MOFs and studied its applications in asymmetric catalytic.The Chapter 1 is the review of the concept and characteristic of MOFs, the meaning of chiral catalysis. And here we mainly described the application and synthesis of chiral MOFs, especially the PSM preparation of chiral MOFs. Finally, we described the research content and significance of this paper.In Chapter 2, we synthesized a new L-proline derivative by organic synthesis theoretical, which was bonded to the pores of Cr-MIL-101-NH2 and the Cr-MIL-101-Pa was obtained. The Cr-MIL-101-Pa is active in catalyticing asymmetric aldol reactions, while with no ee values was detected. The characteristics of 1H-NMR, P-XRD, BET, TG, CD and TPD-MS were conducted to study the reason for no ee values. The results indicate that the subject which producted after PSM blockes the pores of Cr-MIL-101-Pa. Further more, the NaHCO3 used in organic reaction treatment proceed attaches to Cr-MIL-101-Pa and is alkaline which can catalyze aldol reaction. The result provided some experience and methods for chooseing organic reactions and postsyntheicing modification of MOFs.In Chapter 3, the heterogeneous catalysts Cr-MIL-101/Pa-A、Cr-MIL-101/L-A、Cr-MIL-101/Pa and Cr-MIL-101/L were prepared by applying encapsulation theory and PSM method using Cr-MIL-101-NH2 as a carrier to load L-proline and its derivative. Here, we provide some reference for postsyntheicing modification of chiral MOFs catalyst via comparing catalysts ability of the catalysts for asymmetric aldol reaction.
Keywords/Search Tags:Metal-organic frameworks, Postsynthetic modification, L-proline, Chrial catalysis
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