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Synthesis Of Organosoluble Zirconium Phosphonates With Different Arm Length Supported Homogeneous Ruthenium Catalysts And Application In The Asymmetric Catalysis

Posted on:2011-07-26Degree:MasterType:Thesis
Country:ChinaCandidate:T T ChenFull Text:PDF
GTID:2181360302997852Subject:Organic Chemistry
Abstract/Summary:PDF Full Text Request
In this thesis, using low-cost and facile L-phenylalanine as the raw material, the organosoluble zirconium phosphonates with different arm length (n=2-6) had been synthesized by several synthetic steps. Their supported organosoluble ruthenium chiral catalysts had been prepared by the immobolization of homogeneous [Ru(p-cymene)(S-Binap)Cl]Cl chiral catalyst onto the backbone of zirconium phosphonates through the amino and hydroxyl complexing groups, and the homogeni-zation of metal catalyst supported on the backbone of inorganic material was ultilized for the first time.The organosoluble zirconium phosphonates-supported ruthenium chiral catalysts were soluble in CHCl3, CH2Cl2 and THF (0.10-0.33 g/mL) and insoluble in some organic solvents such as hexane, alcohol and petroleum ether. The structure and morphology of organosoluble zirconium phosphon-ates and their supported ruthenium chiral catalysts had been characterized by IR, NMR, TG, XPRD, N2 adsorption and desorption isotherms and TEM.The synthesized organosoluble zirconium phosphonates-supported ruthenium chiral catalysts were applied in the hydrogenation of ethyl pyruvate and the optimum experimental conditions were disccussed in detail. Ethyl 2-hydroxylpropionate in 92.6% yield and 72.4% e.e. was obtained at 80℃for 1 h in mixed C2H5OH and CH2C12 solvents (v/v=l:1) and 40 atm hydrogen pressure using 6c as catalyst. After the completion of the catalytic proccess, the catalyst can be precipitated and centrifugated by two-phase separation technique (liquid/solid separation) utilizing the immiscibility of the ruthenium chiral catalyst in some organic solvents, but the catalytic properties reduced after three reusing times.
Keywords/Search Tags:Homogenous catalyst, Two-phase Separation, Supported, Ruthenium, Asymmetric Catalysis
PDF Full Text Request
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