CN101073779B - Quaternary-ammonium poly-L-leucine catalyst, its production and use - Google Patents
Quaternary-ammonium poly-L-leucine catalyst, its production and use Download PDFInfo
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Abstract
The invention is concerned with the polyquaternium-L-leucine activator and the preparation and application. The activator is the connection of the quaternary ammonium with amido and poly-L-leucine. It is: the quaternary ammonium with amido leads the polymerization of L-Leu NCA to get the activator. The activator is fit for the asymmetry epoxy of alpha and beta-unsaturation ketone, the characteristics is: the using quantity of the activator is small, the reactive speed is quick, the recycle of the activator and the production is convenience, and the activator can cycle use many times.
Description
Technical field
The present invention relates to a kind of quaternary-ammonium poly-L-leucine catalyst and preparation thereof and application; Application is meant this catalyst alkene asymmetric Epoxidation, exactly, is meant this catalyst α; The alpha, beta-unsaturated ketone asymmetric Epoxidation, the technical field of metal catalyst and preparation thereof and application.
Background technology
The optically active epoxy ketone compounds is the synthetic son of one type of important biological compound, through reactions such as selective opening and functional group's conversions, can synthesize many valuable chipal compounds.α, the asymmetry catalysis epoxidation of alpha, beta-unsaturated ketone are one of most important reactions of such optically active epoxy thing of preparation.And in catalytic reaction; Adopt the catalyst of organic molecule as asymmetric epoxidation reaction; Have not containing metal, pollute less, advantages such as toxicity is little, good stability, reaction condition gentleness, to significant with the security and the chemical process greenization of synthetic drug.Juli á reported first polyamino acid in 1980 can the catalysis chalcone compounds asymmetric epoxidation reaction (Angrew.Ch em.Int.Ed.Engl.1980; 19; 929), the Polyalanine enantioselectivity (e e%) of making catalyst reaction can reach 83%, yield 85%.These amino acid polymers are called as synzyme (syntheticenzyme) or synthase (synzyme).Polyaminoacid has the following advantages as the catalyst of asymmetric organic synthesis for native enzyme: be easy to get, inexpensive, be prone to from reactant mixture, to separate, activity stabilized, product photochemistry purity high, be easy to recycling.After this because its potential theoretical research is worth and the application prospect in industrial synthesizing, and increasing researcher begins it is studied, a large amount of research work constantly are seen in report.The reaction of improved polyamino acid catalysis chalcone compounds can make almost Quantitative yield of substrate, and enantioselectivity ee% value is up to 95% (Tetrahedron Lett.2004,45,5069) simultaneously.Yet traditional polyaminoacid catalyst has 3 its application aspect industrialization of factor restriction at least: (1) catalyst amount is big, is about 200% of substrate weight; (2) reaction speed is very slow, generally needs several days time could accomplish (Tetrahedron1984,40,5207); (3) catalyst is gluey, brings very big difficulty to the recovery of practical operation and catalyst.Geller etc. have reported and in the alkene asymmetric epoxidation reaction system of poly-L-leucine catalysis, have added quaternary ammonium salt as phase transfer catalyst; But fast reaction speed; Reduce catalyst amount, but because catalyst still is gluey, product separates and the catalyst recovery problem does not still solve (Tetrahedron Lett.2004; 45,5069).In order to address these problems, the inventor was once immobilized on silica gel with the scion grafting of poly-L-leucine covalency, made catalyst be Powdered; Be convenient to reclaim; But the problem of catalyst amount big (be about substrate weight 400%) does not still solve, and catalyst enantioselectivity e e% value decline (Tetrahedron Lett., 2005 rapidly when recycling; 46,5665).
Summary of the invention
First technical problem that the present invention will solve is to release a kind of quaternary-ammonium poly-L-leucine catalyst.
For solving the problems of the technologies described above, the present invention adopts following technical scheme, it is characterized in that, described catalyst is formed by connecting having amino quaternary ammonium salt and poly-L-leucine, has molecular structural formula as follows:
Wherein, R
1, R
2, R
3Be C
1-C
16Alkyl, substituted alkyl, alkoxyl, substituted alkoxy, substituted aryl or substituted heterocyclic radical, X
-Be anion F
-, Cl
-, B r
-, I
-, SO
4 2-, BF
4 -Or PF
6 -, n>=1, average chain length m=10～60.
Second technical problem that the present invention will solve provides a kind of preparation method of quaternary-ammonium poly-L-leucine catalyst.
For solving the problems of the technologies described above, the present invention adopts following technical scheme.Cause L-Leu NCA polymerization to have amino quaternary ammonium salt, make quaternary-ammonium poly-L-leucine catalyst, do with the relevant chemical reaction skeleton symbol of preparation
Specify technical scheme of the present invention at present.
A kind of quaternary-ammonium poly-L-leucine alkene Preparation of catalysts method is characterized in that concrete operations: add 100～300g anhydrous tetrahydro furan among the L-Leu NCA of 7.8g, room temperature and nitrogen protection are stirred down, obtain settled solution; To the quaternary ammonium salt of described solution adding 1～6mmol, room temperature and nitrogen protection were stirred 72 hours down; Filter, the ether washing, oven dry, porphyrize get the powdery product quaternary-ammonium poly-L-leucine catalyst, yield 33%～91%, average chain length m=10～60 of product.
The 3rd technical problem that the present invention will solve is to release described quaternary-ammonium poly-L-leucine catalyst to be used for catalysis α, the method for the asymmetric epoxidation reaction of alpha, beta-unsaturated ketone.
For solving above-mentioned technical problem, the present invention adopts following technical scheme:
Described catalyst is used for α; The method of the asymmetric epoxidation reaction of alpha, beta-unsaturated ketone; It is characterized in that; With the quaternary ammonium salt poly-L-leucine catalyst of 0.1～2mmol, the α of 10mmol, beta-unsaturated ketone compound and 80g dimethoxy-ethane drop into 80g water, stir 30 minutes under the room temperature; Add the 2.4g SODIUM PERCARBONATE, stirred 5 minutes～12 hours under the room temperature, it is complete that TLC tracks to raw material reaction; Suction filtration, with the abundant washing leaching cake of ethyl acetate, filtrating merges; With the abundant washing leaching cake of deionized water, reclaim catalyst; Organic facies is used saturated common salt water washing, anhydrous sodium sulfate drying; Decompression is solvent evaporated down, and silica gel column chromatography separates, and obtains epoxidation product, and yield is 90%～99%; Utilize chiral column (chiralpak AD chiral phase) to carry out HPLC and analyze, flowing phase is n-hexane: (90: 1, v: v), the enantioselectivity ee% value that obtains epoxides was up to 99.4% to isopropyl alcohol, and described catalyst can be recycled.
The catalyst that reclaims can repeatedly recycle, and recycles the catalyst after seven times, and its activity and enantioselectivity e e% value still remain unchanged.
Compare with background technology, the present invention has the following advantages:
1. catalyst amount reduces significantly, is merely α, the 1mol% of alpha, beta-unsaturated ketone consumption.
2. reaction speed is fast, and minimum needs a few minutes, can make α, the complete epoxidation of alpha, beta-unsaturated ketone.
3. catalyst is Powdered, and product separation and catalyst recovery are easy.
4. reaction conversion ratio and enantioselectivity e e% value are high, and reaction conversion ratio is up to 99%, and enantioselectivity e e% value is up to 99.4%.
The specific embodiment
Embodiment 1: cause L-Leu NCA polymerization, average chain length m=10 with chlorination N-aminopropyl-N-methylimidazole salt ([Pamim] Cl).
Add 2.5g L-Leu NCA in the reaction bulb, the 50g anhydrous tetrahydro furan, room temperature and nitrogen protection are stirred down, obtain settled solution.Add 0.264g [Pamin] Cl to described solution, room temperature and nitrogen protection were stirred 72 hours down, and filtration, ether washing, oven dry, porphyrize get 1.4g white powder product [Pamim] Cl-PLL 10 catalyst, yield 73%.[Pamim] Cl-PLL 10 catalyst are one of quaternary-ammonium poly-L-leucine catalysts, the average chain length m=10 of product.
Embodiment 2: cause L-Leu NCA polymerization, average chain length m=30 with chlorination N-aminopropyl-N-methylimidazole salt ([Pamim] Cl).
Add 2.5g L-Leu NCA in the reaction bulb, the 50g anhydrous tetrahydro furan, room temperature and nitrogen protection are stirred down, obtain settled solution.Add 0.088g [Pamin] Cl to described solution, room temperature and nitrogen protection were stirred 72 hours down, and filtration, ether washing, oven dry, porphyrize get 1.2g white powder product [Pamim] Cl-P LL 30 catalyst, yield 63%.[Pamim] Cl-PLL 30 catalyst are one of quaternary-ammonium poly-L-leucine catalysts, the average chain length m=30 of product.
Embodiment 3: cause L-Leu NCA polymerization, average chain length m=60 with chlorination N-aminopropyl-N-methylimidazole salt ([Pamim] Cl).
Add 2.5g L-Leu NCA in the reaction bulb, the 50g anhydrous tetrahydro furan, room temperature and nitrogen protection are stirred down, obtain settled solution.Add 0.044g [Pamin] Cl to described solution, room temperature and nitrogen protection were stirred 72 hours down, and filtration, ether washing, oven dry, porphyrize get 1.1g white powder product [Pamim] Cl-PLL60 catalyst, yield 57%.[Pamim] Cl-PLL60 catalyst is one of quaternary-ammonium poly-L-leucine catalyst, the average chain length m=60 of product.
Embodiment 4: cause L-Leu NCA polymerization, average chain length m=30 with bromination N-aminopropyl-N-methylimidazole salt ([Pamim] Br).
Add 2.5g L-Leu NCA in the reaction bulb, the 50g anhydrous tetrahydro furan, room temperature and nitrogen protection are stirred down, obtain settled solution.Add 0.22g [Pamin] B r to described solution, room temperature and nitrogen protection were stirred 72 hours down, and filtration, ether washing, oven dry, porphyrize get 1.7g white powder product [Pamin] Br-PLL 30 catalyst, yield 91%.[Pamin] Br-PLL 30 catalyst are one of quaternary-ammonium poly-L-leucine catalysts, the average chain length m=30 of product.
Embodiment 5: with N-aminopropyl-N-methylimidazole hexafluorophosphate ([Pamim] PF
6) initiation L-Leu NCA polymerization, average chain length m=30.
Add 2.5g L-Leu NCA in the reaction bulb, the 50g anhydrous tetrahydro furan, room temperature and nitrogen protection are stirred down, obtain settled solution.Add 0.14g [Pamim] PF to described solution
6, room temperature and nitrogen protection were stirred 11 days down, and filtration, ether washing, oven dry, porphyrize get 0.84g yellow powder powder product [Pamim] PF
6-PLL30 catalyst, yield 33%.[Pamim] PF
6-PLL30 catalyst is one of quaternary-ammonium poly-L-leucine catalyst, the average chain length m=30 of product.
Embodiment 6: with N-aminopropyl-N-methyl imidazolium tetrafluoroborate ([Pamim] B F
4) initiation L-Leu NCA polymerization, average chain length m=30.
Add 2.5g L-Leu NCA in the reaction bulb, the 50g anhydrous tetrahydro furan, room temperature and nitrogen protection are stirred down, obtain settled solution.Add 0.11g [Pamim] BF to described solution
4, room temperature and nitrogen protection were stirred 72 hours down, and filtration, ether washing, oven dry, porphyrize get 1.14g white powder product [Pamim] BF
4-PLL30 catalyst, yield 43%.[Pamim] BF
4-PLL30 catalyst is one of quaternary-ammonium poly-L-leucine catalyst, the average chain length m=30 of product.
Embodiment 7: cause L-LeuNCA polymerization, average chain length m=30 with sal-ammoniac butyl tributyl ammonium ([TB AA] Cl).
Add 2.5g L-Leu NCA in the reaction bulb, the 50g anhydrous tetrahydro furan, room temperature and nitrogen protection are stirred down, obtain settled solution.Add 0.15g [TB AA] Cl to described solution, room temperature and nitrogen protection were stirred 72 hours down, and filtration, ether washing, oven dry, porphyrize get 1.27g white powder product [TB AA] Cl-PLL30 catalyst, yield 65%.[TB AA] Cl-PLL 30 catalyst are one of quaternary-ammonium poly-L-leucine catalysts, the average chain length m=30 of product.
Embodiment 8: cause L-Leu NCA polymerization, average chain length m=30 with zephiran chloride diethyl amino propyl ammonium ([BD EA] Cl).
Add 2.5g L-Leu N CA in the reaction bulb, the 50g anhydrous tetrahydro furan, room temperature and nitrogen protection are stirred down, obtain settled solution.Add 0.13g [BD EA] Cl to described solution, room temperature and nitrogen protection were stirred 72 hours down, and filtration, ether washing, oven dry, porphyrize get 1.35g white powder product [BD EA] Cl-PLL30 catalyst, yield 70%.[BD EA] Cl-PLL 30 catalyst are one of quaternary-ammonium poly-L-leucine catalysts, the average chain length m=30 of product.
Embodiment 9: [Pamim] Br-PLL30 catalyst chalcone asymmetric Epoxidation.
[Pamim] Br-PLL30 catalyst of 0.1～2mmol, chalcone and the 80g dimethoxy-ethane of 10mmol are dropped into 80g water, stirred 30 minutes under the room temperature; Add the 2.4g SODIUM PERCARBONATE, stirred 15 minutes under the room temperature, suction filtration, with the abundant washing leaching cake of ethyl acetate, filtrating merges; With the abundant washing leaching cake of deionized water, reclaim catalyst; Organic facies is used saturated common salt water washing, anhydrous sodium sulfate drying; Decompression is solvent evaporated down, and silica gel column chromatography separates, and gets the 0.22g epoxidation product, and yield is 98%; Utilize chiral column (chiralpak AD chiral phase) to carry out HPLC and analyze, flowing phase is n-hexane: (90: 1, v: v), the enantioselectivity ee% value that obtains epoxides was 94% to isopropyl alcohol.Described catalyst can be recycled.
Embodiment 10: the application of catalyst [Pamim] Br-PLL 30 in the chalcone asymmetric epoxidation reaction.
[Pamim] Br-PLL 30 catalyst of 2mmol, chalcone and the 80g dimethoxy-ethane of 10mmol are dropped into 80g water, stirred 30 minutes under the room temperature; Add the 2.4g SODIUM PERCARBONATE, stirred 1 hour under the room temperature, suction filtration, with the abundant washing leaching cake of ethyl acetate, filtrating merges; With the abundant washing leaching cake of deionized water, reclaim catalyst; Organic facies is used saturated common salt water washing, anhydrous sodium sulfate drying; Decompression is solvent evaporated down, and silica gel column chromatography separates, and gets the 0.22g epoxidation product, and yield is 98%; Utilize chiral column (chiralpak AD chiral phase) to carry out HP LC and analyze, flowing phase is n-hexane: (90: 1, v: v), the enantioselectivity e e% value that obtains epoxides was 96% to isopropyl alcohol.Described catalyst can be recycled.
Embodiment 11: the application of catalyst [Pamim] Br-PLL 30 in (E)-1-(4-chlorphenyl)-3-phenylpropyl alcohol-2-alkene-1-ketone asymmetric epoxidation reaction.
[Pamim] Br-PLL 30 catalyst of 2mmol, (E)-1-(4-chlorphenyl)-3-phenylpropyl alcohol-2-alkene-1-ketone and the 80g dimethoxy-ethane of 10mmol are dropped into 80g water, stirred 30 minutes under the room temperature; Add the 2.4g SODIUM PERCARBONATE, stirred 30 minutes under the room temperature, suction filtration, with the abundant washing leaching cake of ethyl acetate, filtrating merges; With the abundant washing leaching cake of deionized water, reclaim catalyst; Organic facies is used saturated common salt water washing, anhydrous sodium sulfate drying; Decompression is solvent evaporated down, and silica gel column chromatography separates, and gets the 0.27g epoxidation product, and yield is 99%; Utilize chiral column (chiralpakAD chiral phase) to carry out HP L C and analyze, flowing phase is n-hexane: (90: 1, v: v), the enantioselectivity e e% value that obtains epoxides was 99.4% to isopropyl alcohol.Described catalyst can be recycled.
Embodiment 12: the application of catalyst [Pamim] Br-PLL 30 in (E)-1-(4-methoxyphenyl)-3-phenylpropyl alcohol-2-alkene-1-ketone asymmetric epoxidation reaction.
[Pamim] Br-PLL 30 catalyst of 2mmol, (E)-1-(4-methoxyphenyl)-3-phenylpropyl alcohol-2-alkene-1-ketone and the 80g dimethoxy-ethane of 10mmol are dropped into 80g water, stirred 30 minutes under the room temperature; Add the 2.4g SODIUM PERCARBONATE, stirred 10 minutes under the room temperature, suction filtration, with the abundant washing leaching cake of ethyl acetate, filtrating merges; With the abundant washing leaching cake of deionized water, reclaim catalyst; Organic facies is used saturated common salt water washing, anhydrous sodium sulfate drying; Decompression is solvent evaporated down, and silica gel column chromatography separates, and gets the 0.25g epoxidation product, and yield is 94%; Utilize chiral column (chiralpak AD chiral phase) to carry out HPLC and analyze, flowing phase is n-hexane: (90: 1, v: v), the enantioselectivity ee% value that obtains epoxides was 96% to isopropyl alcohol.Described catalyst can be recycled.
Embodiment 13: the application of catalyst [Pamim] Br-PLL 30 in (E)-3-(4-methoxyphenyl)-1-phenylpropyl alcohol-2-alkene-1-ketone asymmetric epoxidation reaction.
[Pamim] Br-PLL 30 catalyst of 2mmol, (E)-3-(4-methoxyphenyl)-1-phenylpropyl alcohol-2-alkene-1-ketone and the 80g dimethoxy-ethane of 10mmol are dropped into 80g water, stirred 30 minutes under the room temperature; Add the 2.4g SODIUM PERCARBONATE, stirred 30 minutes under the room temperature, suction filtration, with the abundant washing leaching cake of ethyl acetate, filtrating merges; With the abundant washing leaching cake of deionized water, reclaim catalyst; Organic facies is used saturated common salt water washing, anhydrous sodium sulfate drying; Decompression is solvent evaporated down, and silica gel column chromatography separates, and gets the 0.25g epoxidation product, and yield is 94%; Utilize chiral column (chiralpak AD chiral phase) to carry out HPLC and analyze, flowing phase is n-hexane: (90: 1, v: v), the enantioselectivity e e% value that obtains epoxides was 95% to isopropyl alcohol.Described catalyst can be recycled.
Embodiment 14: the application of catalyst [Pamim] Cl-PLL 30 in the chalcone asymmetric epoxidation reaction.
[Pamim] Cl-PLL 30 catalyst of 0.1mmol, chalcone and the 80g dimethoxy-ethane of 10mmol are dropped into 80g water, stirred 30 minutes under the room temperature; Add the 2.4g SODIUM PERCARBONATE, stirred 12 hours under the room temperature, suction filtration, with the abundant washing leaching cake of ethyl acetate, filtrating merges; With the abundant washing leaching cake of deionized water, reclaim catalyst; Organic facies is used saturated common salt water washing, anhydrous sodium sulfate drying; Decompression is solvent evaporated down, and silica gel column chromatography separates, and gets the 0.23g epoxidation product, and yield is 94%; Utilize chiral column (chiralpak AD chiral phase) to carry out HPLC and analyze, flowing phase is n-hexane: (90: 1, v: v), the enantioselectivity e e% value that obtains epoxides was 96% to isopropyl alcohol.Described catalyst can be recycled.
Embodiment 15: the application of catalyst [Pamim] Cl-P LL 30 in the chalcone asymmetric epoxidation reaction.
[Pamim] Cl-PLL 30 catalyst of 0.5mmol, chalcone and the 80g dimethoxy-ethane of 10mmol are thrown 80g water, stirred 30 minutes under the room temperature; Add the 2.4g SODIUM PERCARBONATE, stirred 12 hours under the room temperature, suction filtration, with the abundant washing leaching cake of ethyl acetate, filtrating merges; With the abundant washing leaching cake of deionized water, reclaim catalyst; Organic facies is used saturated common salt water washing, anhydrous sodium sulfate drying; Decompression is solvent evaporated down, and silica gel column chromatography separates, and gets the 0.24g epoxidation product, and yield is 99%; Utilize chiral column (chiralpak AD chiral phase) to carry out HPLC and analyze, flowing phase is n-hexane: (90: 1, v: v), the enantioselectivity e e% value that obtains epoxides was 99.4% to isopropyl alcohol.Described catalyst can be recycled.
Embodiment 16: the application of catalyst [Pamim] Cl-P LL30 in the chalcone asymmetric epoxidation reaction.
[Pamim] Cl-PLL 30 catalyst of 1mmol, chalcone and the 80g dimethoxy-ethane of 10mmol are dropped into 80g water, stirred 30 minutes under the room temperature; Add the 2.4g SODIUM PERCARBONATE, stirred 12 hours under the room temperature, suction filtration, with the abundant washing leaching cake of ethyl acetate, filtrating merges; With the abundant washing leaching cake of deionized water, reclaim catalyst; Organic facies is used saturated common salt water washing, anhydrous sodium sulfate drying; Decompression is solvent evaporated down, and silica gel column chromatography separates, and gets the 0.24g epoxidation product, and yield is 99%; Utilize chiral column (chiralpak AD chiral phase) to carry out HPLC and analyze, flowing phase is n-hexane: (90: 1, v: v), the enantioselectivity ee% value that obtains epoxides was 99.4% to isopropyl alcohol.Described catalyst can be recycled.
Embodiment 17: the application of catalyst [Pamim] Cl-PLL 30 in the chalcone asymmetric epoxidation reaction.
[Pamim] Cl-PLL 30 catalyst of 2mmol, chalcone and the 80g dimethoxy-ethane of 10mmol are dropped into 80g water, stirred 30 minutes under the room temperature; Add the 2.4g SODIUM PERCARBONATE, stirred 15 minutes under the room temperature, suction filtration, with the abundant washing leaching cake of ethyl acetate, filtrating merges; With the abundant washing leaching cake of deionized water, reclaim catalyst; Organic facies is used saturated common salt water washing, anhydrous sodium sulfate drying; Decompression is solvent evaporated down, and silica gel column chromatography separates, and gets the 0.22g epoxidation product, and yield is 93%; Utilize chiral column (chiralpak AD chiral phase) to carry out HPLC and analyze, flowing phase is n-hexane: (90: 1, v: v), the enantioselectivity e e% value that obtains epoxides was 93.6% to isopropyl alcohol.Described catalyst can be recycled.
Catalyst of the present invention is specially adapted to α; The asymmetric Epoxidation of alpha, beta-unsaturated ketone; Have that catalyst amount is few, reaction speed is fast, product and catalyst recovery is convenient, catalyst can repeatedly recycle, yield and the high characteristics of enantioselectivity e e% value, has better industrial application prospect.
Claims (3)
1. a quaternary-ammonium poly-L-leucine catalyst is characterized in that, described catalyst is formed by connecting having amino quaternary ammonium salt and poly-L-leucine, has molecular structural formula as follows:
Wherein, R
1, R
2, R
3Be C
1-C
16Alkyl, substituted alkyl, alkoxyl, substituted alkoxy, substituted aryl or substituted heterocyclic radical, X
-Be anion F
-, Cl
-, Br
-, I
-, SO
4 2-, BF
4 -Or PF
6 -, n>=1, average chain length m=10～60.
2. the preparation method of the described quaternary-ammonium poly-L-leucine catalyst of claim 1; It is characterized in that; Add 100～300g anhydrous tetrahydro furan in the L-leucine N-carboxy acid anhydride of concrete operations: 7.8g, room temperature and nitrogen protection are stirred down, obtain settled solution; To the amino quaternary ammonium salt that has of described solution adding 1～6mmol, room temperature and nitrogen protection were stirred 72 hours down; Filter, the ether washing, oven dry, porphyrize get the powdery product quaternary-ammonium poly-L-leucine catalyst, yield 33%～91%, average chain length m=10～60 of product.
3. the described quaternary-ammonium poly-L-leucine catalyst of claim 1 is used for α; The method of the asymmetric epoxidation reaction of alpha, beta-unsaturated ketone; It is characterized in that; With the quaternary-ammonium poly-L-leucine catalyst of 0.1～2mmol, the α of 10mmol, alpha, beta-unsaturated ketone compound and 80g dimethoxy-ethane drop in the 80g water, stir 30 minutes under the room temperature; Add the 2.4g SODIUM PERCARBONATE, stirred 5 minutes～12 hours under the room temperature, it is complete that thin-layer chromatography tracks to raw material reaction; Suction filtration, with the abundant washing leaching cake of ethyl acetate, filtrating merges; With the abundant washing leaching cake of deionized water, reclaim catalyst; Organic facies is used saturated common salt water washing, anhydrous sodium sulfate drying; Decompression is solvent evaporated down, and silica gel column chromatography separates, and obtains epoxidation product, and yield is 90%～99%; Utilize chiral column chiralpak AD chiral phase to carry out efficient liquid phase chromatographic analysis; Flowing phase is the solution of n-hexane and isopropyl alcohol; Wherein the volume ratio of n-hexane and isopropyl alcohol is 90: 1; The enantioselectivity e e% value that obtains epoxides is up to 99.4%, and described catalyst can be recycled.
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