CN109225330B - A highly loaded and highly stable chiral porous phosphotungstic acid catalyst and its preparation - Google Patents
A highly loaded and highly stable chiral porous phosphotungstic acid catalyst and its preparation Download PDFInfo
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- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 title claims description 38
- 239000003377 acid catalyst Substances 0.000 title claims description 22
- 238000002360 preparation method Methods 0.000 title claims description 9
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- 238000006243 chemical reaction Methods 0.000 claims description 22
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- 238000001035 drying Methods 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 12
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 claims description 9
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- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
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- 239000000523 sample Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/643—Pore diameter less than 2 nm
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
- C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
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Abstract
本发明涉及绿色化工和纳米材料技术领域，特别涉及一种由手性烟碱离子液体有机硅和12‑磷钨酸构成的手性多孔催化剂。一种高负载高稳定性的手性多孔磷钨酸催化剂，该手性多孔磷钨酸催化剂的孔径为1.5～2 nm，比表面积95～106 cc/g，磷钨酸负载量以催化剂总重计为70～72%，可用于苯乙烯与H2O2的不对称双羟化反应且具有显著的稳定性。本发明还涉及该高负载高稳定性的手性多孔磷钨酸催化剂的制备。本发明制备的催化剂具有高达70%以上的多酸含量和显著的稳定性，具有手性催化能力、可用于苯乙烯的不对称双羟化反应，且能回收利用达7次以上而活性不变，磷钨酸的流失率仅为2%。
The invention relates to the technical fields of green chemical industry and nanomaterials, in particular to a chiral porous catalyst composed of chiral nicotine ionic liquid organosilicon and 12-phosphotungstic acid. A chiral porous phosphotungstic acid catalyst with high load and high stability, the pore size of the chiral porous phosphotungstic acid catalyst is 1.5-2 nm, the specific surface area is 95-106 cc/g, and the loading amount of phosphotungstic acid is the total weight of the catalyst Calculated as 70-72%, it can be used for asymmetric bishydroxylation of styrene and H 2 O 2 and has remarkable stability. The invention also relates to the preparation of the chiral porous phosphotungstic acid catalyst with high load and high stability. The catalyst prepared by the invention has a polyacid content as high as more than 70% and remarkable stability, has chiral catalytic ability, can be used for asymmetric bishydroxylation of styrene, and can be recycled for more than 7 times without changing the activity. , the loss rate of phosphotungstic acid is only 2%.
Description
Technical Field
The invention relates to the technical field of green chemical industry and nano materials, in particular to a chiral porous catalyst consisting of chiral nicotine ionic liquid organic silicon and 12-phosphotungstic acid.
Background of the patent
Various heteropolyacids including phosphotungstic acid, phosphomolybdic acid and the like are recognized heterogeneous green catalysts, have strong acidity and oxidation reduction, can replace inorganic corrosive strong acid or Lewis acid, are used for alkylation, acylation, isomerization, esterification, polycondensation, hydrolysis and other reactions, can also be used for alkane, alkene, alcohol phenol, desulfurization, ring opening, even photodegradation and other oxidation reactions, and have the advantages of high catalytic activity, mild reaction conditions and the like, but the phosphotungstic acid does not have stereoselectivity, is easy to dissolve in water and polar solvents, and causes corrosion to equipment, environmental pollution and difficulty in catalyst recovery.
The method is characterized in that a proper high-specific-area nano and porous carrier is preferably selected, such as silica gel or silica, activated carbon, molecular sieves, MOFs, various clay minerals and the like, polyacid is dispersed and loaded on the carrier through post-treatment processes such as impregnation, adsorption, grafting and the like, and the loaded porous phosphotungstic acid catalyst is prepared. The synthesis method is characterized in that a synthesis raw material of heteropoly acid is directly introduced into pore channels of a porous material, phosphotungstic acid is synthesized in the pore channels, namely 'ship in bottle', or the synthesis is directly introduced into silica gel or molecular sieve, silica sol and phosphotungstic acid are mixed by adopting a sol-gel method, or the synthesis is directly introduced into a metal organic MOF material, a novel MOFs material with embedded phosphotungstic acid is spontaneously formed during high-temperature hydrothermal treatment, the in-situ synthesis idea utilizes the space effect of nanometer framework pore channels, the loss of polyacid molecules is limited, the load capacity of the phosphotungstic acid is greatly increased, but an organic anchoring agent, a template agent or an organic ligand is commonly used in the preparation process, the preparation process is relatively complex, and the catalysts are not chiral (wenlangmo, minze. petrochemical, 2000, 29(1): 49-55; wangmy, li, yucca, guchunku, etc.. industrial catalysis, 2007, 15(10) 1-4; zhao Lei, Lian hong bud, cone, etc. Henan chemical engineering 2012(23): 21-25).
The Ionic liquid is also a recognized green solvent (IL), the functional Ionic liquid is obtained by molecular design, and has special catalytic activity, optical, electric, magnetic and other properties, and the chiral Ionic liquid can provide a special solvent system for asymmetric reaction and even participate in the identification and synthesis of chiral molecules. In recent years, there is a method of "acid-base pairing", wherein phosphotungstic acid, various organic amines, quaternary ammonium salts, ionic liquids and the like form a solid catalyst, and polyacid molecules are bound by the action of basic groups, so that the adsorbability and selectivity of the catalyst are improved. A variety of chiral amines, chiral quaternary ammonium salts, chiral ionic liquids have been paired with polyacids for asymmetric Michael addition, Aldol condensation and Diels-Alder cycloaddition (S.Z. Luo, J.Y. Li, H.xu, et al. Org. Lett. 2007, 9: 3675-3678; Q. Gao, S.M. Lu, Y. Liu, et al. Tetrahedron Lett. 2011, 52: 3779-3781; Q. Gao, Y. Liu, S.M. Lu, et al. Green chem. 2011, 13: 1983-1985; Q. Chen, C.Xin, L.L. Lou, et al. J. Inorg. Organomet. Polym. 2013, 23: 467-471), chiral ionic liquids with phosphotungstic acids also exhibit good hydroxylation reactions in styrene hydroxylation catalysts (C.Y. Zh. Zal. Zh. 2016, 79: 49-52). It must be noted that ionic liquids and phosphotungstic acid are also readily soluble in water and most polar organic solvents, and part of the quaternary ammonium salts or long alkyl chains of ionic liquids may lead to high dispersibility in non-polar solvents, so that after a certain period of reaction, more significant catalyst loss and reduction in catalytic activity occur.
The activity of the solid catalyst is generally considered to be inferior to that of a homogeneous catalyst, the main reason is that enough catalytic components and raw materials are in the same phase and can be in full contact and reaction, and one of the solutions is to prepare the catalyst into a nano-porous structure to improve the reaction efficiency. The technical problem of the present invention is to provide a catalyst with high loading rate, high selectivity and high stability, which makes the research of such green catalyst difficult. However, in consideration of the current chiral fine chemicals such as pesticides, antibiotics or additives, the chiral separation and purification with high consumption and high pollution are mostly adopted in the large-scale production, or expensive and highly toxic noble metal homogeneous complexes are used as catalysts, or a microorganism/enzyme catalysis technology which is easily influenced by the environment and is easy to deteriorate is used, so the chiral polyacid solid catalyst still has the advantages of economy and environment.
Disclosure of Invention
The technical problem solved by the invention is as follows: aiming at the defects of the load capacity and the stability of the existing chiral porous phosphotungstic acid catalyst, how to provide a novel chiral porous phosphotungstic acid catalyst with high load and high stability.
The technical scheme adopted by the invention is as follows: a high-load high-stability chiral porous phosphotungstic acid catalyst has a pore diameter of 1.5-2 nm, a specific surface area of 95-106 cc/g, and a phosphotungstic acid load of 70-72% based on the total weight of the catalyst, and can be used for styrene and H2O2Has remarkable stability.
The preparation method of the high-load high-stability chiral porous phosphotungstic acid catalyst comprises the following steps:
step one, sequentially adding 1.6 parts by mass of natural S-nicotine and 2.4-3 parts by mass of chloropropyltriethoxysilane into 20-50 parts by mass of absolute ethyl alcohol, heating until reflux reaction is carried out for 12-24 h, and removing the solvent by reduced pressure distillation to obtain yellow viscous ionic liquid organic silicon;
and secondly, dissolving 9.6 parts by mass of 12-phosphotungstic acid in 20-50 parts by mass of absolute ethanol, adding 4-4.6 parts by mass of yellow viscous ionic liquid organic silicon, mixing and stirring at normal temperature for 3-6 h, standing for 12-24 h, pouring out clear liquid to obtain light orange precipitate, placing the light orange precipitate in 20-50 parts by mass of absolute ethanol, adding 1.2-3.6 parts by mass of phosphoric acid, uniformly mixing, transferring to a stainless steel closed reaction kettle, curing at 85-95 ℃ for 24-48 h, recovering orange solid, and drying at 35-45 ℃ for 5-7 days to obtain the high-load high-stability chiral porous phosphotungstic acid catalyst.
To verify the chiral performance of the catalyst, asymmetric dihydroxylation of styrene was used as a probe reaction, with the following results:
preferred catalysts are styrene, 30% H2O2(the dosage ratio is 0.1: 1: 4) are sequentially added into 50 parts by mass of distilled water for reaction, the reaction is carried out for 1.5 to 2 hours at the temperature of 55 to 65 ℃, catalyst particles are recovered by centrifugal filtration, vacuum drying is carried out for 8 hours at the temperature of 65 ℃ for reuse, filtrate is extracted by 50 parts by mass of ethyl acetate, extract liquor is collected, the solvent is removed by reduced pressure distillation to obtain white crude product, and the white crude product is dissolved in the white crude product0.1-0.5 part by mass of petroleum ether at the temperature of 60-90 ℃, filtering and drying to obtain the pure R-phenyl glycol. The yield of the obtained R-phenyl glycol is 82-90%, and the enantiomeric excess (e.e.) of the R-phenyl glycol is 90-95% compared with a standard product.
In order to verify the high stability of the catalyst, the catalyst is continuously used for 7 times under the same process condition, the tungsten content of the chiral porous phosphotungstic acid catalyst obtained by each recovery is detected by ICP (inductively coupled plasma) and compared with the initial catalyst, and the loss rate is not more than 2%.
The following comparative experiments are adopted to confirm the mechanism and the advantages of the stability of the catalyst, respectively prepare a non-silicon chiral ionic liquid phosphotungstic acid catalyst and an inorganic silicon oxide phosphotungstic acid catalyst, and verify the performance and the stability of the catalyst in the reaction:
1) calcining the catalyst at 450-550 ℃ for 2-3 h, removing an organic part of an ionic liquid to obtain an off-white catalyst, wherein the off-white catalyst is used for asymmetric dihydroxylation reaction of styrene, the yield of phenyl glycol is only 28-35%, the stereoselectivity is almost zero, and the loss rate of phosphotungstic acid reaches 39-42%.
2) The n-butyl chloride is used for replacing chloropropyl triethoxysilane in the catalyst preparation process, the obtained ionic liquid is reacted with 12-phosphotungstic acid to prepare the catalyst, the synthesis steps are the same, the catalyst is used for the asymmetric dihydroxylation reaction of styrene, the yield of R-phenyl glycol is 72-76%, the enantiomeric excess value (e.e.) is 84-90%, and the loss rate of phosphotungstic acid reaches 10-16%.
The invention has the beneficial effects that: the invention uses the by-product of tobacco industryS-Synthesizing chiral ionic liquid organic silicon by using nicotine as a raw material, and carrying out simple processes such as precipitation curing and the like on the organic silicon and 12-phosphotungstic acid to obtain the novel chiral porous phosphotungstic acid catalyst. Compared with the prior art, the catalyst has polyacid content of more than 70 percent, remarkable stability and chiral catalytic ability, can be used for asymmetric dihydroxylation of styrene, can be recycled for more than 7 times without changing the activity, has the loss rate of phosphotungstic acid of only 2 percent, meets the requirements of modern green chemical industry, and provides an effective idea for development and application of chiral polyacid catalysts.
Drawings
FIG. 1 shows the yield distribution of multiple styrene dihydroxylation reactions and the stability data of phosphotungstic acid catalyst.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The present invention will be further described with reference to the following examples. Unless otherwise specified, the technical means used in the present invention are well known to those skilled in the art. In addition, the embodiments should be considered illustrative, and not restrictive, of the scope of the invention, which is defined solely by the claims. It will be apparent to those skilled in the art that various changes or modifications in the components and amounts of the materials used in these embodiments can be made without departing from the spirit and scope of the invention.
Example 1
1) Sequentially adding 1.6 parts by mass of natural S-nicotine and 3 parts by mass of chloropropyltriethoxysilane into 50 parts by mass of absolute ethyl alcohol, heating to reflux reaction for 24 hours, and removing the solvent by reduced pressure distillation to obtain yellow viscous ionic liquid organic silicon;
2) dissolving 9.6 parts by mass of 12-phosphotungstic acid in 50 parts by mass of absolute ethyl alcohol, adding 4.6 parts by mass of ionic liquid organic silicon, mixing and stirring at normal temperature for 6 hours, standing for 24 hours, pouring out clear liquid to obtain light orange precipitate, placing the light orange precipitate in 50 parts by mass of absolute ethyl alcohol, adding 3.6 parts by mass of industrial phosphoric acid, uniformly mixing, transferring to a stainless steel closed reaction kettle, curing at 95 ℃ for 48 hours, recovering orange solid, and drying at 45 ℃ for 7 days to obtain the chiral porous phosphotungstic acid catalyst.
Example 2
1) Sequentially adding 1.6 parts by mass of natural S-nicotine and 2.8 parts by mass of chloropropyltriethoxysilane into 40 parts by mass of absolute ethyl alcohol, heating to reflux for 20 hours, and removing the solvent by reduced pressure distillation to obtain yellow viscous ionic liquid organic silicon;
2) dissolving 9.6 parts by mass of 12-phosphotungstic acid in 40 parts by mass of absolute ethyl alcohol, adding 4.4 parts by mass of ionic liquid organic silicon, mixing and stirring at normal temperature for 5 hours, standing for 20 hours, pouring out clear liquid to obtain light orange precipitate, placing the light orange precipitate in 40 parts by mass of absolute ethyl alcohol, adding 2.8 parts by mass of industrial phosphoric acid, uniformly mixing, transferring to a stainless steel closed reaction kettle, curing at 95 ℃ for 40 hours, recovering orange solid, and drying at 45 ℃ for 6 days to obtain the chiral porous phosphotungstic acid catalyst.
Example 3
1) Sequentially adding 1.6 parts by mass of natural S-nicotine and 2.6 parts by mass of chloropropyltriethoxysilane into 30 parts by mass of absolute ethyl alcohol, heating to reflux for 16 hours, and removing the solvent by reduced pressure distillation to obtain yellow viscous ionic liquid organic silicon;
2) dissolving 9.6 parts by mass of 12-phosphotungstic acid in 30 parts by mass of absolute ethyl alcohol, adding 4.2 parts by mass of ionic liquid organic silicon, mixing and stirring at normal temperature for 4 hours, standing for 16 hours, pouring out clear liquid to obtain light orange precipitate, placing the light orange precipitate in 30 parts by mass of absolute ethyl alcohol, adding 2 parts by mass of industrial phosphoric acid, uniformly mixing, transferring to a stainless steel closed reaction kettle, curing at 85 ℃ for 32 hours, recovering orange solid, and drying at 35 ℃ for 7 days to obtain the chiral porous phosphotungstic acid catalyst.
Example 4
1) Sequentially adding 1.6 parts by mass of natural S-nicotine and 2.4 parts by mass of chloropropyltriethoxysilane into 20 parts by mass of absolute ethyl alcohol, heating to reflux for 12 hours, and removing the solvent by reduced pressure distillation to obtain yellow viscous ionic liquid organic silicon;
2) dissolving 9.6 parts by mass of 12-phosphotungstic acid in 20 parts by mass of absolute ethyl alcohol, adding 4 parts by mass of ionic liquid organic silicon, mixing and stirring for 3 hours at normal temperature, standing for 12 hours, pouring out clear liquid to obtain light orange precipitate, placing the light orange precipitate in 20 parts by mass of absolute ethyl alcohol, adding 1.2 parts by mass of industrial phosphoric acid, uniformly mixing, transferring to a stainless steel closed reaction kettle, curing at 85 ℃ for 24 hours, recovering orange solid, and drying at 35 ℃ for 5 days to obtain the chiral porous phosphotungstic acid catalyst.
In order to verify the property of the catalyst in the aspect of chiral catalysis, the catalyst obtained in the above example is applied to the asymmetric dihydroxylation reaction of styrene, and the specific steps are as follows:
example 5
The catalyst obtained in example 1 was mixed with styrene and 30% H2O2Adding 50 parts by mass of distilled water in sequence (the dosage ratio is 0.1: 1: 4) for reaction, reacting for 1.5 h at 65 ℃, centrifugally filtering and recovering catalyst particles, drying for 8h under vacuum at 65 ℃ for reuse, extracting filtrate with 50 parts by mass of ethyl acetate, collecting extract liquor, distilling under reduced pressure to remove solvent to obtain white crude product, dissolving the white crude product in 0.1 part by mass of petroleum ether at 60-90 ℃ for recrystallization, filtering and drying to obtain the pure product of the R-phenyl glycol. The yield of R-phenylethanediol obtained was 90% with an enantiomeric excess (e.e.) of 95% compared to the standard.
The above experiment was repeated 7 times as shown in FIG. 1, and it can be seen that
Example 6
The catalyst obtained in example 2 was mixed with styrene and 30% H2O2Adding 50 parts by mass of distilled water in sequence (the dosage ratio is 0.1: 1: 4) for reaction, reacting for 2h at 55 ℃, centrifugally filtering and recovering catalyst particles, drying for 8h at 65 ℃ in vacuum, extracting the filtrate with 50 parts by mass of ethyl acetate, collecting extract liquor, distilling under reduced pressure to remove the solvent to obtain a white crude product, dissolving the white crude product in 0.3 part by mass of petroleum ether at 60-90 ℃ for recrystallization, filtering and drying to obtain the pure product of the R-phenyl glycol. The yield of R-phenylethanediol obtained was 88% with an enantiomeric excess (e.e.) of 93% compared to the standard.
Example 7
The catalyst obtained in example 3 was mixed with styrene and 30% H2O2Adding 50 parts by mass of distilled water in sequence (the dosage ratio is 0.1: 1: 4) for reaction, reacting for 1.5 h at 55 ℃, centrifugally filtering and recovering catalyst particles, drying for 8h under vacuum at 65 ℃ for reuse, extracting filtrate with 50 parts by mass of ethyl acetate, collecting extract liquor, distilling under reduced pressure to remove solvent to obtain white crude product, dissolving the white crude product in 0.4 part by mass of petroleum ether at 60-90 ℃ for recrystallization, filtering and drying to obtain the pure product of the R-phenyl glycol. The yield of R-phenylethanediol obtained was 85% with an enantiomeric excess (e.e.) of 92% compared to the standard.
Example 8
The catalyst obtained in example 4Agent with styrene, 30% H2O2Adding 50 parts by mass of distilled water in sequence (the dosage ratio is 0.1: 1: 4) for reaction, reacting for 2 hours at 65 ℃, centrifugally filtering and recovering catalyst particles, drying for 8 hours at 65 ℃ in vacuum for reuse, extracting filtrate with 50 parts by mass of ethyl acetate, collecting extract liquor, distilling under reduced pressure to remove solvent to obtain white crude product, dissolving the white crude product in 0.5 part by mass of petroleum ether at 60-90 ℃ for recrystallization, filtering and drying to obtain the pure product of the R-phenyl glycol. The yield of R-phenylethanediol obtained was 82% with an enantiomeric excess (e.e.) of 90% compared to the standard.
In order to verify the mechanism and the advantages of the stability of the catalyst, a non-silicon chiral ionic liquid phosphotungstic acid catalyst and a non-organic silicon oxide phosphotungstic acid catalyst are respectively prepared, and the following comparative experiments are carried out:
example 9
The catalyst of the example 1 is calcined at 550 ℃ for 2h, and the off-white catalyst is obtained after removing the organic part of the ionic liquid, and is used for asymmetric dihydroxylation reaction of styrene, the yield of the phenyl glycol is only 28%, the stereoselectivity is almost zero, and the loss rate of the phosphotungstic acid reaches 42%.
Example 10
The catalyst of the embodiment 2 is calcined at 450 ℃ for 3h, and the off-white catalyst is obtained after the removal of the organic part of the ionic liquid and is used for the asymmetric dihydroxylation reaction of styrene, the yield of the phenyl glycol is only 35 percent, the stereoselectivity is almost zero, and the loss rate of the phosphotungstic acid reaches 39 percent.
Example 11
N-butyl chloride is used for replacing chloropropyl triethoxysilane in the catalyst preparation process, the obtained ionic liquid is reacted with 12-phosphotungstic acid to prepare the catalyst, the synthesis steps are the same as example 3, the catalyst is used for asymmetric dihydroxylation of styrene, the yield of R-phenyl glycol is 76%, the enantiomeric excess value (e.e.) is 90%, and the loss rate of the phosphotungstic acid reaches 10%.
Example 12
N-butyl chloride is used for replacing chloropropyl triethoxysilane in the catalyst preparation process, the obtained ionic liquid is reacted with 12-phosphotungstic acid to prepare the catalyst, the synthesis steps are the same as example 4, the catalyst is used for asymmetric dihydroxylation of styrene, the yield of R-phenyl glycol is 72%, the enantiomeric excess value (e.e.) is 84%, and the phosphotungstic acid loss rate reaches 16%.
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