CN1868595A - Chiral schiff base-metal heterogeneous epoxidation catalyst and its prepn. method - Google Patents
Chiral schiff base-metal heterogeneous epoxidation catalyst and its prepn. method Download PDFInfo
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Abstract
A multi-phase epoxidizing catalyst with high activity, chiral selectivity and stability, and short reaction time is prepared through using sulfonyl group to axially fix the complex of the chiral Schiff base and metal to inorganic carrier and/or polymer carrier.
Description
Technical field
The present invention relates to a kind of epoxidation catalyst of chiral schiff base-metal, relate in particular to a kind of chirality heterogeneous epoxidation catalyst by the axial immobilized chiral schiff base-metal of sulfonic group.
The invention still further relates to above-mentioned Preparation of catalysts method.
Background technology
Over past ten years, people are huge and be the trend of cumulative year after year to the demand of single enantiomer chipal compounds, and this demand is mainly reflected in fields such as medicine, agricultural chemicals and fine chemicals.Wherein, the chiral epoxy thing can transform by asymmetric open loop and functional group and obtain a large amount of dissimilar chipal compounds, therefore the epoxides of synthesis of chiral enjoys people to pay close attention to, wherein the chiral epoxy compound of chromene derivative is the very important intermediate [US5 of a class that is used for synthetic treatment hypertension drug, 352,814; US 5,639, and 889].[ZL 95192225.4 with Chiral Mn (salen) complex compound of sparing phase; US 5,420, and 314; US 5,599,957] or other chiral schiff base metal complex compound [US 5,602,267] to make chiral epoxy compound as the asymmetric Epoxidation of the non-functional group of catalyst alkene be a kind of very effective approach.But product and catalyst are not easily separated, product is difficult for purifying because Mn (salen) catalytic body exists, catalyst is stable inadequately and catalyst is difficult to shortcomings such as recovery, and its commercial Application still is subjected to certain restriction.
Comparatively speaking, heterogeneous asymmetry catalysis not only possesses outside the advantages such as product separates easily with catalyst, the easy purifying of product, but also possesses the advantage that catalyst can recycling.Therefore heterogeneousization of catalyst causes various countries scientist's attention gradually in recent years.China also is in blank basically in the research field of utilizing the direct synthesis of chiral pharmaceutical intermediate of heterogeneous asymmetry catalysis epoxidation technology, has only a kind of report [ZL 00122944.3] of chiral schiff base-metal epoxidation catalyst of polymerization: Chiral Mn (salen) complex compound autohemagglutination is formed insoluble polymer be used for asymmetric Epoxidation.This Preparation of catalysts is relatively complicated, and also swelling and make overanxious washing become loaded down with trivial details relatively easily of polymer.
Recently, document [Catal.Rev.-Sci.Eng.46 (2004) 419] summarized with Mn (salen) immobilized not only can the isolating active position in the inorganic nano duct strengthening the stability of catalyst, but also may utilize the asymmetry of the surface of solids and the solid space in the nano-pore to improve chiral selectivity.Though [Chem.Rev.102 (2002) 3495 for early stage document; Chem.Soc.Rev.33 (2004) 108] on summarized many immobilized Mn (salen) and the preparation heterogeneous catalyst, but these catalyst often prepare relative complex, the activity of gained is relative with the ee value even mutually relatively poor, and follow certain leakage, from commercial Application a certain distance is arranged still.
In sum, still need to improve for heterogeneous Mn (salen) Preparation of catalysts: 1, a kind of more simple but effective method of needs development is immobilized on nano material with Mn (salen); 2, this heterogeneous catalyst will have suitable stability, and promptly heterogeneous catalyst can recycle; 3, to guarantee that heterogeneous catalyst has suitable catalytic activity; 4, also be the most important, need utilize the distinctive character of carrier to improve the chiral selectivity of asymmetric catalysis.
Summary of the invention
The object of the present invention is to provide the axially chirality heterogeneous epoxidation catalyst of immobilized chiral schiff base-metal of a kind of sulfonic group.
Another purpose of the present invention is to provide above-mentioned Preparation of catalysts method.
For achieving the above object, the heterogeneous epoxidation catalyst of chiral schiff base-metal provided by the invention, its structure as shown in the formula:
In the formula: R
1-R
4Separate;
R
1=C
1-C
10Alkyl or aryl, F, Cl, halogen or the NO of Br
2
R
2=C
1-C
10Alkyl or aryl, F, Cl, halogen or the NO of Br
2
R
3=C
1-C
10Alkyl or aryl, the adjacent diamines of chirality is 1R, 2R or 1S, 2S configuration;
R
4=directly connect sulphur atom and carrier singly-bound or contain C
1-C
16With heteroatomic organic group;
M=Ti, V, Cr, Mn, Co, Ni, Cu, Zn, Al, Ru are or/and Pd;
Carrier is that the inorganic silicon dioxide carrier of material, organic group modified of inorganic porous earth silicon material, hybrid inorganic-organic hole wall or other can grafting R
4Sulfonic organic insoluble polymer carrier.
Described catalyst, the inorganic silicon dioxide carrier of described inorganic porous earth silicon material and organic group modified is meant silica gel, SBA-15 or MCM-41.
When described catalyst, carrier are the material of inorganic porous silica or hybrid inorganic-organic hole wall, R
4Be connected on the silicon atom; When carrier is organic insoluble polymer, R
4Be connected on the carbon atom.
The method of the above-mentioned catalyst of preparation provided by the invention the steps include:
A) with inorganic porous earth silicon material in 100-180 ℃ of vacuum activation processing 2-8 hour, cool to room temperature under the normal pressure nitrogen, every gram earth silicon material adds the 0.2-2 milliliter and contains sulfydryl or contain the estersil of phenyl and the toluene of 10-70 milliliter, under the nitrogen protection under normal pressure, in 100-125 ℃ of reaction 6-24 hour, toluene wash is used in cooling in the air, filtration, and air dry must contain the inorganic silicon dioxide carrier of sulfydryl or phenyl;
B) the every gram adding of the product of step a 1-10 ml concn is 30% hydrogen peroxide, in 0-30 ℃ of reaction 6-24 hour, filters, and washs neutrality; Under the nitrogen protection, be cooled to 0-60 ℃, the sulfonated reagent that adds the 1-10 milliliter by every gram carried out sulfonation 1-6 hour, the solid suction filtration, washed neutrality, obtained containing sulfonic carrier; For the inorganic silicon dioxide carrier that contains phenyl, in 100-180 ℃ of vacuum activation processing 2-8 hour;
C) the every gram of the product of step b adds the inorganic salts of 0.5-5.5 mM or the aqueous solution of inorganic base, and room temperature reaction 1-6 hour, filter, wash neutrality;
D) complex compound of the metal-schiff bases of the every gram adding of the product of step c 0.1-2.0 mM and the methyl alcohol or the ethanol of 30-60 milliliter, 60-90 ℃ was reacted 3-10 hour, filter, the ethanol washing, air dry gets the target catalyst;
Sulfydryl among the step a is meant aryl sulfydryl or fat-based sulfydryl; Phenyl is meant the phenyl that direct phenyl and alkyl or hetero atom replace;
Sulfonated reagent among the step b is the concentrated sulfuric acid, oleum or chlorosulfonic acid.
Described preparation method, the condition of vacuum activation processing was 120 ℃ of vacuum activation processing 4 hours.Described preparation method is characterized in that, the sulfydryl among the step a is mercaptopropyl trimethoxysilane (HS (CH
2)
3Si (OMe)
3); Phenyl is phenyl triethoxysilane (PhSi (OEt)
3), benzyl triethoxysilane (PhCH
2Si (OEt)
3), phenethyl trimethoxy silane (Ph (CH
2)
2Si (OMe)
3) and N-phenyl propyl trimethoxy silane (PhNH (CH
2)
3Si (OMe)
3).
Described preparation method is characterized in that, the carrier among the step c refers to the inorganic silicon dioxide carrier of material, organic group modified of inorganic porous earth silicon material, hybrid inorganic-organic hole wall or other can grafting R
4Sulfonic organic insoluble polymer carrier.
Described preparation method is characterized in that, inorganic salts among the step c or inorganic base are NaOH, NaHCO
3, Na
2CO
3, KOH, KHCO
3Or K
2CO
3
Described preparation method is characterized in that, the inorganic salts among the step c or the concentration of inorganic base aqueous solution are the 0.005-0.5 mol.
Described preparation method is characterized in that, the complex compound of the metal-schiff bases in the steps d is the chloride of chiral schiff base-metal.
Compared with prior art, the present invention has the following advantages:
1, the invention provides a kind of preparation method who adopts the axial immobilized metal-schiff base complex of sulfonic group, this heterogeneous catalyst prepares easily, post-reaction treatment is simple to operate, only need simple overanxiously get final product separating catalyst and product, and the also easier relatively purifying of product.
2, this heterogeneous catalyst is applied to asymmetric epoxidation reaction, the activity of gained and chiral selectivity can significantly be higher than does not have immobilized even phase catalyst, and the general heterogeneous catalyst of reporting in the document often can only obtain than even mutually low activity and chiral selectivity.
3 and this heterogeneous catalyst show advantages of higher stability, still can keep constant relatively conversion ratio and chiral selectivity recycling 5 times.Yet even phase catalyst often can only use once.
The specific embodiment
In order to further specify the present invention, adopt the chiral schiff base catalysis asymmetric Epoxidation that contains Mn as embodiment, but it does not limit the defined invention scope of each accessory claim.
Involved in the present invention:
The organic group that contains sulfydryl refers to sulfydryl and can link to each other with phenyl ring or fat group, most preferably is mercaptopropyl trimethoxysilane (HS (CH
2)
3Si (OMe)
3).The concentration of described hydrogen peroxide preferred 30%.
The preferred phenyl triethoxysilane of the organic group (PhSi (OEt) that contains phenyl
3), benzyl triethoxysilane (PhCH
2Si (OEt)
3), phenethyl trimethoxy silane (Ph (CH
2)
2Si (OMe)
3With N-phenyl propyl trimethoxy silane (PhNH (CH
2)
3Si (OMe)
3The concentrated sulfuric acid of the described concentrated sulfuric acid preferred 98%, the oleum of oleum preferred 10%.
The mesoporous material that contains the hybrid inorganic-organic hole wall of sulfydryl, wherein the hydridization hole wall refers to the organic group that contains phenyl bridged bond or ethane bridged bond in the hole wall, preferred ethane bridged bond; The preferred propyl group sulfydryl of mercapto groups wherein.The concentration of described hydrogen peroxide preferred 30%.
The preferred polystyrene resin of insoluble polymer that contains phenyl, the concentrated sulfuric acid of the described concentrated sulfuric acid preferred 98%, the oleum of oleum preferred 10%.
Inorganic salts or inorganic base are NaOH, NaHCO
3, Na
2CO
3Or KOH, KHCO
3, K
2CO
3, preferred NaHCO
3
The temperature of grafting reaction refers at counterflow condition, 80 ℃ of preferred alcohol counterflow conditions, and metal refers to Ti, V, Cr, Mn, Co, Ni, Cu, Zn, Al, Ru, Pd, preferred Mn, Co.The structure of schiff bases such as accompanying drawing, wherein, R
1-R
3Separate, R
1=C
1-C
10Alkyl or aryl, F, Cl, halogen or the NO of Br
2, the preferred tertiary butyl; R
2=C
1-C
10Alkyl or aryl, F, Cl, halogen or the NO of Br
2, the preferred tertiary butyl; R
3=C
1-C
10Alkyl or aryl, preferred cyclohexyl and phenyl; The adjacent diamines of chirality is 1R, 2R or 1S, 2S configuration.Described grafting refers to from axial direction and is connected on the carrier by sulfonic group.The heterogeneous catalyst of gained detects the scope of amount of the metal (salen) of grafting to the carrier between 0.01-0.1mmol/g through elementary analysis.
Embodiment 1
The MCM-41 (aperture 1.6nm) of (1) 3 gram handles the HS (CH that the back adds 150ml dry toluene and 6ml at heating, vacuum
2)
3Si (OMe)
3, in 120 ℃ of grafting 18h, overanxious then washing and drying.
(2) use 30% H again
2O
2The precursor 24h that 27ml oxidation step 1 obtains adds 0.33g NaHCO after the overanxious washing
3The 20ml aqueous solution at room temperature reaction 3h, overanxious washing and drying.
(3) step 2 is obtained complex compound (1.0mmol, the wherein R of precursor backflow grafting M (salen) in the ethanol of 60ml
1=t-Bu, R
2=t-Bu, R
3=Ph, the adjacent diamines of chirality is (1S, 2S) configuration, metal=Mn) 5 hours.The heterogeneous catalyst that can make is numbered A.
Embodiment 2
With embodiment 1, just step 1 changes into: carrier adopts the hybrid inorganic-organic materials that contains the propane sulfydryl [the synthetic Micro.Meso.Mater.77 (2005) 257 that sees for details] of ethane bridged bond, and adopts the complex compound (R wherein of M (salen) in the step 3
1=t-Bu, R
2=t-Bu, R
3=-(CH
2)
4-, the adjacent diamines of chirality is that (M=Mn), the heterogeneous catalyst of system is numbered B. for 1R, 2R) configuration
Embodiment 3
The SBA-15 (aperture 7.6nm) of (1) 3 gram handles the PhSi (OEt) that the back adds 150ml dry toluene and 7ml at heating, vacuum
3, in 120 ℃ of grafting 18h, overanxious then washing and drying.(2) the precursor heating, vacuum that step 1 is obtained is handled the concentrated sulfuric acid of back adding 10ml in 100 degree sulfonation 8 hours, overanxious then washing and drying.Again with 0.33g NaHCO
3The 20ml aqueous solution overanxious washing and drying behind room temperature reaction 3h.(3) complex compound (1.0mmol, the wherein R of the catalyst precarsor that step 2 is obtained backflow grafting M (salen) in the ethanol of 60ml
1=t-Bu, R
2=t-Bu, R
3=-(CH
2)
4-, the adjacent diamines of chirality is that (M=Mn) heterogeneous catalyst that can make in 5 hours is numbered C. for 1S, 2S) configuration
Embodiment 4
With embodiment 3, change the SBA-15 in the step (1) into SiO
2(aperture 9.7nm) and the oleum that changes the sulfonation condition in the step (2) into 10ml 10% be sulfonation 2h at room temperature, and other conditions are identical, and the heterogeneous catalyst of gained is numbered D.
Embodiment 5
The SiO of (1) 3 gram
2(aperture 9.7nm) handles the Ph (CH that the back adds 150ml dry toluene and 7ml at heating, vacuum
2)
2Si (OEt)
3, in 120 ℃ of grafting 18h, overanxious then washing and drying.(2) the precursor heating, vacuum that step 1 obtained is handled 10% oleum that the back adds 10ml sulfonation 2h at room temperature, overanxious then washing and drying.Again with 0.33g NaHCO
3The 20ml aqueous solution overanxious washing and drying behind room temperature reaction 3h.(3) the carrier heating, vacuum of gained in the step 2 is handled the MeSi (OMe) that the back adds 150ml dry toluene and 6ml
3, in 120 ℃ of grafting 18h, overanxious then washing and drying.(4) complex compound (1.0mmol, the wherein R of the catalyst precarsor that step 3 is obtained backflow grafting M (salen) in the ethanol of 60ml
1=t-Bu, R
2=t-Bu, R
3=Ph, the adjacent diamines of chirality is that (M=Mn) heterogeneous catalyst that can make in 5 hours is numbered E. for 1S, 2S) configuration
Embodiment 6
With embodiment 5, just with the Ph (CH in the step 1
2)
2Si (OEt)
3Change PhNH (CH into
2)
3Si (OEt)
3, prepared heterogeneous catalyst is numbered F.
Embodiment 7
With embodiment 5, just the complex compound with the M in the step 4 (salen) replaces with (R wherein
l=t-Bu, R
2=t-Bu, R
3=-(CH
2)
4-, the adjacent diamines of chirality is that (M=Mn), the heterogeneous catalyst of gained is numbered G. for 1R, 2R) configuration
Embodiment 8
With embodiment 5, just with the Ph (CH in the step 1
2)
2Si (OEt)
3Change PhNH (CH into
2)
3Si (OEt)
3, and the complex compound of the M in the step 4 (salen) replaced with (R wherein
1=t-Bu, R
2=t-Bu, R
3=-(CH
2)
4-, the adjacent diamines of chirality is that (M=Mn), the heterogeneous catalyst of gained is numbered H. for 1R, 2R) configuration
Embodiment 9
(1) restrains polystyrene resin and the 2g NaHCO that has sulfonic acid functional with 3
3The 20ml aqueous solution overanxious washing and drying behind room temperature reaction 3h.(2) complex compound (1.0mmol, the wherein R of the precursor that step 1 is obtained backflow grafting M (salen) in the ethanol of 60ml
1=t-Bu, R
2=t-Bu, R
3=-(CH
2)
4-, the adjacent diamines of chirality is that (M=Mn) heterogeneous catalyst that can make in 5 hours is numbered I. for 1R, 2R) configuration
Embodiment 10
With embodiment 4, just in step 3, adopt the complex compound (R wherein of M (salen)
1=t-Bu, R
2=t-Bu, R
3=-(CH
2)
4-, the adjacent diamines of chirality is that (M=Co), the heterogeneous catalyst of system is numbered L. for 1R, 2R) configuration
Embodiment 11
Multi-phase chiral catalyst A, C, D, E and corresponding two even phase Mn (salen) Cl catalyst are respectively applied for AMS asymmetry catalysis epoxidation reaction and its reaction condition is identical.
With 0.015mmol Mn (salen) Cl catalyst or contain same amount Mn (salen) heterogeneous catalyst, 1mmol substrate alkene, be dissolved in the 3ml carrene, adjustment to 20 degree with mixture adds 3.64ml 0.55M liquor natrii hypochloritis (2mmol) in above-mentioned solution.Two-phase mixture is stirring reaction 24 hours under 20 degree.Reaction finishes the back and removes even phase catalyst with column chromatography method, removes solid catalyst with overanxious method, and filtrate is analyzed productive rate and enantio-selectivity (permethylated beta-schardinger dextrin-chirality capillary chromatographic column) with gas chromatograph, the results are shown in Table 1.Use heterogeneous catalyst can improve chiral selectivity greatly, can see that ee value 26% significantly brings up to 77% under the heterogeneous condition by what spare phase.See Table 1.
Embodiment 12
Multi-phase chiral catalyst A, E, F and even accordingly phase Mn (salen) Cl catalyst is respectively applied for cinnamic asymmetry catalysis epoxidation reaction and its each reaction condition is identical.Reaction condition is with embodiment 9, but the 4-phenyl pyridine oxide (additive) that also will add 0.38mmol more simultaneously reaction temperature be controlled at 0 degree, other conditionally completes are identical, the results are shown in Table 2.Even can find that heterogeneous catalyst when catalyst consumption reduces to half (0.75%mmol), still can obtain conversion ratio, chemo-selective and the chiral selectivity suitable with even phase catalyst.See Table 2.
Embodiment 13
Multi-phase chiral catalyst B, G, H, I and corresponding even phase Mn (salen) Cl catalyst thereof are respectively applied for 6-cyano group-2, and the asymmetry catalysis epoxidation reaction of 2-methyl chromene and its each reaction condition are identical.Reaction condition is with embodiment 9, but also will add the 4-phenyl pyridine oxide (additive) of 0.38mmol again, and the reaction time becomes 6h, and other conditionally completes are identical, the results are shown in Table 3.The heterogeneous catalyst that can find to use same amount just can complete reaction at 4.5h, even phase catalyst then needs the reaction time of 6h, and the chiral selectivity of heterogeneous catalyst gained also significantly is higher than even phase catalyst, and the ee value brings up to heterogeneous 90% by 80% of even phase.See Table 3.
Embodiment 14
Recycle the performance example.
To contain heterogeneous catalyst D, the 1mmol of 0.045mmol Mn (salen) AMS, be dissolved in the 9ml carrene, with the adjustment to 20 of mixture degree, in above-mentioned solution, add the liquor natrii hypochloritis (6mmol) of 11ml0.55M.Two-phase mixture is stirring reaction 24 hours under 20 degree.Reaction finishes the overanxious washing solid catalyst in back and is used further to epoxidation reaction next time, the results are shown in Table 4.Use the ee value that still keeps higher and constant for 5 times even can see heterogeneous catalyst, and even phase catalytic machine often can only be used once just inefficacy, heterogeneous catalyst has improved the stability of catalyst greatly.See Table 4.
The reaction result of table 1. heterogeneous catalyst catalysis asymmetric Epoxidation AMS
Catalyst | Reaction time (h) | Conversion ratio (%) | Optical selective (%) |
Even phase A E | 6 24 24 | 100 89.4 55.3 | 26.4 77.3 58.5 |
Even phase C D | 6 24 24 | 100 65.6 64.2 | 55.0 73.6 75.8 |
The cinnamic reaction result of table 2. heterogeneous catalyst catalysis asymmetric Epoxidation
Catalyst | Catalytic amount mmol% | Reaction time (h) | Conversion ratio (%) | Selectivity (%) | Optical selective (%) |
Even phase A E F | 1.5 1.5 1.5 0.75 | 6 24 24 24 | 100 91.5 100 100 | 100 87.6 95.2 95.8 | 58.2 52.5 58.5 59.2 |
Table 3. heterogeneous catalyst catalysis asymmetric Epoxidation 6-cyano group-2, the reaction result of 2-methyl chromene
Catalyst | Reaction time (h) | Conversion ratio (%) | Optical selective (%) |
Even phase B G H I | 6 6 6 4.5 6 | 97.0 74.3 98.3 100 99.4 | 80.1 84.6 86.5 90.6 87.9 |
Table 4. heterogeneous catalyst recycle performance
Catalyst D | Reaction time (h) | Conversion ratio (%) | Optical selective (%) |
Even phase 1st 2nd 3rd 4th 5th | 6 24 24 24 24 24 | 100 64.2 55.7 47.4 35.7 40.5 | 55.0 75.8 73.5 76.3 74.6 77.4 |
Claims (10)
1, a kind of heterogeneous epoxidation catalyst of chiral schiff base-metal, its structure as shown in the formula:
In the formula: R
1-Ru is separate;
R
1=C
1-C
10Alkyl or aryl, F, Cl, halogen or the NO of Br
2
R
2=C
1-C
10Alkyl or aryl, F, Cl, halogen or the NO of Br
2
R
3=C
1-C
10Alkyl or aryl, the adjacent diamines of chirality is 1R, 2R or 1S, 2S configuration;
R
4=directly connect sulphur atom and carrier singly-bound or contain C
1-C
16With heteroatomic organic group;
M=Ti, V, Cr, Mn, Co, Ni, Cu, Zn, Al, Ru are or/and Pd;
Carrier is that the inorganic silicon dioxide carrier of material, organic group modified of inorganic porous earth silicon material, hybrid inorganic-organic hole wall or other can grafting R
4Sulfonic organic insoluble polymer carrier.
2, the catalyst of claim 1 is characterized in that, the inorganic silicon dioxide carrier of described inorganic porous earth silicon material and organic group modified is meant silica gel, SBA-15 or MCM-41.
3, the catalyst of claim 1 is characterized in that, when carrier is the material of inorganic porous silica or hybrid inorganic-organic hole wall, and R
4Be connected on the silicon atom; When carrier is organic insoluble polymer, R
4Be connected on the carbon atom.
4, the described Preparation of catalysts method of claim 1, its key step is:
A) with inorganic porous earth silicon material in 100-180 ℃ of vacuum activation processing 2-8 hour, cool to room temperature under the normal pressure nitrogen, every gram earth silicon material adds the 0.2-2 milliliter and contains sulfydryl or contain the estersil of phenyl and the toluene of 10-70 milliliter, under the nitrogen protection under normal pressure, in 100-125 ℃ of reaction 6-24 hour, toluene wash is used in cooling in the air, filtration, and air dry must contain the inorganic silicon dioxide carrier of sulfydryl or phenyl;
B) the every gram adding of the product of step a 1-10 ml concn is 30% hydrogen peroxide, in 0-30 ℃ of reaction 6-24 hour, filters, and washs neutrality; Under the nitrogen protection, be cooled to 0-60 ℃, the sulfonated reagent that adds the 1-10 milliliter by every gram carried out sulfonation 1-6 hour, the solid suction filtration, washed neutrality, obtained containing sulfonic carrier; For the inorganic silicon dioxide carrier that contains phenyl, in 100-180 ℃ of vacuum activation processing 2-8 hour;
C) the every gram of the product of step b adds the inorganic salts of 0.5-5.5 mM or the aqueous solution of inorganic base, and room temperature reaction 1-6 hour, filter, wash neutrality;
D) complex compound of the metal-schiff bases of the every gram adding of the product of step c 0.1-2.0 mM and the methyl alcohol or the ethanol of 30-60 milliliter, 60-90 ℃ was reacted 3-10 hour, filter, the ethanol washing, air dry gets the target catalyst;
Sulfydryl among the step a is meant aryl sulfydryl or fat-based sulfydryl; Phenyl is meant the phenyl that direct phenyl and alkyl or hetero atom replace;
Sulfonated reagent among the step b is the concentrated sulfuric acid, oleum or chlorosulfonic acid.
5. the preparation method of claim 4 is characterized in that, the condition of vacuum activation processing was 120 ℃ of vacuum activation processing 4 hours.
6, the preparation method of claim 4 is characterized in that, the sulfydryl among the step a is a mercaptopropyl trimethoxysilane; Phenyl is phenyl triethoxysilane, benzyl triethoxysilane, phenethyl trimethoxy silane or N-phenyl propyl trimethoxy silane.
7, the preparation method of claim 4 is characterized in that, the carrier among the step c refers to the inorganic silicon dioxide carrier of material, organic group modified of inorganic porous earth silicon material, hybrid inorganic-organic hole wall or other can grafting R
4Sulfonic organic insoluble polymer carrier.
8, the preparation method of claim 4 is characterized in that, inorganic salts among the step c or inorganic base are NaOH, NaHCO
3, Na
2CO
3, KOH, KHCO
3Or K
2CO
3
9, the preparation method of claim 4 is characterized in that, the inorganic salts among the step c or the concentration of inorganic base aqueous solution are the 0.005-0.5 mol.
10, the preparation method of claim 4 is characterized in that, the complex compound of the metal-schiff bases in the steps d is the chloride of chiral schiff base-metal.
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CN1170834C (en) * | 2000-08-30 | 2004-10-13 | 中国科学院大连化学物理研究所 | Epoxidizing catalyst for polymerizing chiral Xifu alkali-metal |
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