CN105854950A - Supported chiral catalyst magnetic nanoparticles and preparation method and application thereof - Google Patents
Supported chiral catalyst magnetic nanoparticles and preparation method and application thereof Download PDFInfo
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- CN105854950A CN105854950A CN201610287374.5A CN201610287374A CN105854950A CN 105854950 A CN105854950 A CN 105854950A CN 201610287374 A CN201610287374 A CN 201610287374A CN 105854950 A CN105854950 A CN 105854950A
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- chiral
- particle
- magnetic nano
- chiral catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 239000002122 magnetic nanoparticle Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229920000642 polymer Polymers 0.000 claims abstract description 26
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 238000010550 living polymerization reaction Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 44
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 28
- 239000000047 product Substances 0.000 claims description 25
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- 238000001291 vacuum drying Methods 0.000 claims description 16
- 239000012265 solid product Substances 0.000 claims description 15
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 14
- 239000002077 nanosphere Substances 0.000 claims description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 150000007970 thio esters Chemical group 0.000 claims description 12
- -1 Dithiobenzoic acid cumenyl ester Chemical class 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 6
- 230000008878 coupling Effects 0.000 claims description 5
- 238000010168 coupling process Methods 0.000 claims description 5
- 238000005859 coupling reaction Methods 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000010257 thawing Methods 0.000 claims description 4
- 238000006117 Diels-Alder cycloaddition reaction Methods 0.000 claims description 2
- 230000001351 cycling effect Effects 0.000 claims description 2
- 238000002955 isolation Methods 0.000 claims description 2
- 230000003252 repetitive effect Effects 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 11
- 238000011914 asymmetric synthesis Methods 0.000 abstract description 2
- 238000005698 Diels-Alder reaction Methods 0.000 abstract 1
- 239000005864 Sulphur Substances 0.000 abstract 1
- 238000006352 cycloaddition reaction Methods 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 238000011084 recovery Methods 0.000 description 5
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 208000035126 Facies Diseases 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- AXMVYSVVTMKQSL-UHFFFAOYSA-N UNPD142122 Natural products OC1=CC=C(C=CC=O)C=C1O AXMVYSVVTMKQSL-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 229940117916 cinnamic aldehyde Drugs 0.000 description 2
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 0 **=C*(F)=CC=C Chemical compound **=C*(F)=CC=C 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000006736 Huisgen cycloaddition reaction Methods 0.000 description 1
- 238000005873 Huisgen reaction Methods 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000001902 propagating effect Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
Classifications
-
- 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
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
- C07B37/10—Cyclisation
- C07B37/12—Diels-Alder reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B53/00—Asymmetric syntheses
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/69—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to carbon-to-carbon double or triple bonds
-
- 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
- B01J2231/324—Cyclisations via conversion of C-C multiple to single or less multiple bonds, e.g. cycloadditions
- B01J2231/326—Diels-Alder or other [4+2] cycloadditions, e.g. hetero-analogues
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses supported chiral catalyst magnetic nanoparticles and a preparation method and application thereof, and belongs to the technical field of chiral catalysis and asymmetric synthesis. According to the key points of the technical scheme, Macmillan chiral monomers are homopolymerized through RAFT living polymerization to obtain a chiral polymer with the chain end containing active double sulphur ester groups, the chiral polymer is coupled with magnetic nanoparticles RAFT with the surfaces in keyed connection double bonds to form the supported chiral catalyst magnetic nanoparticles of the following structure shown in the description. The invention further discloses a specific preparation method of the supported chiral catalyst magnetic nanoparticles and application thereof in Diels-Alder ring cycloaddition reaction. The supported chiral catalyst magnetic nanoparticles can be separated through magnet attraction, and therefore catalyst recycling and repeated utilization are achieved.
Description
Technical field
The invention belongs to chiral catalysis and asymmetric synthesis technical field, be specifically related to a kind of loaded chiral catalyst magnetic
Nanoparticle and its preparation method and application.
Background technology
In traditional radical polymerization system, number of free radical is higher, and chain transfer reaction is irreversible, is susceptible to freedom
The termination reaction of base, causes the degree of polymerization to reduce, reacts uncontrollable.If adding the special type that chain transfer constant is high in polymerization system
Chain-transferring agent so that carry out transfer of degrading between Propagating Radical and this chain-transferring agent, thus reduce the concentration of free radical, just have
Reversible addition-fracture transfer (RAFT) active free radical polymerization may be realized, thus carry out living control polymerization.
And magnetic nano-particle has, and specific surface area is big, Active sites is many, surface reaction activity is high, high adsorption capacity
The excellent properties such as high with catalytic efficiency, provides essential condition for nanoparticle for catalyst, thus it has in terms of catalysis
Important application.
Additionally, people's method of modifying the most direct to magnetic nano-particle is exactly Surface coating in recent years, form magnetic core
Shell structure so that it is wider application and different field.As far as we know, the method that some efficient couplings are had been developed, example
Huisgen reaction, alkynes and the 1,3-Dipolar Cycloaddition of azide, sulfydryl-alkene clicking chemistry such as copper catalysis.
Summary of the invention
Present invention solves the technical problem that and there is provided a kind of loaded chiral catalyst magnetic nano-particle and preparation side thereof
Method and application, first pass through RAFT living polymerization and Macmillan chiral monomer carries out homopolymerization obtain the end of the chain containing active pair of sulfur
The chiral polymer chain of ester group, then it is urged with the magnetic nano-particle RAFT coupling formation loaded chiral of surface keyed jointing double bond
Agent magnetic nano-particle, makes the polymer chain being connected on nanosphere have controllability, and the advantage that can be effectively grafted, can lead to again
Cross magnet adsorption to separate, thus reach the recovery of catalyst and reuse, utilize this loaded chiral catalyst magnetic nano particle
Son in catalytic asymmetric reaction in addition to obtaining the chiral product of high yield and highly-solid selectively, it is also possible to realize catalyst
Magneto separate and repeat recycle feature, reduce production cost.
The present invention solves that above-mentioned technical problem adopts the following technical scheme that, a kind of loaded chiral catalyst magnetic nano particle
Son, it is characterised in that: first pass through RAFT living polymerization and Macmillan chiral monomer is carried out homopolymerization obtain the end of the chain containing active
The chiral polymer of double thioester groupsAgain by itself and the magnetic nano particle of surface keyed jointing double bond
Sub-RAFT coupling forms loaded chiral catalyst magnetic nano-particle, and it has a following structure:
The preparation method of loaded chiral catalyst magnetic nano-particle of the present invention, it is characterised in that concrete steps
For: weigh surface and there is the Fe of double bond3O4Nanosphere 0.15g joins in reaction bulb, after ultrasonic disperse 5-30min, is sequentially added into
The end of the chain containing the chiral polymer 0.1-0.5g of active pair of thioester group, azodiisobutyronitrile 4mg, dimethylformamide 30mL and
Triethylamine 1mL, freezes after taking out 5 times at N2Under the conditions of in 40-100 DEG C react 48h, reaction terminate rear Magneto separate, solid product is successively
It is centrifuged three times with oxolane and methanol are each, solid product is placed in vacuum drying oven and prepares negative in 40 DEG C of vacuum drying 48h
Supported chiral catalyst magnetic nano-particle.
Limiting further, the concrete preparation process of the described end of the chain chiral polymer containing active pair of thioester group is: depend on
The secondary Macmillan of weighing chiral monomer, dithiobenzoic acid cumenyl ester and azodiisobutyronitrile are dissolved in dimethylformamide
In, wherein Macmillan chiral monomer, dithiobenzoic acid cumenyl ester are 100-with the mol ratio of azodiisobutyronitrile
150:1:0.2, seals after being completely dissolved, and uses five methods of freeze thawing to carry out the oxygen in removing system, reaction bulb is placed on oil bath pan
In in 40-100 DEG C of stirring reaction 24h, after reaction terminates, precipitate in ether, centrifugal, solid oxolane is dissolved, then
Precipitating in ether, precipitation repeatedly until monomer eliminates completely, obtains the product as light yellow solid end of the chain in 30 DEG C of dry 48h and contains
The chiral polymer of the double thioester group of activity.
Limiting further, the concrete synthetic route of described loaded chiral catalyst magnetic nano-particle is:
Loaded chiral catalyst magnetic nano-particle of the present invention answering in Diels-Alder cycloaddition reaction
With, after wherein loaded chiral catalyst magnetic nano-particle is reclaimed by Magnetic Isolation, repetitive cycling uses.
The present invention compared with prior art has the advantage that
1, by RAFT living polymerization synthetic polymer, the polymer chain being connected on magnetic nano-particle is made to have controlled
Property；
2, by the method for RAFT coupling, polymer and magnetic nano-particle are carried out the most controlled grafting；
3, the preparation method of loaded chiral catalyst magnetic nano-particle is simple and environmental protection；
4, the polymer chain hung can improve particle dispersibility in reaction medium, thus improves catalyst further
Catalysis activity, and high catalysis activity can be demonstrated as solubility line polymer carried catalyst.
Detailed description of the invention
By the following examples the foregoing of the present invention is described in further details, but this should be interpreted as this
The scope inventing above-mentioned theme is only limitted to below example, and all technology realized based on foregoing of the present invention belong to this
Bright scope.
Embodiment 1
The preparation of the end of the chain chiral polymer containing active pair of thioester group
Weigh Macmillan chiral monomer (2.76g, 9.1279mmol), dithiobenzoic acid cumenyl ester successively
(16.28mg, 0.06mmol) and azodiisobutyronitrile (2mg, 0.0122mmol) are dissolved in 5mL dimethylformamide, the most molten
Seal after solution.Use five methods of freeze thawing to carry out the oxygen in removing system, reaction bulb is placed in oil bath pan in 70 DEG C of stirring reactions
24h.After reaction terminates, precipitate in ether, centrifugal, solid is dissolved with minimal amount of oxolane, then precipitates in ether,
Precipitation repeatedly, eliminates completely until monomer.Product as light yellow solid is obtained containing active pair of thioester group in 30 DEG C of dry 48h
Chiral polymer.Mn=18700, PDI=1.59.
Embodiment 2
The preparation of the end of the chain chiral polymer containing active pair of thioester group
Weigh Macmillan chiral monomer (1.814g, 5.999mmol), dithiobenzoic acid cumenyl ester successively
(16.28mg, 0.06mmol) and azodiisobutyronitrile (2mg, 0.0122mmol) are dissolved in 5mL dimethylformamide, the most molten
Seal after solution.Use five methods of freeze thawing to carry out the oxygen in removing system, reaction bulb is placed in oil bath pan in 70 DEG C of stirring reactions
24h.After reaction terminates, precipitate in ether, centrifugal.Solid is dissolved with minimal amount of oxolane, then precipitates in ether,
Precipitation repeatedly, eliminates completely until monomer.Product as light yellow solid is obtained containing active pair of thioester group in 30 DEG C of dry 48h
Chiral polymer.Mn=3590, PDI=1.14.
Embodiment 3
The preparation of loaded chiral catalyst magnetic nano-particle
Weigh surface and there is the Fe of double bond3O4Nanosphere 0.15g joins in reaction bulb, after ultrasonic disperse 5-30min, depends on
Chiral polymer 0.1g, azodiisobutyronitrile 4mg, dimethylformamide 30mL and the triethylamine that secondary addition embodiment 1 prepares
1mL.Freeze after taking out 5 times at N2Under the conditions of in 70 DEG C react 48h.Reaction terminates rear Magneto separate, and solid product uses oxolane successively
Each with methanol centrifugal three times, solid product is placed in vacuum drying oven and prepares loaded chiral catalysis in 40 DEG C of vacuum drying 48h
Agent magnetic nano-particle.△ m=0.08g, the load capacity of loaded chiral catalyst magnetic nano-particle is 1.15mmol/g.
Embodiment 4
The preparation of loaded chiral catalyst magnetic nano-particle
Weigh surface and there is the Fe of double bond3O4Nanosphere 0.15g joins in reaction bulb, after ultrasonic disperse 5-30min, depends on
Chiral polymer 0.3g, azodiisobutyronitrile 4mg, dimethylformamide 30mL and the triethylamine that secondary addition embodiment 1 prepares
1mL.Freeze after taking out 5 times at N2Under the conditions of in 70 DEG C react 48h.Reaction terminates rear Magneto separate, and solid product uses oxolane successively
Each with methanol centrifugal three times, solid product is placed in vacuum drying oven and prepares loaded chiral catalysis in 40 DEG C of vacuum drying 48h
Agent magnetic nano-particle.△ m=0.25g, the load capacity of loaded chiral catalyst magnetic nano-particle is 2.1mmol/g.
Embodiment 5
The preparation of loaded chiral catalyst magnetic nano-particle
Weigh surface and there is the Fe of double bond3O4Nanosphere 0.15g joins in reaction bulb, after ultrasonic disperse 5-30min, depends on
Chiral polymer 0.5g, azodiisobutyronitrile 4mg, dimethylformamide 30mL and the triethylamine that secondary addition embodiment 1 prepares
1mL.Freeze after taking out 5 times at N2Under the conditions of in 100 DEG C react 48h.Reaction terminates rear Magneto separate, and solid product uses oxolane successively
Each with methanol centrifugal three times, solid product is placed in vacuum drying oven and prepares chiral catalyst magnetic in 40 DEG C of vacuum drying 48h
Property nanoparticle.△ m=0.41g, the load capacity of loaded chiral catalyst magnetic nano-particle is 2.42mmol/g.
Embodiment 6
The preparation of loaded chiral catalyst magnetic nano-particle
Weigh surface and there is the Fe of double bond3O4Nanosphere 0.15g joins in reaction bulb, after ultrasonic disperse 5-30min, depends on
Chiral polymer 0.1g, azodiisobutyronitrile 4mg, dimethylformamide 30mL and the triethylamine that secondary addition embodiment 2 prepares
1mL.Freeze after taking out 5 times at N2Under the conditions of in 40 DEG C react 48h.Reaction terminates rear Magneto separate, and solid product uses oxolane successively
Each with methanol centrifugal three times, solid product is placed in vacuum drying oven and prepares loaded chiral catalysis in 40 DEG C of vacuum drying 48h
Agent magnetic nano-particle.△ m=0.085g, the load capacity of loaded chiral catalyst magnetic nano-particle is 1.19mmol/g.
Embodiment 7
The preparation of loaded chiral catalyst magnetic nano-particle
Weigh surface and there is the Fe of double bond3O4Nanosphere 0.15g joins in reaction bulb, after ultrasonic disperse 5-30min, depends on
Chiral polymer 0.3g, azodiisobutyronitrile 4mg, dimethylformamide 30mL and the triethylamine that secondary addition embodiment 2 prepares
1mL.Freeze after taking out 5 times at N2Under the conditions of in 70 DEG C react 48h.Reaction terminates rear Magneto separate, and solid product uses oxolane successively
Each with methanol centrifugal three times, solid product is placed in vacuum drying oven and prepares loaded chiral catalysis in 40 DEG C of vacuum drying 48h
Agent magnetic nano-particle.△ m=0.27g, the load capacity of loaded chiral catalyst magnetic nano-particle is 2.13mmol/g.
Embodiment 8
The preparation of loaded chiral catalyst magnetic nano-particle
Weigh surface and there is the Fe of double bond3O4Nanosphere 0.15g joins in reaction bulb, after ultrasonic disperse 5-30min, depends on
Chiral polymer 0.5g, azodiisobutyronitrile 4mg, dimethylformamide 30mL and the triethylamine that secondary addition embodiment 2 prepares
1mL.Freeze after taking out 5 times at N2Under the conditions of in 100 DEG C react 48h.Reaction terminates rear Magneto separate, and solid product uses oxolane successively
Each with methanol centrifugal three times, solid product is placed in vacuum drying oven and prepares loaded chiral catalysis in 40 DEG C of vacuum drying 48h
Agent magnetic nano-particle.△ m=0.4g, the load capacity of loaded chiral catalyst magnetic nano-particle is 2.4mmol/g.
Embodiment 9
The loaded chiral catalyst magnetic Nano of embodiment 5 preparation of the amount 10% of substrate materials is added in test tube
Grain, acetonitrile/water (0.6mL), trifluoroacetic acid (0.0114g, 0.1mmol), cyclopentadiene (0.168mL, 1.96mmol), cinnamic aldehyde
(0.0636mL, 0.48mmol), reacts 24h under room temperature, thin layer chromatography follows the tracks of reaction to terminal, after completion of the reaction, and centrifugation,
Lower floor's solids with methanol is washed 3 times, recycles and reuses, and supernatant ether (3 × 10mL) extracts three times, merges organic facies, dense
Contracting, obtains pure addition compound product (petroleum ether: ethyl acetate=50:1), calculating productivity of weighing, nuclear magnetic resonance, NMR through column chromatography for separation
Hydrogen spectrum confirms target product.Appropriate NaBH is added in product4, room temperature reaction 48h.30h reaction 75%.After completion of the reaction,
It is spin-dried for solvent, adds q. s. methylene chloride, with distillation washing 3 times, collect organic facies, concentrate and obtain pure products through column chromatography for separation
(petroleum ether: ethyl acetate=16:1).By high performance liquid chromatography (HPLC) OJ-H chiral column separating chiral material, obtain product
Ee (endo) value be 86%, ee (exo) value is 83%, and yield is 99%.
Embodiment 10
The loaded chiral catalyst magnetic prepared of embodiment 7 preparation adding the amount 10% of substrate materials in test tube is received
Rice grain, water (0.6mL), trifluoroacetic acid (0.0114g, 0.1mmol), cyclopentadiene (0.168mL, 1.96mmol), cinnamic aldehyde
(0.0636mL, 0.48mmol), reacts 24h under room temperature, thin layer chromatography follows the tracks of reaction to terminal, after completion of the reaction, and centrifugation,
Lower floor's solids with methanol fully washs 3 times, and vacuum drying is reclaimed, and supernatant ether (3 × 10mL) extracts three times, merges organic
Phase, concentrates, obtains pure addition compound product (petroleum ether: ethyl acetate=50:1), calculating productivity of weighing, nuclear-magnetism through column chromatography for separation
Resonance hydrogen spectrum confirms target product.Appropriate NaBH is added in product4, room temperature reaction 48h.Reaction 30h product yield is
80%.After completion of the reaction, it is spin-dried for solvent, adds q. s. methylene chloride, with distillation washing 3 times, collect organic facies, concentrate through post layer
Analysis isolated pure products (petroleum ether: ethyl acetate=16:1).Separated by high performance liquid chromatography (HPLC) OJ-H chiral column
Chiral material, ee (endo) value obtaining product is 89%, and ee (exo) value is 91%, and yield is 99%.
Embodiment 11
By the Fe of the load Macmillan catalyst of recovery in embodiment 93O4Nanosphere repeats real as chiral catalyst
Execute example 9.Reaction 30h product yield is 75%, and ee (endo) value obtaining product is 85%, and ee (exo) value is 86%, and yield is
89%.
Embodiment 12
By the Fe of the load Macmillan catalyst of recovery in embodiment 103O4Nanosphere repeats real as chiral catalyst
Execute example 10.Reaction 30h product yield is 70%.Ee (endo) value obtaining product is 86%, and ee (exo) value is 90%, yield
It is 97%.
Embodiment 13
By the Fe of the load Macmillan catalyst of recovery in embodiment 113O4Nanosphere repeats real as chiral catalyst
Execute example 9.Reaction 30h product yield is 80%, and ee (endo) value obtaining product is 86%, and ee (exo) value is 79%, and yield is
90%.
Embodiment 14
By the Fe of the load Macmillan catalyst of recovery in embodiment 123O4Nanosphere repeats real as chiral catalyst
Execute example 10.Reaction 30h product yield is 75%, and ee (endo) value obtaining product obtaining product is 87%, and ee (exo) value is
89%, yield is 96%.
Embodiment above describes the ultimate principle of the present invention, principal character and advantage, the technical staff of the industry should
Understanding, the present invention is not restricted to the described embodiments, and the simply explanation present invention's described in above-described embodiment and description is former
Reason, under the scope without departing from the principle of the invention, the present invention also has various changes and modifications, and these changes and improvements each fall within
In the scope of protection of the invention.
Claims (5)
1. a loaded chiral catalyst magnetic nano-particle, it is characterised in that: first pass through RAFT living polymerization pair
Macmillan chiral monomer carries out homopolymerization and obtains the end of the chain chiral polymer containing active pair of thioester group
Again it is formed with the magnetic nano-particle RAFT coupling of surface keyed jointing double bond
Loaded chiral catalyst magnetic nano-particle, it has a following structure:
2. the preparation method of the loaded chiral catalyst magnetic nano-particle described in a claim 1, it is characterised in that concrete
Step is: weighs surface and has the Fe of double bond3O4Nanosphere 0.15g joins in reaction bulb, after ultrasonic disperse 5-30min, successively
Add the end of the chain containing the chiral polymer 0.1-0.5g of active pair of thioester group, azodiisobutyronitrile 4mg, dimethylformamide
30mL and triethylamine 1mL, freezes after taking out 5 times at N2Under the conditions of react 48h in 40-100 DEG C, reaction terminates rear Magneto separate, and solid produces
Thing is centrifuged three times with oxolane and methanol are each successively, is placed in vacuum drying oven by solid product and is vacuum dried 48h in 40 DEG C
Prepare loaded chiral catalyst magnetic nano-particle.
The preparation method of loaded chiral catalyst magnetic nano-particle the most according to claim 2, it is characterised in that described
The end of the chain concrete preparation process of chiral polymer containing active pair of thioester group is: weigh successively Macmillan chiral monomer,
Dithiobenzoic acid cumenyl ester and azodiisobutyronitrile are dissolved in dimethylformamide, wherein Macmillan chiral monomer,
Dithiobenzoic acid cumenyl ester is 100-150:1:0.2 with the mol ratio of azodiisobutyronitrile, seals, adopt after being completely dissolved
Carry out the oxygen in removing system by five methods of freeze thawing, reaction bulb is placed in oil bath pan in 40-100 DEG C of stirring reaction 24h, reaction
After end, precipitation in ether, centrifugal, solid oxolane to be dissolved, then precipitates in ether, precipitation is repeatedly until monomer
Eliminate completely, obtain the product as light yellow solid end of the chain chiral polymer containing active pair of thioester group in 30 DEG C of dry 48h.
The preparation method of loaded chiral catalyst magnetic nano-particle the most according to claim 2, it is characterised in that concrete
Synthetic route be:
5. the answering in Diels-Alder cycloaddition reaction of the loaded chiral catalyst magnetic nano-particle described in claim 1
With, after wherein loaded chiral catalyst magnetic nano-particle is reclaimed by Magnetic Isolation, repetitive cycling uses.
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| CN104804145A (en) * | 2015-04-17 | 2015-07-29 | 河南师范大学 | Chiral catalyst loaded amphiphilic random copolymer grafted hair-like polymer microsphere as well as preparation method and application thereof |
| CN105195228A (en) * | 2015-10-08 | 2015-12-30 | 河南师范大学 | Fe3O4-loaded chiral catalyst and preparation method and application thereof |
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| CN104804145A (en) * | 2015-04-17 | 2015-07-29 | 河南师范大学 | Chiral catalyst loaded amphiphilic random copolymer grafted hair-like polymer microsphere as well as preparation method and application thereof |
| CN105195228A (en) * | 2015-10-08 | 2015-12-30 | 河南师范大学 | Fe3O4-loaded chiral catalyst and preparation method and application thereof |
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