CN105854950B - A kind of loaded chiral catalyst magnetic nano-particle and its preparation method and application - Google Patents
A kind of loaded chiral catalyst magnetic nano-particle and its preparation method and application Download PDFInfo
- Publication number
- CN105854950B CN105854950B CN201610287374.5A CN201610287374A CN105854950B CN 105854950 B CN105854950 B CN 105854950B CN 201610287374 A CN201610287374 A CN 201610287374A CN 105854950 B CN105854950 B CN 105854950B
- Authority
- CN
- China
- Prior art keywords
- particle
- magnetic nano
- chiral
- loaded
- chiral catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 239000002122 magnetic nanoparticle Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229920000642 polymer Polymers 0.000 claims abstract description 25
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 150000007970 thio esters Chemical class 0.000 claims abstract description 13
- 238000010550 living polymerization reaction Methods 0.000 claims abstract description 5
- 238000006117 Diels-Alder cycloaddition reaction Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 40
- 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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- 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 17
- 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
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- ZGRWZUDBZZBJQB-UHFFFAOYSA-N benzenecarbodithioic acid Chemical compound SC(=S)C1=CC=CC=C1 ZGRWZUDBZZBJQB-UHFFFAOYSA-N 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 238000010257 thawing Methods 0.000 claims description 4
- 230000001351 cycling effect Effects 0.000 claims description 2
- -1 is centrifuged Substances 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 8
- 238000000926 separation method Methods 0.000 abstract description 6
- 238000004064 recycling Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 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
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 4
- 239000012074 organic phase 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
- 238000004440 column chromatography Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 2
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 229930016911 cinnamic acid Natural products 0.000 description 2
- 235000013985 cinnamic acid Nutrition 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 239000002904 solvent Substances 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
- 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
- 238000005481 NMR spectroscopy 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
- 239000005864 Sulphur Substances 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
- 238000005253 cladding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 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
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002244 precipitate Substances 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
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance 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
-
- B01J35/33—
-
- 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
Abstract
The invention discloses a kind of loaded chiral catalyst magnetic nano-particles and its preparation method and application, belong to chiral catalysis and asymmetric syntheses technical field.Technical solution of the present invention main points are as follows: homopolymerization is carried out to Macmillan chiral monomer by RAFT living polymerization first and obtains chiral polymer of the end of the chain containing active double thioester groupsAgain the magnetic nano-particle RAFT of itself and the bonded double bond in surface is coupled to form loaded chiral catalyst magnetic nano-particle, be had the following structure:
Description
Technical field
The invention belongs to chiral catalysis and asymmetric syntheses technical fields, and in particular to a kind of loaded chiral catalyst is magnetic
Nanoparticle and its preparation method and application.
Background technique
In traditional free radical polymerization system, number of free radical is higher, and chain transfer reaction is irreversible, is easy to happen freedom
The termination of base is reacted, and the degree of polymerization is caused to reduce, and is reacted uncontrollable.If the high special type of chain transfer constant is added in polymerization system
Chain-transferring agent, to reduce the concentration of free radical, just has so that carrying out degeneration transfer between Propagating Radical and the chain-transferring agent
It can be able to achieve reversible addition-fracture transfer (RAFT) active free radical polymerization, to carry out living control polymerization.
And magnetic nano-particle is with large specific surface area, Active sites are more, surface reaction activity is high, adsorption capacity is strong
With the excellent properties such as catalytic efficiency height, necessary condition is provided for catalyst for nanoparticle, thus it has in terms of catalysis
Important application.
In addition, people are exactly surface cladding to the most direct method of modifying of magnetic nano-particle in recent years, magnetic core is formed
Shell structure applies it widely and different field.As far as we know, some methods being efficiently coupled, example has been developed
1,3- Dipolar Cycloaddition, the sulfydryl-alkene clicking chemistry of the Huisgen reaction, alkynes and azide that are catalyzed such as copper.
Summary of the invention
The technical problem to be solved by the present invention is to provide a kind of loaded chiral catalyst magnetic nano-particle and its preparation sides
Method and application carry out homopolymerization to Macmillan chiral monomer by RAFT living polymerization first and obtain the end of the chain containing active double sulphur
The chiral polymer chain of ester group, then the magnetic nano-particle RAFT of itself and the bonded double bond in surface is coupled and to form loaded chiral and urges
Agent magnetic nano-particle, making to connect polymer chain on nanosphere has controllability, and the advantages of can effectively be grafted, and can lead to
Magnet adsorbing separation is crossed, to reach the recycling and reuse of catalyst, utilizes the loaded chiral catalyst magnetic nano particle
Son other than obtaining the chiral product of high yield and highly-solid selectively, can also realize catalyst in catalytic asymmetric reaction
Magneto separate and repeat be recycled the characteristics of, reduce production cost.
The present invention adopts the following technical scheme that solve above-mentioned technical problem, a kind of loaded chiral catalyst magnetic nano particle
Son, it is characterised in that: homopolymerization is carried out to Macmillan chiral monomer by RAFT living polymerization first and obtains the end of the chain containing active
The chiral polymer of double thioester groupsAgain by the magnetism of itself and the bonded double bond in surface
Nanoparticle RAFT is coupled to form loaded chiral catalyst magnetic nano-particle, has the following structure:
The preparation method of loaded chiral catalyst magnetic nano-particle of the present invention, it is characterised in that specific steps
Are as follows: weigh the Fe that surface has double bond3O4Nanosphere 0.15g is added in reaction flask, after ultrasonic disperse 5-30min, is sequentially added
Chiral polymer 0.1-0.5g of the end of the chain containing active double thioester groups, azodiisobutyronitrile 4mg, dimethylformamide 30mL and
Triethylamine 1mL freezes after taking out 5 times in N2Under the conditions of in 40-100 DEG C of reaction 48h, Magneto separate after reaction, solid product is successively
It is respectively centrifuged three times with tetrahydrofuran and methanol, solid product is placed in a vacuum drying oven and is made negative in 40 DEG C of vacuum drying 48h
Supported chiral catalyst magnetic nano-particle.
It further limits, the specific preparation process of chiral polymer of the end of the chain containing active double thioester groups are as follows: according to
Secondary Macmillan chiral monomer, dithiobenzoic acid isopropylbenzene base ester and the azodiisobutyronitrile of weighing is dissolved in dimethylformamide
In, wherein the molar ratio of Macmillan chiral monomer, dithiobenzoic acid isopropylbenzene base ester and azodiisobutyronitrile is 100-
150:1:0.2 is sealed after being completely dissolved, and using five methods of freeze thawing come the oxygen in removing system, reaction flask is placed on oil bath pan
In be stirred to react in 40-100 DEG C for 24 hours, after reaction, precipitated in ether, be centrifuged, solid is dissolved with tetrahydrofuran, then
It is precipitated in ether, precipitating obtains the product as light yellow solid end of the chain in 30 DEG C of dry 48h and contain repeatedly until monomer eliminates completely
The chiral polymer of active double thioester groups.
It further limits, the specific synthetic route of the loaded chiral catalyst magnetic nano-particle are as follows:
Loaded chiral catalyst magnetic nano-particle answering in Diels-Alder cycloaddition reaction of the present invention
With repetitive cycling uses after wherein loaded chiral catalyst magnetic nano-particle is recycled by Magnetic Isolation.
Compared with the prior art, the present invention has the following advantages:
1, by RAFT living polymerization synthetic polymer, making to connect the polymer chain on magnetic nano-particle has controllably
Property；
2, polymer and magnetic nano-particle are carried out by effectively controllable grafting by the method for RAFT coupling；
3, the preparation method of loaded chiral catalyst magnetic nano-particle is simple and environmentally friendly；
4, the polymer chain hung can be improved dispersibility of the particle in reaction medium, to further increase catalyst
Catalytic activity, and can show high catalytic activity as soluble line polymer carried catalyst.
Specific embodiment
Above content of the invention is described in further details by the following examples, but this should not be interpreted as to this
The range for inventing above-mentioned theme is only limitted to embodiment below, and all technologies realized based on above content of the present invention belong to this hair
Bright range.
Embodiment 1
The preparation of chiral polymer of the end of the chain containing active double thioester groups
Successively weigh Macmillan chiral monomer (2.76g, 9.1279mmol), dithiobenzoic acid isopropylbenzene base ester
(16.28mg, 0.06mmol) and azodiisobutyronitrile (2mg, 0.0122mmol) are dissolved in 5mL dimethylformamide, completely molten
It is sealed after solution.Using five methods of freeze thawing come the oxygen in removing system, reaction flask is placed in oil bath pan and is stirred to react in 70 DEG C
24h.After reaction, it is precipitated in ether, is centrifuged, the minimal amount of tetrahydrofuran of solid is dissolved, then is precipitated in ether,
Precipitating is multiple, until monomer eliminates completely.Product as light yellow solid is obtained containing active double thioester groups in 30 DEG C of dry 48h
Chiral polymer.Mn=18700, PDI=1.59.
Embodiment 2
The preparation of chiral polymer of the end of the chain containing active double thioester groups
Successively weigh Macmillan chiral monomer (1.814g, 5.999mmol), dithiobenzoic acid isopropylbenzene base ester
(16.28mg, 0.06mmol) and azodiisobutyronitrile (2mg, 0.0122mmol) are dissolved in 5mL dimethylformamide, completely molten
It is sealed after solution.Using five methods of freeze thawing come the oxygen in removing system, reaction flask is placed in oil bath pan and is stirred to react in 70 DEG C
24h.After reaction, it precipitates, is centrifuged in ether.The minimal amount of tetrahydrofuran of solid is dissolved, then is precipitated in ether,
Precipitating is multiple, until monomer eliminates completely.Product as light yellow solid is obtained containing active double thioester groups 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 the Fe that surface has double bond3O4Nanosphere 0.15g is added in reaction flask, after ultrasonic disperse 5-30min, according to
Chiral polymer 0.1g, azodiisobutyronitrile 4mg, dimethylformamide 30mL and triethylamine made from secondary addition embodiment 1
1mL.Freeze after taking out 5 times in N2Under the conditions of in 70 DEG C of reaction 48h.Magneto separate after reaction, solid product successively use tetrahydrofuran
It is respectively centrifuged with methanol three times, solid product is placed in a vacuum drying oven, loaded chiral catalysis is made 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 are 1.15mmol/g.
Embodiment 4
The preparation of loaded chiral catalyst magnetic nano-particle
Weigh the Fe that surface has double bond3O4Nanosphere 0.15g is added in reaction flask, after ultrasonic disperse 5-30min, according to
Chiral polymer 0.3g, azodiisobutyronitrile 4mg, dimethylformamide 30mL and triethylamine made from secondary addition embodiment 1
1mL.Freeze after taking out 5 times in N2Under the conditions of in 70 DEG C of reaction 48h.Magneto separate after reaction, solid product successively use tetrahydrofuran
It is respectively centrifuged with methanol three times, solid product is placed in a vacuum drying oven, loaded chiral catalysis is made 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 are 2.1mmol/g.
Embodiment 5
The preparation of loaded chiral catalyst magnetic nano-particle
Weigh the Fe that surface has double bond3O4Nanosphere 0.15g is added in reaction flask, after ultrasonic disperse 5-30min, according to
Chiral polymer 0.5g, azodiisobutyronitrile 4mg, dimethylformamide 30mL and triethylamine made from secondary addition embodiment 1
1mL.Freeze after taking out 5 times in N2Under the conditions of in 100 DEG C of reaction 48h.Magneto separate after reaction, solid product successively use tetrahydrofuran
It is respectively centrifuged with methanol three times, solid product is placed in a vacuum drying oven, chiral catalyst magnetic is made in 40 DEG C of vacuum drying 48h
Property nanoparticle.△ m=0.41g, the load capacity of loaded chiral catalyst magnetic nano-particle are 2.42mmol/g.
Embodiment 6
The preparation of loaded chiral catalyst magnetic nano-particle
Weigh the Fe that surface has double bond3O4Nanosphere 0.15g is added in reaction flask, after ultrasonic disperse 5-30min, according to
Chiral polymer 0.1g, azodiisobutyronitrile 4mg, dimethylformamide 30mL and triethylamine made from secondary addition embodiment 2
1mL.Freeze after taking out 5 times in N2Under the conditions of in 40 DEG C of reaction 48h.Magneto separate after reaction, solid product successively use tetrahydrofuran
It is respectively centrifuged with methanol three times, solid product is placed in a vacuum drying oven, loaded chiral catalysis is made 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 are 1.19mmol/g.
Embodiment 7
The preparation of loaded chiral catalyst magnetic nano-particle
Weigh the Fe that surface has double bond3O4Nanosphere 0.15g is added in reaction flask, after ultrasonic disperse 5-30min, according to
Chiral polymer 0.3g, azodiisobutyronitrile 4mg, dimethylformamide 30mL and triethylamine made from secondary addition embodiment 2
1mL.Freeze after taking out 5 times in N2Under the conditions of in 70 DEG C of reaction 48h.Magneto separate after reaction, solid product successively use tetrahydrofuran
It is respectively centrifuged with methanol three times, solid product is placed in a vacuum drying oven, loaded chiral catalysis is made 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 are 2.13mmol/g.
Embodiment 8
The preparation of loaded chiral catalyst magnetic nano-particle
Weigh the Fe that surface has double bond3O4Nanosphere 0.15g is added in reaction flask, after ultrasonic disperse 5-30min, according to
Chiral polymer 0.5g, azodiisobutyronitrile 4mg, dimethylformamide 30mL and triethylamine made from secondary addition embodiment 2
1mL.Freeze after taking out 5 times in N2Under the conditions of in 100 DEG C of reaction 48h.Magneto separate after reaction, solid product successively use tetrahydrofuran
It is respectively centrifuged with methanol three times, solid product is placed in a vacuum drying oven, loaded chiral catalysis is made 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 are 2.4mmol/g.
Embodiment 9
Loaded chiral catalyst magnetic Nano prepared by the embodiment 5 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 acid
(0.0636mL, 0.48mmol) reacts for 24 hours at room temperature, and thin-layer chromatography tracking reaction to terminal, after completion of the reaction, is centrifugated,
Lower layer's solid is washed 3 times with methanol, is recycled and reused, and supernatant is extracted three times with ether (3 × 10mL), merges organic phase, dense
Contracting, obtains pure addition product (petroleum ether: ethyl acetate=50:1) through column chromatography for separation, and weighing calculates yield, nuclear magnetic resonance
Hydrogen spectrum confirmation target product.Suitable NaBH is added into product4, react at room temperature 48h.30h reaction 75%.After completion of the reaction,
It is spin-dried for solvent, q. s. methylene chloride is added, with distillation washing 3 times, collects organic phase, concentration obtains 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 substance, product is obtained
Ee (endo) value be 86%, ee (exo) value be 83%, yield 99%.
Embodiment 10
The loaded chiral catalyst magnetism obtained that the preparation of embodiment 7 of the amount 10% of substrate materials is added in test tube is received
Rice grain, water (0.6mL), trifluoroacetic acid (0.0114g, 0.1mmol), cyclopentadiene (0.168mL, 1.96mmol), cinnamic acid
(0.0636mL, 0.48mmol) reacts for 24 hours at room temperature, and thin-layer chromatography tracking reaction to terminal, after completion of the reaction, is centrifugated,
Lower layer's solid is sufficiently washed 3 times with methanol, and vacuum drying recycling, supernatant is extracted three times with ether (3 × 10mL), is merged organic
Phase, concentration, obtains pure addition product (petroleum ether: ethyl acetate=50:1) through column chromatography for separation, and weighing calculates yield, nuclear-magnetism
Resonate hydrogen spectrum confirmation target product.Suitable NaBH is added into product4, react at room temperature 48h.Reacting 30h product yield is
80%.After completion of the reaction, it is spin-dried for solvent, q. s. methylene chloride is added, with distillation washing 3 times, organic phase is collected, is concentrated through column layer
Analyse isolated pure products (petroleum ether: ethyl acetate=16:1).Pass through high performance liquid chromatography (HPLC) OJ-H chirality post separation
Chiral material, it is 91% that ee (endo) value for obtaining product, which is 89%, ee (exo) value, yield 99%.
Embodiment 11
By the Fe of the load Macmillan catalyst recycled in embodiment 93O4Nanosphere repeats real as chiral catalyst
Apply example 9.Reacting 30h product yield is 75%, and it is 86% that ee (endo) value for obtaining product, which is 85%, ee (exo) value, and yield is
89%.
Embodiment 12
By the Fe of the load Macmillan catalyst recycled in embodiment 103O4Nanosphere repeats real as chiral catalyst
Apply example 10.Reacting 30h product yield is 70%.It is 90% that ee (endo) value for obtaining product, which is 86%, ee (exo) value, yield
It is 97%.
Embodiment 13
By the Fe of the load Macmillan catalyst recycled in embodiment 113O4Nanosphere repeats real as chiral catalyst
Apply example 9.Reacting 30h product yield is 80%, and it is 79% that ee (endo) value for obtaining product, which is 86%, ee (exo) value, and yield is
90%.
Embodiment 14
By the Fe of the load Macmillan catalyst recycled in embodiment 123O4Nanosphere repeats real as chiral catalyst
Apply example 10.Reacting 30h product yield is 75%, and ee (endo) value for obtaining product for obtaining product is that 87%, ee (exo) value is
89%, yield 96%.
Embodiment above describes basic principles and main features of the invention and advantage, the technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe originals of the invention
Reason, under the range for not departing from the principle of the invention, various changes and improvements may be made to the invention, these changes and improvements are each fallen within
In the scope of protection of the invention.
Claims (5)
1. a kind of loaded chiral catalyst magnetic nano-particle, it is characterised in that: pass through RAFT living polymerization pair first
Macmillan chiral monomer carries out homopolymerization and obtains chiral polymer of the end of the chain containing active double thioester groups
Again the magnetic nano-particle RAFT of itself and the bonded double bond in surface is coupled to form loaded chiral catalyst magnetic nano-particle,
It has the following structure:
2. a kind of preparation method of loaded chiral catalyst magnetic nano-particle described in claim 1, it is characterised in that specific
Step are as follows: weigh the Fe that surface has double bond3O4Nanosphere 0.15g is added in reaction flask, after ultrasonic disperse 5-30min, successively
Chiral polymer 0.1-0.5g, azodiisobutyronitrile 4mg, dimethylformamide of the end of the chain containing active double thioester groups is added
30mL and triethylamine 1mL freezes after taking out 5 times in N2Under the conditions of in 40-100 DEG C of reaction 48h, Magneto separate, solid produce after reaction
Object is successively respectively centrifuged three times with tetrahydrofuran and methanol, and solid product is placed in a vacuum drying oven in 40 DEG C of vacuum drying 48h
Loaded chiral catalyst magnetic nano-particle is made.
3. the preparation method of loaded chiral catalyst magnetic nano-particle according to claim 2, it is characterised in that described
The specific preparation process of chiral polymer of the end of the chain containing active double thioester groups are as follows: successively weigh Macmillan chiral monomer,
Dithiobenzoic acid isopropylbenzene base ester and azodiisobutyronitrile are dissolved in dimethylformamide, wherein Macmillan chiral monomer,
Dithiobenzoic acid isopropylbenzene base ester and the molar ratio of azodiisobutyronitrile are 100-150:1:0.2, seal, adopt after being completely dissolved
With five methods of freeze thawing come the oxygen in removing system, reaction flask is placed in oil bath pan and is stirred to react in 40-100 DEG C for 24 hours, reaction
After, it is precipitated in ether, is centrifuged, solid is dissolved with tetrahydrofuran, then is precipitated in ether, precipitated repeatedly until monomer
It eliminates completely, obtains chiral polymer of the product as light yellow solid end of the chain containing active double thioester groups in 30 DEG C of dry 48h.
4. the preparation method of loaded chiral catalyst magnetic nano-particle according to claim 2, it is characterised in that specific
Synthetic route are as follows:
5. loaded chiral catalyst magnetic nano-particle answering in Diels-Alder cycloaddition reaction described in claim 1
With repetitive cycling uses after wherein loaded chiral catalyst magnetic nano-particle is recycled by Magnetic Isolation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610287374.5A CN105854950B (en) | 2016-05-03 | 2016-05-03 | A kind of loaded chiral catalyst magnetic nano-particle and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610287374.5A CN105854950B (en) | 2016-05-03 | 2016-05-03 | A kind of loaded chiral catalyst magnetic nano-particle and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105854950A CN105854950A (en) | 2016-08-17 |
| CN105854950B true CN105854950B (en) | 2019-01-18 |
Family
ID=56630190
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610287374.5A Expired - Fee Related CN105854950B (en) | 2016-05-03 | 2016-05-03 | A kind of loaded chiral catalyst magnetic nano-particle and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105854950B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111871458A (en) * | 2020-08-20 | 2020-11-03 | 淮北师范大学 | Magnetic material supported chiral imidazolium salt catalyst and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2016
- 2016-05-03 CN CN201610287374.5A patent/CN105854950B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 甲基丙烯酸甲酯的RAFT聚合研究;朱金丽等;《化学世界》;20160225(第2期);第101-106页 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105854950A (en) | 2016-08-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108816287B (en) | Uio-66 in-situ immobilized carboxyl functionalized ionic liquid composite material and preparation and application thereof | |
| CN103447092B (en) | Graphene oxide supported Schiff base palladium catalyst as well as preparation method and application thereof | |
| CN103407992B (en) | Method for preparing hydrophilic temperature and pH dual-sensitive graphene through thiol-ene click chemistry method | |
| CN104069891A (en) | Preparation method of polymeric-microsphere-carrier immobilized N-hydroxyphthalimide catalyst | |
| CN113083236B (en) | Preparation method and application of magnetic MOFs-biochar composite material | |
| CN103897123A (en) | Method for preparing nuclear-shell type magnetic composite microsphere with surface rich in nickel ions and application of nuclear-shell type magnetic composite microsphere | |
| CN109021246B (en) | Temperature-responsive metal organic framework nanocrystal and preparation method and application thereof | |
| CN110961084A (en) | Preparation method of modified chitosan aerogel and application of modified chitosan aerogel in adsorption of lithium ions | |
| CN105964306B (en) | It is a kind of based on poly ion liquid magnetic nano-particle, preparation method and its application in three component reactions | |
| CN105854950B (en) | A kind of loaded chiral catalyst magnetic nano-particle and its preparation method and application | |
| CN112058236B (en) | Preparation of ferrocenyl metal-organic framework microspheres and application of ferrocenyl metal-organic framework microspheres in gold recovery | |
| CN109174049B (en) | Preparation method and application of imprinted porous lithium/rubidium ion adsorption material | |
| CN102086304B (en) | Iron phthalocyanine prepolymer/Fe3O4 nanometer hybrid magnetic material and preparation method thereof | |
| CN102174196B (en) | Method for preparing high-molecular-weight conducting polyaniline material | |
| CN109535393B (en) | Preparation method of microporous organic polymer nano-microspheres and product thereof | |
| CN110026248A (en) | The method and application of a kind of catalyst, the catalyst preparation aeroge adsorbent material | |
| CN111793196B (en) | Tetra- (4-aldehyde- (1, 1-biphenyl)) methane-based conjugated organic microporous polymer and preparation method thereof | |
| CN104368390B (en) | A kind of surface grafting multiple spot bridge connects support type TEMPO catalyst and preparation thereof | |
| CN105195228B (en) | A kind of Fe3O4Load type chiral catalyst and its preparation method and application | |
| CN104744617B (en) | Five yuan of melon ring bridging acrylate copolymer microballoons and preparation method and application | |
| CN103626904B (en) | A kind of polymethyl methacrylate being coated with zeroth order Nanoscale Iron and preparation method thereof | |
| CN103755927B (en) | The preparation method of cadmium sulfide/poly-3-hexyl thiophene/carbon nano tube compound material | |
| CN112279984A (en) | Method for preparing catalytic nano-microspheres by polymerization-induced self-assembly | |
| CN112121862A (en) | Magnetic immobilized platinum catalyst and preparation method and application thereof | |
| CN107880220B (en) | Synthetic method of polymerized chiral amino acid ligand, product and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190118 Termination date: 20200503 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |