CN107880220B - Synthetic method of polymerized chiral amino acid ligand, product and application thereof - Google Patents
Synthetic method of polymerized chiral amino acid ligand, product and application thereof Download PDFInfo
- Publication number
- CN107880220B CN107880220B CN201711065842.5A CN201711065842A CN107880220B CN 107880220 B CN107880220 B CN 107880220B CN 201711065842 A CN201711065842 A CN 201711065842A CN 107880220 B CN107880220 B CN 107880220B
- Authority
- CN
- China
- Prior art keywords
- amino acid
- chiral amino
- polystyrene
- chiral
- synthesizing
- 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.)
- Active
Links
- 150000001413 amino acids Chemical class 0.000 title claims abstract description 65
- 239000003446 ligand Substances 0.000 title claims abstract description 31
- 238000010189 synthetic method Methods 0.000 title description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 239000004793 Polystyrene Substances 0.000 claims abstract description 28
- 229920002223 polystyrene Polymers 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000000839 emulsion Substances 0.000 claims abstract description 13
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 13
- 239000004005 microsphere Substances 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 10
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 5
- 238000007865 diluting Methods 0.000 claims abstract description 5
- 238000010556 emulsion polymerization method Methods 0.000 claims abstract description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- -1 amino acid compound Chemical class 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 238000000502 dialysis Methods 0.000 claims description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical class [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 claims description 2
- 238000001308 synthesis method Methods 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 238000007122 ortho-metalation reaction Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005865 alkene metathesis reaction Methods 0.000 description 1
- 150000003862 amino acid derivatives Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 229960001945 sparteine Drugs 0.000 description 1
- SLRCCWJSBJZJBV-AJNGGQMLSA-N sparteine Chemical compound C1N2CCCC[C@H]2[C@@H]2CN3CCCC[C@H]3[C@H]1C2 SLRCCWJSBJZJBV-AJNGGQMLSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
- C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/165—Polymer immobilised coordination complexes, e.g. organometallic complexes
- B01J31/1658—Polymer immobilised coordination complexes, e.g. organometallic complexes immobilised by covalent linkages, i.e. pendant complexes with optional linking groups, e.g. on Wang or Merrifield resins
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
- C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic System
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- 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
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0269—Complexes comprising ligands derived from the natural chiral pool or otherwise having a characteristic structure or geometry
- B01J2531/0275—Complexes comprising ligands derived from the natural chiral pool or otherwise having a characteristic structure or geometry derived from amino acids
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for synthesizing chiral amino acid ligand, a product and application thereof, which takes chiral amino acid and acryloyl chloride as raw materials to prepare chiral amino acid containing allyl; synthesizing polystyrene microspheres with uniform photoinitiator layers on the surfaces by an emulsion polymerization method; diluting the obtained polystyrene emulsion with a solvent until the solid content is 0.5-3%, adding the prepared chiral amino acid containing acryloyl accounting for 25-200% of the solid content in the polystyrene emulsion, reacting for 1-4 hours under the irradiation of an ultraviolet lamp, and removing unreacted monomers to obtain the polymerized chiral amino acid ligand. The invention has the advantages of high reaction yield, mild conditions, high chiral amino acid grafting rate and strong catalytic activity.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and relates to a synthetic method of a chiral amino acid ligand, a product and application thereof, which can be applied to improving the yield of a synthesized planar chiral ferrocene compound.
Background
The planar chiral ferrocene compound can be conveniently converted into a chiral ligand, and has wide and deep research in the fields of asymmetric catalysis, material science and biomedicine. Planar chirality is introduced into the ferrocene skeleton, the most common method being diastereomer ortho-metalation induced by various chiral prosthetic groups. The Snieckus topic group develops asymmetric ortho-metalation reaction by utilizing external chiral base, such as (-) -sparteine, and the method can directly obtain a planar chiral ferrocene compound but needs equivalent lithium reagent, chiral base and harsh reaction conditions; the Ogasarwara subject group utilizes olefin metathesis ring-closing reaction to synthesize planar chiral ferrocene, but the catalyst is expensive and difficult to obtain and the reaction condition is harsh; the group of the project of the remaining gold right discovers that the chiral mono-protected amino acid can be used as a ligand to realize the asymmetric C-H bond functionalization of a prochiral substrate; the Shanghai organic industry can use a commercially available chiral amino acid derivative as a ligand to synthesize the planar chiral ferrocene compound, and the chiral amino acids with different substituents have influence on the synthesis yield of the planar chiral ferrocene compound.
Disclosure of Invention
The invention aims to provide a synthetic method of a polymerization chiral amino acid ligand for improving the yield of a planar chiral ferrocene compound. The method solves the problem that when the existing chiral amino acid ligand is applied to the synthetic process of the planar chiral ferrocene compound, the yield of the planar chiral ferrocene compound is not high.
It is a further object of the present invention to provide a product prepared by the above process.
It is a further object of the present invention to provide the use of the above products.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for synthesizing a polymerized chiral amino acid ligand is characterized in that optically pure chiral amino acid reacts with acryloyl chloride to introduce unsaturated bonds on the chiral amino acid, an amino acid monomer containing acryloyl groups and polystyrene wrapping a photoinitiator are polymerized under the ultraviolet light initiation condition, so that the chiral amino acid and the polystyrene are linked together through the photoinitiator, and the method comprises the following steps:
(1) chiral amino acid and acryloyl chloride are used as raw materials to react to prepare chiral amino acid containing allyl;
(2) synthesizing polystyrene microspheres with uniform photoinitiator layers on the surfaces by an emulsion polymerization method;
(3) and (3) diluting the polystyrene emulsion obtained in the step (2) by adding a solvent until the solid content is 0.5-3%, adding the acryloyl group-containing chiral amino acid prepared in the step (1) accounting for 25-200% of the solid content in the polystyrene emulsion, reacting for 1-4 hours under the irradiation of an ultraviolet lamp, and removing unreacted monomers to obtain the polymerized chiral amino acid ligand.
The invention utilizes the chiral amino acid which is easy to obtain commercially as a raw material, efficiently synthesizes the polymerized chiral amino acid ligand with high grafting density, can be applied to realizing the asymmetric coupling reaction of double C-H bonds, improves the yield of the synthesized planar chiral ferrocene compound, and is expected to realize the recycling of the catalyst.
The chiral amino acid compound is an optical pure compound with R or S configuration with the following structure:
The method for synthesizing the chiral amino acid containing allyl in the step (1) specifically comprises the following steps: chiral amino acid and acryloyl chloride are used as raw materials, the raw materials are stirred in an ice bath to react for 1-4 hours under an alkaline condition, hydrochloric acid is added to adjust the pH value of a reaction solution to 2, and a reaction product is extracted by an organic solvent and dried to prepare the corresponding chiral amino acid containing acryloyl.
The synthesis method of the polystyrene microsphere with the uniform photoinitiator layer on the surface in the step (2) specifically comprises the following steps: synthesizing polystyrene microspheres by an emulsion polymerization method, slowly adding a photoinitiator 2- [ p- (2-hydroxy-2-methyl propiophenone) ] -ethylene glycol-methacrylate (HMEM) at the end of reaction, copolymerizing the initiator and residual styrene monomers on the surfaces of the polystyrene microspheres to form a uniform photoinitiator layer, and dialyzing and purifying a product after the reaction is finished.
The diluting solvent added in the step (3) is one or a combination of water, methanol, ethanol, acetone and tetrahydrofuran; the ultraviolet lamp is a 300-1100 nm xenon lamp ultraviolet source.
And (3) dialyzing the polymerized chiral amino acid ligand obtained in the step (3) or washing the polymerized chiral amino acid ligand for multiple times by using one or more solutions of methanol, ethanol, acetone and tetrahydrofuran containing 20-80% of water, purifying, and freeze-drying to obtain a product.
The invention provides a polymeric chiral amino acid ligand prepared according to any one of the methods described above.
The invention provides application of a polymerized chiral amino acid ligand in improving the yield of a synthesized planar chiral ferrocene compound.
The invention has the following advantages:
(1) the ligand raw material adopts commercially available chiral amino acid, and the source is wide and easy to obtain;
(2) the method for connecting the chiral amino acid and the polystyrene by the photoinitiator can achieve higher chiral amino acid load rate, and can effectively control the load rate of the chiral amino acid by adjusting the adding amount of the chiral amino acid monomer containing acryloyl;
(3) in the method, acid and alkali substances are not added in the synthesis process of the polymerized amino acid ligand, so that the active center of the chiral amino acid is not damaged;
(4) the polymerized chiral amino acid ligand synthesized by the method can be applied to the synthesis of chiral ferrocene compounds, and extremely high enantioselectivity and excellent yield are obtained.
Detailed Description
The present invention is further illustrated by examples.
Example 1:
synthesis of N-allyl chiral amino acid:
reaction scheme 1
Dissolving the amino acid (50 mmol) in the formula in 20 mL of sodium hydroxide solution (pH 10), and gradually dropwise adding acryloyl chloride (50 mmol) within 30min under the condition of ice bath stirring; after reacting for 2 hours, raising the temperature of the system to room temperature, and adding hydrochloric acid to adjust the pH value of the reaction to 2; after the reaction is finished, adding ethyl acetate to extract a product out of a reaction system, adding an organic phase, drying by anhydrous sodium sulfate, filtering, then spin-drying most of the organic solvent, and standing and drying overnight to obtain pale particles.
Synthesis of polystyrene emulsion:
firstly weighing 0.1 g of SDS and 0.03 g of KPS respectively, adding the SDS and the KPS into a three-neck flask after adding water to dissolve the SDS and the KPS, adding 2g of styrene into the three-neck flask, vacuumizing a reaction system, filling nitrogen for about 4 times to ensure that oxygen in the system can be removed, adding an N2 air bag for protection to ensure that the reaction system is always carried out under the protection of nitrogen, and adjusting the reaction temperature to 80 DEGoC. At this time, the reaction was started, and after 2 hours of the polymerization reaction, the reaction system apparatus was protected from light. Meanwhile, 1.8 g of photoinitiator (1.0 g of HMEM +8.0 g of acetone) is slowly dripped into the reaction system through a constant-pressure dropping funnel, and the dripping speed is strictly controlled to be one drop per 5-6 seconds. After the addition of the photoinitiator was completed, the reaction was stirred for 2.5 h. And finally, after the reaction is finished, filling the reaction solution into a dialysis bag, and immersing the dialysis bag into deionized water for dialysis until the conductivity of the deionized water is constant. The polystyrene microsphere has the particle size of 80 nm and good particle size distribution measured by dynamic light scattering.
Preparing a polymerized chiral amino acid ligand by photoinitiated polymerization:
taking 25g of the polystyrene emulsion with the solid content of 1%, dissolving 0.25g N-allyl acyl chiral amino acid monomer in 25g of water, adding the solution into the polystyrene emulsion, vacuumizing the system and refilling nitrogen for 4 times so as to ensure that the whole reaction is carried out under the protection of nitrogen. Then under the irradiation of an ultraviolet lamp, the reaction is carried out for 2.5 h. And after the reaction is finished, putting the reaction solution into a dialysis bag, and immersing the dialysis bag into deionized water for dialysis to remove impurities such as micromolecules in the emulsion until the conductivity of the deionized water is constant. The particle size of the polystyrene microsphere is 110 nm and the particle size distribution is good through dynamic light scattering measurement.
Example 2:
synthesis of N-allyl chiral amino acid:
reaction formula 2
Dissolving the amino acid (50 mmol) in the formula in 20 mL of sodium hydroxide solution (pH 10), and gradually dropwise adding acryloyl chloride (50 mmol) within 30min under the condition of ice bath stirring; after reacting for 2 hours, raising the temperature of the system to room temperature, and adding hydrochloric acid to adjust the pH value of the reaction to 2; after the reaction is finished, adding ethyl acetate to extract a product out of a reaction system, adding an organic phase, drying by anhydrous sodium sulfate, filtering, then spin-drying most of the organic solvent, and standing for drying overnight to obtain a transparent oily liquid.
Synthesis of polystyrene emulsion: as in example 1
Preparing a polymerized chiral amino acid ligand by photoinitiated polymerization:
taking 25g of the polystyrene emulsion with the solid content of 1%, dissolving 0.25g N-allyl acyl chiral amino acid monomer in 25g of acetone, adding the acetone into the polystyrene emulsion, vacuumizing the system and refilling nitrogen for 4 times so as to ensure that the whole reaction is carried out under the protection of nitrogen. Then under the irradiation of an ultraviolet lamp, the reaction is carried out for 2.5 h. And after the reaction is finished, the reaction liquid is white, the reaction liquid is stood, the supernatant is removed, 50% acetone containing water is added to wash and precipitate for multiple times, and the polymerized chiral amino acid ligand is obtained after freeze drying.
Application example:
reaction formula 3:
to a Schlenk reaction flask were added benzofuran (0.6 mmol) and DMA (1.5mL), followed by ammoniaAmino acid (0.06 mmol), palladium acetate (0.03 mmol), potassium carbonate (0.45 mmol), benzoquinone (0.03 mmol), water (1.2 mmol) and ferrocene (0.3 mmol). The reaction was carried out for 10 hours under an air atmosphere, and after the reaction was completed, the reaction was quenched with saturated sodium bicarbonate and extracted with ethyl acetate. The organic phases were combined, washed successively with water and saturated brine, dried over anhydrous sodium sulfate, filtered, the solvent residue was removed under reduced pressure and the desired product was obtained by column chromatography (ethyl acetate/petroleum ether =1/10, v/v, 2% Et)3N). The results of the experiment are as follows:
Claims (6)
1. a method for synthesizing a polymerized chiral amino acid ligand is characterized in that optically pure chiral amino acid reacts with acryloyl chloride to introduce unsaturated bonds on the chiral amino acid, an amino acid monomer containing acryloyl groups and polystyrene wrapping a photoinitiator are polymerized under the ultraviolet light initiation condition, so that the chiral amino acid and the polystyrene are linked together through the photoinitiator, and the method comprises the following steps:
(1) chiral amino acid and acryloyl chloride are used as raw materials to react to prepare chiral amino acid containing allyl;
(2) synthesizing polystyrene microspheres with uniform photoinitiator layers on the surfaces by an emulsion polymerization method;
(3) diluting the polystyrene emulsion obtained in the step (2) by adding a solvent until the solid content is 0.5-3%, adding the acryloyl group-containing chiral amino acid prepared in the step (1) accounting for 25-200% of the solid content in the polystyrene emulsion, reacting for 1-4 hours under the irradiation of an ultraviolet lamp, removing unreacted monomers to obtain a polymerized chiral amino acid ligand, wherein,
the method for synthesizing the chiral amino acid containing allyl in the step (1) specifically comprises the following steps: chiral amino acid and acryloyl chloride are used as raw materials, the raw materials are stirred in an ice bath to react for 1-4 hours under an alkaline condition, hydrochloric acid is added to adjust the pH value of a reaction solution to 2, and a reaction product is extracted by an organic solvent and dried to prepare the corresponding chiral amino acid containing acryloyl;
the synthesis method of the polystyrene microsphere with the uniform photoinitiator layer on the surface in the step (2) specifically comprises the following steps: synthesizing polystyrene microspheres by an emulsion polymerization method, slowly adding a photoinitiator 2- [ p- (2-hydroxy-2-methyl propiophenone) ] -ethylene glycol-methacrylate (HMEM) at the end of reaction, copolymerizing the initiator and residual styrene monomers on the surfaces of the polystyrene microspheres to form a uniform photoinitiator layer, and dialyzing and purifying a product after the reaction is finished.
2. The method for synthesizing a polymeric chiral amino acid ligand according to claim 1, wherein the chiral amino acid compound is an optically pure compound with an R or S configuration having the following structure:
3. The method for synthesizing polymeric chiral amino acid ligand according to claim 1 or 2, wherein the diluting solvent added in step (3) is one or more of water, methanol, ethanol, acetone and tetrahydrofuran; the ultraviolet lamp is a 300-1100 nm xenon lamp ultraviolet source.
4. The method for synthesizing the chiral amino acid ligand polymer according to claim 3, wherein the chiral amino acid ligand polymer obtained in the step (3) is purified by dialysis or washing with one or more of methanol, ethanol, acetone and tetrahydrofuran containing 20-80% of water for many times, and then is freeze-dried to obtain the product.
5. A polymeric chiral amino acid ligand prepared according to the method of any one of claims 1-4.
6. Use of a polymeric chiral amino acid ligand according to claim 5 to increase the yield of synthetic planar chiral ferrocene compounds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711065842.5A CN107880220B (en) | 2017-11-02 | 2017-11-02 | Synthetic method of polymerized chiral amino acid ligand, product and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711065842.5A CN107880220B (en) | 2017-11-02 | 2017-11-02 | Synthetic method of polymerized chiral amino acid ligand, product and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107880220A CN107880220A (en) | 2018-04-06 |
| CN107880220B true CN107880220B (en) | 2020-03-27 |
Family
ID=61778482
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711065842.5A Active CN107880220B (en) | 2017-11-02 | 2017-11-02 | Synthetic method of polymerized chiral amino acid ligand, product and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107880220B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113651908B (en) * | 2021-09-14 | 2023-07-25 | 北京市计量检测科学研究院 | Polystyrene fluorescent microsphere modified by biological intrinsic substance and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102964390A (en) * | 2012-11-27 | 2013-03-13 | 中国科学院上海有机化学研究所 | Planar chiral ferrocene compound and synthetic method and application thereof |
| CN104030940A (en) * | 2014-06-24 | 2014-09-10 | 齐鲁工业大学 | Synthesis method of N-propenoyl-amino acid chiral polymerizable monomer |
| CN105504159A (en) * | 2016-02-02 | 2016-04-20 | 中南大学 | Bonded chiral amino alcohol polymer and preparation method and application thereof |
-
2017
- 2017-11-02 CN CN201711065842.5A patent/CN107880220B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102964390A (en) * | 2012-11-27 | 2013-03-13 | 中国科学院上海有机化学研究所 | Planar chiral ferrocene compound and synthetic method and application thereof |
| CN104030940A (en) * | 2014-06-24 | 2014-09-10 | 齐鲁工业大学 | Synthesis method of N-propenoyl-amino acid chiral polymerizable monomer |
| CN105504159A (en) * | 2016-02-02 | 2016-04-20 | 中南大学 | Bonded chiral amino alcohol polymer and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 一种疏水型可聚合光引发剂的合成、表征及其应用;王益亨等;《合成纤维》;20151231;第44卷(第5期);第1-4页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107880220A (en) | 2018-04-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Polborn et al. | Biomimetic Catalysis with Immobilised Organometallic Ruthenium Complexes: Substrate‐and Regioselective Transfer Hydrogenation of Ketones | |
| CN104069891B (en) | The preparation method of the immobilized HP catalyst of a kind of polymer microballoon | |
| CN101412792B (en) | Method for synthesizing bead form polymeric acylating reagent | |
| CN111285768B (en) | Polyion liquid type chiral copper amino acid catalyst and preparation method thereof | |
| CN103601856A (en) | Supported chiral catalyst polymer microspheres, and preparation method and application thereof | |
| CN110003481A (en) | A kind of preparation method of the miscellaneous arm star polymer of eight arms | |
| CN104892810B (en) | A kind of method that photopolymerization prepares porous polymer particles after first assembling | |
| CN107880220B (en) | Synthetic method of polymerized chiral amino acid ligand, product and application thereof | |
| Ren et al. | Thermoresponsive chiral stationary phase functionalized with the copolymer of β-cyclodextrin and N-isopropylacrylamide for high performance liquid chromatography | |
| CN103599759B (en) | A kind of preparation method of adsorbent of Selective Separation ciprofloxacin in water environment | |
| CN105964306B (en) | It is a kind of based on poly ion liquid magnetic nano-particle, preparation method and its application in three component reactions | |
| CN102634007B (en) | Polyethylene glycol polymer containing dopamine, preparation method for same and application thereof | |
| Liang et al. | Engineering thiol-ene click chemistry for the preparation of a chiral stationary phase based on a [4+ 6]-type homochiral porous organic cage for enantiomeric separation in normal-phase and reversed-phase high performance liquid chromatography | |
| CN102059105A (en) | Oligopeptide-simulated CSP (Chiral Stationary Phase) and preparation method thereof | |
| CN112321628A (en) | Preparation method of beta-dimethylphenyl silicon substituted organic nitrile compound | |
| CN105504159B (en) | A kind of bonded chiral amino alkoxide polymer and its preparation method and application | |
| CN106831583B (en) | N, N- dialkyl group substituted pyrazolecarboxylic ionic liquid, preparation method and its method for catalyzing and synthesizing propene carbonate | |
| CN112430228B (en) | Chiral 2, 3-dihydrobenzo [ b ] thiophene 1, 1-dioxide, derivative and preparation method | |
| CN108102050A (en) | A kind of high-intensity water absorbent resin balls and preparation method thereof | |
| CN114524801A (en) | Method for efficiently producing esomeprazole sodium based on mobile phase | |
| IT8922661A1 (en) | PROCEDURE FOR THE DIRECT SYNTHESIS OF ALCOHOLS FROM OLEFINS, CARBON OXIDES AND HYDROGEN, PROMOTED BY A SUPPORTED RHODIUM CATALYST | |
| CN105399899B (en) | A kind of Preparation method and use of the molecularly imprinted polymer of the fat of catalyzing glycerol three hydrolysis | |
| CN112898326A (en) | Preparation method and application of organic boron compound, and preparation method and application of beta-hydroxy compound | |
| CN112808316B (en) | Chitosan/polyvinyl alcohol composite film loaded nano-copper catalyst and application thereof | |
| CN105348429B (en) | A kind of oleanolic acid molecularly imprinted polymer and preparation method thereof, purposes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |