CN107880220A - Synthetic method of polymerizing chiral amino acid ligand and products thereof and application - Google Patents
Synthetic method of polymerizing chiral amino acid ligand and products thereof and application Download PDFInfo
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- CN107880220A CN107880220A CN201711065842.5A CN201711065842A CN107880220A CN 107880220 A CN107880220 A CN 107880220A CN 201711065842 A CN201711065842 A CN 201711065842A CN 107880220 A CN107880220 A CN 107880220A
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- amino acid
- chiral amino
- polymerizing
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- 150000001413 amino acids Chemical class 0.000 title claims abstract description 58
- 239000003446 ligand Substances 0.000 title claims abstract description 24
- 230000000379 polymerizing effect Effects 0.000 title claims abstract description 23
- 238000010189 synthetic method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 239000004793 Polystyrene Substances 0.000 claims abstract description 26
- 229920002223 polystyrene Polymers 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000000839 emulsion Substances 0.000 claims abstract description 13
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims abstract description 8
- 239000004005 microsphere Substances 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- -1 amino acid Compound Chemical class 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- 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
- 238000001035 drying Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 230000000977 initiatory effect Effects 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 230000003287 optical effect Effects 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
- 238000005406 washing Methods 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 3
- 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
- 210000000481 breast Anatomy 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000000502 dialysis Methods 0.000 claims description 2
- 239000003999 initiator Substances 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
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 125000003107 substituted aryl group Chemical group 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
- 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
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 238000007334 copolymerization reaction Methods 0.000 claims 1
- 239000011859 microparticle Substances 0.000 claims 1
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical compound CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 claims 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 125000003275 alpha amino acid group Chemical group 0.000 abstract description 4
- 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
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 125000002252 acyl group Chemical group 0.000 description 4
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 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
- 230000033228 biological regulation Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 238000006116 polymerization 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
- 239000000126 substance Substances 0.000 description 2
- 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
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 150000003862 amino acid derivatives Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000004054 benzoquinones Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000000638 solvent extraction Methods 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
- 230000003068 static effect Effects 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 Table
-
- 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
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The present invention relates to a kind of synthetic method of chiral amino acid part and products thereof and application, and using chiral amino acid and acryloyl chloride as raw material, reaction prepares the chiral amino acid containing pi-allyl；There is the polystyrene microsphere of uniform light trigger layer by the method synthetic surface of emulsion polymerization；Gained polystyrene emulsion solubilizer is diluted to solid content as 0.5 ~ 3%; addition accounts for the prepared chiral amino acid containing acryloyl group of solids content 25 ~ 200% in polystyrene emulsion; under ultra violet lamp, react 1 ~ 4 hour, polymerizing chiral amino acid ligand is obtained after removing unreacted monomer.It is an advantage of the invention that reaction yield is high, mild condition, chiral amino acid grafting rate is high, and catalytic activity is strong.
Description
Technical field
The invention belongs to chemical industry synthesis field, is related to a kind of synthetic method of chiral amino acid part and products thereof and answers
With, can be applied to improve synthesis Planar chiral ferrocene compound yield.
Background technology
Planar chiral ferrocene compound can conveniently be converted into chiral ligand, in asymmetry catalysis, material science and biology
Medical domain has extensive research.Planar chiral is introduced into ferrocene frame having ferrocene frame, the most frequently used method is using all kinds of
The diastereomeric of chiral auxiliary induction is ortho-metalated.Snieckus seminars utilize external chiral base, such as (-)-
Sparteine, has developed asymmetric ortho-metalated reaction, and this method can directly obtain the ferrocene chemical combination of planar chiral
Thing, but need the lithium reagent, chiral base and more harsh reaction condition of equivalent；Ogasawara seminars are answered using alkene
Decompose ring closure reaction and synthesized planar chiral ferrocene, but expensive catalyst, it is difficult to obtain, severe reaction conditions；Yu Jinquan class
Topic group finds that chiral mono-protected amino acid can realize the asymmetric c h bond function dough of prochiral substrate as part；On
Sea is organic so commercially available chiral amino acid derivative synthesizes Planar chiral ferrocene compound, found different as part
The chiral amino acid of substituent has an impact to the synthesis yield of Planar chiral ferrocene compound.
The content of the invention
It is an object of the invention to provide a kind of polymerizing chiral amino for being used to improve Planar chiral ferrocene compound yield
The synthetic method of sour part.To solve the building-up process that existing chiral amino acid part is applied to Planar chiral ferrocene compound
When, the problem of yield of Planar chiral ferrocene compound is not high.
Another object of the present invention is to provide the product of above method preparation.
It is yet another object of the invention to provide the application of the said goods.
To achieve these goals, the present invention adopts the following technical scheme that：
A kind of synthetic method of polymerizing chiral amino acid ligand, it is characterised in that by optical homochiral amino acid and acryloyl chloride
Reaction introduces unsaturated bond on chiral amino acid, by the polyphenyl second of the amino acid monomer containing acryloyl group and parcel light trigger
Alkene polymerize under ultraviolet light initiation conditions, chiral amino acid is linked together with polystyrene by light trigger, including under
State step：
（1）Using chiral amino acid and acryloyl chloride as raw material, reaction prepares the chiral amino acid containing pi-allyl；
（2）There is the polystyrene microsphere of uniform light trigger layer by the method synthetic surface of emulsion polymerization；
（3）By step（2）It is 0.5 ~ 3 % that gained polystyrene emulsion solubilizer, which is diluted to solid content, and addition accounts for polystyrene breast
In liquid the step of 25 ~ 200 % of solids content（1）The prepared chiral amino acid containing acryloyl group, under ultra violet lamp, instead
Answer 1 ~ 4 hour, polymerizing chiral amino acid ligand is obtained after removing unreacted monomer.
The chiral amino acid that the present invention is easy to get using business is raw material, has efficiently synthesized the polymerizing chiral of high grafting density
Amino acid ligand, it can be applied to realize the asymmetric coupling reaction of double c h bonds, improve synthesis Planar chiral ferrocene compound
Yield, and it is expected to realize the recycling of catalyst.
Described chiral amino acid compound is the optical pure compound of the R or S configurations with following structure：
、Or；Wherein R1Alkyl selected from C1-C16,
Isopropyl, isobutyl group, the tert-butyl group, benzyl or substituted aryl, wherein R2、R3、R4、R5、R6Arbitrarily it is selected from
H、F、Cl、Br、I、CF3, CHO, Ac, COOMe, C1-C16 alkoxy or C1-C16 alkyl, * be expressed as R or S configurations.
Step（1）In the synthetic method of the chiral amino acid containing pi-allyl be specially：With chiral amino acid and acryloyl chloride
For raw material, in the basic conditions, ice bath stirring reaction 1 ~ 4 hour, afterwards plus hydrochloric acid adjusts reaction solution pH to 2, and reaction product is led to
Organic solvent extraction is crossed, the accordingly chiral amino acid containing acryloyl group is prepared after drying.
Step（2）There is the synthetic method of the polystyrene microsphere of uniform light trigger layer to be specially on surface：Gathered with emulsion
Conjunction method synthetic polystyrene microballoon, light trigger 2- [p- (2- hydroxy-2-methyl phenylpropyl alcohols are slowly added in last stage reaction
Ketone)]-ethylene glycol-methacrylate（HMEM）, initiator is copolymerized with remaining styrene monomer in polystyrene microsphere table
Face, one layer of uniform light-initiated oxidant layer is formed, after reaction terminates, product passes through dialysis purification.
Step（3）In added retarder thinner be water, methanol, ethanol, acetone, one or more of groups in tetrahydrofuran
Close；Uviol lamp used is 300 ~ 1100nm xenon lamp ultraviolet source.
Step（3）Middle gained polymerizing chiral amino acid ligand by dialyse or with aqueous 20 ~ 80 % methanol, ethanol,
Purified in acetone, tetrahydrofuran after one or more of solution washings repeatedly, product is obtained after freeze-drying.
The present invention provides a kind of polymerizing chiral amino acid ligand, is prepared according to any of the above-described methods described.
The present invention provides the receipts that a kind of polymerizing chiral amino acid ligand is used to improve synthesis Planar chiral ferrocene compound
The application of rate.
The invention has the advantages that：
（1）Ligand stock uses commercially available chiral amino acid, and wide material sources are easy to get；
（2）The method for being connected chiral amino acid and polystyrene by light trigger, can reach higher chiral amino
Sour load factor, while chiral amino can effectively be controlled by the addition of chiral amino acid monomer of the regulation containing acryloyl group
The load factor of acid；
（3）The method of the invention is added without acid-base material in polymeric amino acid part building-up process, will not destroy chiral ammonia
The activated centre of base acid；
（4）The polymerizing chiral amino acid ligand that the present invention synthesizes can be applied to the synthesis of chiral ferrocene compound, obtain pole
High enantioselectivity and outstanding yield.
Embodiment
By embodiment, the present invention is described further.
Embodiment 1：
The synthesis of N- allyl acyl group chiral amino acids：
Reaction equation 1
By amino acid in above formula（50 mmol）It is dissolved in 20 mL sodium hydroxide solutions（pH 10）, under ice bath stirring condition, 30
Acryloyl chloride is progressively added dropwise in min（50 mmol）；After reacting 2h, system temperature is increased to room temperature, adds hydrochloric acid regulation reaction pH
To 2；After the completion of reaction, add ethyl acetate that product is extracted into reaction system, organic addition anhydrous sodium sulfate drying, revolved after filtering
Most of organic solvent is done, placement obtains pale coloured particles after being dried overnight.
The synthesis of polystyrene emulsion：
SDS is weighed first, and KPS each 0.1 g, 0.03 g add three-necked flask after being dissolved in water, and three are added weighing styrene 2g
Mouth flask, is vacuumized, inflated with nitrogen 4 times or so to reaction system, to guarantee the oxygen in removing system, adds N2 air bags to protect,
So that reaction system is carried out under nitrogen protection all the time, reaction temperature is adjusted to 80oC.Now reaction starts, and polymerisation 2 is small
Shi Hou, lucifuge processing is carried out to reaction system device.Simultaneously by 1.8 g light triggers（1.0 g HMEM+8.0 g acetone）Pass through
Constant pressure funnel is slowly added dropwise into reaction system, and the speed that strict control is added dropwise, drop speed was dripped for every 5~6 seconds one.It is light-initiated
After agent is added dropwise, reaction continues to stir 2.5 h.Finally, after reaction terminates, reaction solution is fitted into bag filter and immerses deionization
Water is dialysed, until the electrical conductivity of deionized water is constant.Dynamic light scattering measures the nm of polystyrene microsphere particle diameter 80, particle diameter distribution
Well.
Light initiation polymerization prepares polymerizing chiral amino acid ligand：
The above-mentioned polystyrene emulsion for taking 25 g solid contents to be 1 %, 0.25 g N- allyl acyl group chiral amino acid monomers are dissolved in
In 25 g water, add in polystyrene emulsion, inflated with nitrogen is vacuumized again to the system 4 times, to ensure entirely to react in nitrogen
Protection is lower to be carried out.Afterwards again under ultra violet lamp, reaction carries out 2.5 h.After question response terminates, reaction solution is white, is filled
Enter to immerse in deionized water in bag filter and dialyse, to remove the impurity such as the small molecule in emulsion, until the electrical conductivity of deionized water
It is invariable.Dynamic light scattering measures the nm of polystyrene microsphere particle diameter 110, and particle diameter distribution is good.
Embodiment 2：
The synthesis of N- allyl acyl group chiral amino acids：
Reaction equation 2
By amino acid in above formula（50mmol）It is dissolved in 20 mL sodium hydroxide solutions（pH 10）, under ice bath stirring condition,
Acryloyl chloride is progressively added dropwise in 30min（50mmol）；After reacting 2h, system temperature is increased to room temperature, adds hydrochloric acid regulation reaction
PH to 2；After the completion of reaction, add ethyl acetate that product is extracted into reaction system, organic addition anhydrous sodium sulfate drying, after filtering
Most of organic solvent is spin-dried for, placement obtains transparent oily liquid after being dried overnight.
The synthesis of polystyrene emulsion：Such as embodiment 1
Light initiation polymerization prepares polymerizing chiral amino acid ligand：
The above-mentioned polystyrene emulsion for taking 25 g solid contents to be 1 %, 0.25g N- allyl acyl group chiral amino acid monomers are dissolved in
In 25g acetone, add in polystyrene emulsion, inflated with nitrogen is vacuumized again to the system 4 times, to ensure entirely to react in nitrogen
Protection is lower to be carried out.Afterwards again under ultra violet lamp, reaction carries out 2.5 h.After question response terminates, reaction solution is white, will react
Supernatant is removed after liquid is static, adds aqueous 50 % acetone washing precipitation repeatedly, the chiral amino being polymerize after freeze-drying
Sour part.
Application example：
Reaction equation 3：
Benzofuran is added into Schlenk reaction bulbs（0.6 mmol）With DMA (1.5mL), amino acid (0.06 is added successively
Mmol), palladium (0.03 mmol), potassium carbonate (0.45 mmol), benzoquinones (0.03 mmol), water (1.2 mmol) He Ermao
Iron (0.3 mmol).10 h are reacted under air atmosphere, after reaction terminates, reaction, ethyl acetate is quenched with saturated sodium bicarbonate
Extraction.Merge organic phase, successively with water and saturated common salt water washing, anhydrous sodium sulfate drying, filtering, removal of solvent under reduced pressure residual
Thing obtains target product (ethyl acetate/petroleum ether=1/10, v/v, 2 % Et through column chromatography for separation3N).Experimental result such as following table：
。
Claims (8)
1. a kind of synthetic method of polymerizing chiral amino acid ligand, it is characterised in that by optical homochiral amino acid and acryloyl
Chlorine reaction introduces unsaturated bond on chiral amino acid, by the polyphenyl of the amino acid monomer containing acryloyl group and parcel light trigger
Ethene polymerize under ultraviolet light initiation conditions, chiral amino acid is linked together with polystyrene by light trigger, including
Following step：
（1）Using chiral amino acid and acryloyl chloride as raw material, reaction prepares the chiral amino acid containing pi-allyl；
（2）There is the polystyrene microsphere of uniform light trigger layer by the method synthetic surface of emulsion polymerization；
（3）By step（2）It is 0.5 ~ 3 % that gained polystyrene emulsion solubilizer, which is diluted to solid content, and addition accounts for polystyrene breast
In liquid the step of 25 ~ 200 % of solids content（1）The prepared chiral amino acid containing acryloyl group, under ultra violet lamp, instead
Answer 1 ~ 4 hour, polymerizing chiral amino acid ligand is obtained after removing unreacted monomer.
2. the synthetic method of polymerizing chiral amino acid ligand as claimed in claim 1, it is characterised in that described chiral amino acid
Compound is the optical pure compound of the R or S configurations with following structure：
、Or；Wherein R1It is alkyl selected from C1-C16, different
Propyl group, isobutyl group, the tert-butyl group, benzyl or substituted aryl, wherein R2、R3、R4、R5、R6Arbitrarily selected from H,
F、Cl、Br、I、CF3, CHO, Ac, COOMe, C1-C16 alkoxy or C1-C16 alkyl, * be expressed as R or S configurations.
3. the synthetic method of polymerizing chiral amino acid ligand according to claim 1 or claim 2, it is characterised in that step（1）In contain
The synthetic method of the chiral amino acid of pi-allyl is specially：Using chiral amino acid and acryloyl chloride as raw material, in the basic conditions,
Ice bath stirring reaction 1 ~ 4 hour, afterwards plus hydrochloric acid adjusts reaction solution pH to 2, and reaction product is extracted by organic solvent, after drying
The accordingly chiral amino acid containing acryloyl group is prepared.
4. the synthetic method of polymerizing chiral amino acid ligand according to claim 1, it is characterised in that step（2）Surface has
The synthetic method for having the polystyrene microsphere of uniform light trigger layer is specially：It is micro- with emulsion polymerisation process synthetic polystyrene
Ball, light trigger 2- [p- (2- hydroxy-2-methyls propiophenone)]-ethylene glycol-methacrylate is slowly added in last stage reaction
（HMEM）, make initiator uniform light-initiated in Surfaces of Polystyrene Microparticles, one layer of formation with remaining styrene monomer copolymerization
Oxidant layer, after reaction terminates, product passes through dialysis purification.
5. the synthetic method of polymerizing chiral amino acid ligand according to claim 1, it is characterised in that step（3）In it is added
Retarder thinner is one or more of combinations in water, methanol, ethanol, acetone, tetrahydrofuran；Uviol lamp used be 300 ~
1100nm xenon lamp ultraviolet source.
6. according to the synthetic method of the polymerizing chiral amino acid ligand of claim 1 or 5, it is characterised in that step（3）Middle institute
Polymerizing chiral amino acid ligand by dialysing or with a kind of in aqueous 20 ~ 80 % methanol, ethanol, acetone, tetrahydrofuran
Or purified after several solns washing repeatedly, obtain product after freeze-drying.
7. a kind of polymerizing chiral amino acid ligand, it is prepared according to any methods describeds of claim 1-6.
8. polymerizing chiral amino acid ligand is used for the receipts for improving synthesis Planar chiral ferrocene compound according to claim 7
The application of rate.
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| 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 |
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| 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 |
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| CN113651908A (en) * | 2021-09-14 | 2021-11-16 | 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 |
| 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 |
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