CN106939059A - The poromeric method of homochiral molecule construction based on 1,1 ' 2 naphthols of connection - Google Patents
The poromeric method of homochiral molecule construction based on 1,1 ' 2 naphthols of connection Download PDFInfo
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- CN106939059A CN106939059A CN201710135347.0A CN201710135347A CN106939059A CN 106939059 A CN106939059 A CN 106939059A CN 201710135347 A CN201710135347 A CN 201710135347A CN 106939059 A CN106939059 A CN 106939059A
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- chiral
- naphthols
- union
- polymer
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- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000010276 construction Methods 0.000 title claims abstract description 10
- 150000004786 2-naphthols Chemical class 0.000 title abstract 2
- 239000003446 ligand Substances 0.000 claims abstract description 24
- 238000007306 functionalization reaction Methods 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 20
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 7
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- 239000002861 polymer material Substances 0.000 claims abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 150000008300 phosphoramidites Chemical class 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 150000002989 phenols Chemical class 0.000 claims description 9
- 150000008301 phosphite esters Chemical class 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 6
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 6
- 150000003335 secondary amines Chemical class 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical class CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 claims description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 2
- 229950011260 betanaphthol Drugs 0.000 claims description 2
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229940043279 diisopropylamine Drugs 0.000 claims description 2
- XVDBWWRIXBMVJV-UHFFFAOYSA-N n-[bis(dimethylamino)phosphanyl]-n-methylmethanamine Chemical compound CN(C)P(N(C)C)N(C)C XVDBWWRIXBMVJV-UHFFFAOYSA-N 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims 3
- WAPNOHKVXSQRPX-UHFFFAOYSA-N 1-phenylethanol Chemical class CC(O)C1=CC=CC=C1 WAPNOHKVXSQRPX-UHFFFAOYSA-N 0.000 claims 1
- 210000000988 bone and bone Anatomy 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 150000002148 esters Chemical group 0.000 claims 1
- 150000002240 furans Chemical class 0.000 claims 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 26
- 239000000178 monomer Substances 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- PPTXVXKCQZKFBN-UHFFFAOYSA-N (S)-(-)-1,1'-Bi-2-naphthol Chemical compound C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=C(O)C=CC2=C1 PPTXVXKCQZKFBN-UHFFFAOYSA-N 0.000 abstract 1
- 230000006698 induction Effects 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 23
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- KQIADDMXRMTWHZ-UHFFFAOYSA-N chloro-tri(propan-2-yl)silane Chemical compound CC(C)[Si](Cl)(C(C)C)C(C)C KQIADDMXRMTWHZ-UHFFFAOYSA-N 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 238000002390 rotary evaporation Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 238000004738 31P MAS NMR Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- ZGYICYBLPGRURT-UHFFFAOYSA-N tri(propan-2-yl)silicon Chemical compound CC(C)[Si](C(C)C)C(C)C ZGYICYBLPGRURT-UHFFFAOYSA-N 0.000 description 3
- QWMJEUJXWVZSAG-UHFFFAOYSA-N (4-ethenylphenyl)boronic acid Chemical class OB(O)C1=CC=C(C=C)C=C1 QWMJEUJXWVZSAG-UHFFFAOYSA-N 0.000 description 2
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical class CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 2
- 238000004410 13C MAS NMR Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- -1 Hydrogen furans Chemical class 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 229940125898 compound 5 Drugs 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- JVVRCYWZTJLJSG-UHFFFAOYSA-N 4-dimethylaminophenol Chemical compound CN(C)C1=CC=C(O)C=C1 JVVRCYWZTJLJSG-UHFFFAOYSA-N 0.000 description 1
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 1
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-dimethylaminopyridine Substances CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 1
- SPFZAUMRFKKIFC-UHFFFAOYSA-N B([O-])([O-])[O-].[K+].C(=C)F.[K+].[K+] Chemical class B([O-])([O-])[O-].[K+].C(=C)F.[K+].[K+] SPFZAUMRFKKIFC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000819038 Chichester Species 0.000 description 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000010961 commercial manufacture process Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- ZQGJEUVBUVKZKS-UHFFFAOYSA-N n,2-dimethylpropan-2-amine Chemical compound CNC(C)(C)C ZQGJEUVBUVKZKS-UHFFFAOYSA-N 0.000 description 1
- KCXYZMFPZHYUFO-UHFFFAOYSA-N n-methyl-n-phosphanylmethanamine Chemical class CN(C)P KCXYZMFPZHYUFO-UHFFFAOYSA-N 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000012719 thermal polymerization 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
- C08F130/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F130/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
- C08J2201/0502—Elimination by evaporation or heat degradation of a liquid phase the liquid phase being organic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2343/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Derivatives of such polymers
- C08J2343/02—Homopolymers or copolymers of monomers containing phosphorus
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to the technology of preparing of polymer, it is desirable to provide one kind joins the poromeric method of homochiral molecule construction of 2 naphthols based on 1,1'.This method includes：Basic framework material is dissolved in after porogenic solvents and adds polymerization initiator；6~48h of stirring polymerization, is distilled to recover solvent, obtains by the porous polymer material of homochiral molecule construction at 60~240 DEG C；The present invention passes through the porous chiral polymer of radical polymerization one-step synthesis method；Do not have additionally to add monomer again in building-up process so that resulting chiral polymer has more preferable chiral induction environment；Basic framework can be used as by designing the BINOL molecules of vinyl functionalization and obtain a series of chiral ligand；Resulting resin aperture is between 0.5~200nm, and specific surface area reaches as high as 1000m2/g。
Description
Technical field
The invention belongs to organic chemistry, Chemical Engineering, physical chemistry, technical field of material chemistry is related to the preparation skill of polymer
Art, more particularly to a kind of poromeric synthesis side of the homochiral molecule construction based on 1,1'- union -2-naphthols (BINOL)
Method.
Background technology
Chirality is an essential characteristic of the Nature.Set about as the demand of the chiral compound of people increasingly increases driving
The development of property catalyst.[a)Peng,Y.；Gong,T.；Zhang,K.；Lin,X.；Liu,Y.；Jiang,J.；Cui,
Y.Nat.Commun.2014,5,4406；b)Bradshaw,D.；Claridge,J.B.；Cussen,E.J.；Prior,T.J.；
Rosseinsky,M.J.Acc.Chem.Res.2005,38,273-282；c)Collins,A.N.；Sheldrake,G.N.；
Crosby,J.Chirality in Industry:Developments in the Commercial Manufacture and
Applications of Optically Active Compounds.John Wiley&Sons:Chichester,1992；d)
Fernández-Pérez,H.；Etayo,P.；Panossian,A.；Vidal-Ferran,A.Chem.Rev.2011,111,
2119-2176；e)Yang,H.；Zhang,L.；Zhong,L.；Yang,Q.；Li,C.Angew.Chem.Int.Ed.2007,46,
6861-6865] the homogeneous chiral catalysts of often have high activity and selectivity.But homogeneous chiral catalyst is difficult to repeat
Utilize, and because utilization ratio low caused by poor stability further limit their practical application.[a)Dai,
L.-X.Angew.Chem.Int.Ed.2004,43,5726-5729；(b)Crabtree,R.H.Chem.Rev.2015,115,
127-150].So design and synthesis have excellent catalytic performance, efficiently, catalyst that is stable and being easily recycled is always to grind
The cost of enantiomer molecule is made to reduce by chiral catalysis for the focus studied carefully.
Porous polymer is strong because of its designability, big specific surface area, regulatable pore passage structure, excellent chemistry and water
The features such as stability and catalysis, absorption, ion exchange, and separation in terms of be widely used.[a)Sun,Q.；Dai,Z.；
Meng,X.；Xiao,F.-S.Chem.Soc.Rev.2015,44,6018-6034；b)Sun,Q.；Dai,Z.；Meng,X.；
Wang,L.；Xiao,F.-S.J.Am.Chem.Soc.ACS Catal.2015,5,4556-4567；c)Kaur,P.；Hupp,
J.T.；Nguyen,S.T.ACS Catal.2011,1,819-835；d)Zhang,Y.；Riduan,
S.N.Chem.Soc.Rev.2012,41,2083-2094]；On the other hand, 1,1'- union -2-naphthols (present invention in
BINOL is referred to) because of its outstanding stereoselectivity and modifiability, it is widely used in designing new hand as plateform molecules
Property part [a) Teichert, J.F.；Feringa,B.L.Angew.Chem.Int.Ed.2010,49,2486-2528；b)van
den Berg,M.；Minnaard,A.J.；Haak,R.M.；Leeman,M.；Schudde,E.P.；Meetsma,A.；
Feringa,B.L.；de Vries,A.H.M.；Maljaars,C.E.P.；Willans,C.E.；Hyett,D.；Boogers,
J.A.F.；Henderickx,H.J.W.；de Vries,J.G.Adv.Synth.Catal.2003,345,308-323；c)d’
Augustin,M.；Palais,L.；Alexakis,A.Angew.Chem.Int.Ed.2005,44,1376-1378；d)Khan,
A.；Yang,L.；Xu,J.；Jin,L.Y.；Zhang,Y.J.Angew.Chem.Int.Ed.2014,53,11257-11260；e)
Wang,X.；Ding,K.J.Am.Chem.Soc.2004,126,10524-10525；f)Fu,W.；Tang,W.ACS
Catal.2016,6,4814-4858；g)Schmitz,C.；Holthusen,K.；Leitner,W.；Franciò,G.ACS
Catal.2016,6,1584-1589].It is well known that by orgnometallic catalyst it is immobilized be expected to improve their stability [a)
Totten,R.K.；Weston,M.H.；Park,J.K.；Farha,O.K.；Hupp,J.T.；Nguyen,S.T.ACS
Catal.2013,3,1454-1459；b)Mo,K.；Yang,Y.；Cui,Y.J.Am.Chem.Soc.2014,136,1746-
1749；c)Yang,D.；Odoh,S.O.；Wang,T.C.；Farha,O.K.；Hupp,J.T.；Cramer,C.J.；
Cagliardi,L.；Gates,B.C.J.Am.Chem.Soc.2015,137,7391-7396；d)McKittrick,M.W.；
Jones,C.W.J.Am.Chem.Soc.2004,126,3052-3053；e)Li,Z.；Xiao,J.-D.；Jiang,H.-L.ACS
Catal.2016,6,5359-5365.] and recycling can also be realized.These all substantially increase their application prospect.
But the method for preparing multi-phase chiral catalyst of existing report is general all comparatively laborious, and various preparation methods are matched somebody with somebody to difference
The general applicability of body is poor.
So as to which how easy and suitable for large-scale production synthesis multi-phase chiral catalyst is still a challenge.
The content of the invention
The technical problem to be solved in the present invention is to overcome deficiency of the prior art to be based on 1,1'- connection -2- there is provided one kind
The poromeric method of homochiral molecule construction of naphthols.
To solve technical problem, solution of the invention is：
A kind of poromeric method of homochiral molecule construction for being based on 1,1'- union -2-naphthols, including step are provided：
According to basic framework material: porogenic solvents: the mass ratio of polymerization initiator is 1: 2~40: 0.001~0.1, by base
This framework material is dissolved in porogenic solvents, then adds polymerization initiator；6~48h of stirring polymerization, distills back at 60~240 DEG C
Solvent is received, is obtained by the porous polymer material of homochiral molecule construction；
The basic framework material is the chiral ligand of the BINOL bases of vinyl functionalization, is by vinyl functionalization
BINOL and amine, alcohol or phenolic compound reaction obtained chiral phosphoramidite ligand or chiral phosphite ester ligand.
In the present invention, the porogenic solvents are tetrahydrofuran, ethyl acetate, ethanol, DMF, N- methyl
Any one in pyrrolidones or 1,2- dichloroethanes.
In the present invention, the polymerization initiator is azodiisobutyronitrile.
In the present invention, the preparation method of the basic framework material is：
(1) 1, the 1'- union -2-naphthols containing 2mmol vinyl functionalization are dissolved in 20mL toluene, then added
3mmol tri- (dimethylamino) phosphine, flow back 12h under the atmosphere of 80 DEG C and nitrogen；React toluene Rotary Evaporators after terminating
It is spin-dried for, then is recrystallized with petroleum ether, obtains methyl substituted chiral phosphoramidite ligand；Or,
(2) the 1,1'- union -2-naphthols of 2mmol vinyl functionalization are dissolved in 10mL PCl3, add two and drip N- methyl pyrroles
After pyrrolidone, 1h is reacted under the atmosphere of 60 DEG C and nitrogen；PCl is removed under reduced pressure3Afterwards, the anhydrous of 50mL is added into reaction system
Tetrahydrofuran, then adds excessive secondary amine and proceeds reaction, obtain the chiral phosphoramidite ligand of substituent substitution；Or
Person,
(3) the 1,1'- union -2-naphthols of 2mmol vinyl functionalization are dissolved in 10mL PCl3, add two and drip N- methyl pyrroles
After pyrrolidone, 1h is reacted under the atmosphere of 60 DEG C and nitrogen；PCl is removed under reduced pressure3Afterwards, 50mL anhydrous four is added into reaction system
Hydrogen furans, 3mmol triethylamines, and 2.4mmol alcohol compounds or phenolic compound are reacted, and obtain chiral phosphite ester
Part.
In the present invention, described secondary amine is diethylamine, diisopropylamine, N- methyl tertbutyl amine, double-(1- phenylethyls)
Any one in amine, cyclohexylamine or morpholine；Described alcohols or phenolic compound is methanol, isopropanol, phenol, 1- phenyl second
Any one in alcohol, 2-TBP or 2,6- DI-tert-butylphenol compounds.
In the present invention, the poromeric aperture prepared between 0.5~200nm, specific surface area 400~
1000m2Between/g.
Compared with prior art, the beneficial effects of the present invention are：
(1) the porous chiral polymer of radical polymerization one-step synthesis method is passed through；
(2) do not have additionally to add monomer again in building-up process so that resulting chiral polymer has more preferable chirality to lure
Lead ring border；
(3) basic framework can be used as obtain a series of chirality by designing the BINOL molecules of vinyl functionalization and match somebody with somebody
Body；
(4) the resin aperture obtained by is between 0.5~200nm, and specific surface area reaches as high as 1000m2/g。
Brief description of the drawings
Fig. 1 is the synthetic route chart of the BINOL parts of styryl functionalization.
In figure, (i) Br2, CH2Cl2；(ii) tri isopropyl chlorosilane, imidazoles, DMAP, N, N- dimethyl methyls
Acid amides；(iii) 4- vinylphenylboronic acids, Pd (PPh3)4, K2CO3, tetrahydrofuran, H2O；(iv) tetrabutyl ammonium fluoride, tetrahydrochysene furan
Mutter.
Fig. 2 is the synthetic route chart of the BINOL parts of vinyl functionalization.
In figure, (v) tetrafluoroethene ylboronic acid potassium, Pd (PPh3)4, K2CO3, tetrahydrofuran, H2O；(vi) tetrabutyl ammonium fluoride,
Tetrahydrofuran.
Fig. 3 is methyl substituted phosphoramidite ligand.
Fig. 4 is the phosphoramidite ligand structural formula of typical vinyl functionalization.
Fig. 5 is the phosphite ester ligand of typical vinyl functionalization.
Fig. 6 is polymer samples in embodiment 113C MAS NMR scheme.
Fig. 7 is polymer samples in embodiment 131P MAS NMR scheme.
Fig. 8 is the N of polymer samples in embodiment 12Adsorption isotherm.
Fig. 9 is the graph of pore diameter distribution of polymer samples in embodiment 1.
Figure 10 is the N of polymer samples in embodiment 62Adsorption isotherm.
Figure 11 is the graph of pore diameter distribution of polymer samples in embodiment 6.
Embodiment
The present invention obtains porous chiral polymer by the step solvent thermal polymerization of chiral molecules one of vinyl functionalization.
Relevant content is stated in detail below by way of specific embodiment.
The preparation of basic framework material
Basic framework material is the chiral ligand of the BINOL bases of vinyl functionalization, is by vinyl functionalization
Chiral phosphoramidite ligand or chiral phosphite ester ligand that BINOL is obtained with amine, alcohol or phenolic compound reaction.Syntheti c route
As depicted in figs. 1 and 2.
The synthesis step of 6,6'- bis- bromo- [1,1'- dinaphthalene] -2,2'- glycol (compound 1) is as follows, and 5.0g BINOL is molten
In 100mL CH2Cl2, wait system temperature to drop to after -10 DEG C, 2.4mL Br2Use 20mL CH2Cl2It is slowly dropped to after dilution
State solution.Completion of dropping uses NaHSO after being further continued for reaction 3h3The aqueous solution quenching.Aqueous phase CH2Cl2Extract and use MgSO4It is dry
It is dry, rotary evaporation CH2Cl2Obtained white solid had both been compound 1.
The synthesis step of bromo- [1,1'- the dinaphthyls] -2,2'- diyls dioxygens two (tri isopropyl silane) (compound 2) of 6,6'- bis-
Rapid as follows, 17.4mL tri isopropyl chlorosilane (TIPSCl) is added drop-wise to containing 15.8g compounds 1,5.33g imidazoles, 9.56g
The DMF solution (150mL) of 4- lutidines.It is stirred at room temperature after 24h, 200mL NaCl solutions are added to reaction above
System.Resulting reaction solution CH2Cl2Extract and use MgSO4Dry, rotary evaporation CH2Cl2Obtained solid is carried with chromatographic column
Compound 2 is obtained after pure.
The 4- ethenylphenyls of 6,6'- bis--(the tri isopropyl silane) (compound of [1,1'- dinaphthyls] -2,2'- diyls dioxygen two
3) synthesis step is as follows, 2g compounds 2,0.98g 4- vinylphenylboronic acids, 0.18g Pd (PPh3)4, 1M K2CO3Solution
15mL and 80mL tetrahydrofuran is in N2Lower backflow 12h.Room temperature is dropped to Deng reaction solution, is extracted with ether and uses MgSO4Dry, rotation
Turn to obtain compound 3 after the solid that evaporation solvent obtains is purified with chromatographic column.
The synthesis step of 6,6'- bis- 4- ethenylphenyls-[1,1'- dinaphthalene] -2,2'- glycol (compound 4) is as follows, 4.6g
Three water tetrabutyl ammonium fluorides be added drop-wise to 5.0g 3 100mL tetrahydrofuran.Etc. continuing to be stirred at room temperature after completion of dropping
After 4h, excessive water quenching is added, is extracted with ether and uses MgSO4Dry, the solid chromatographic column that rotary evaporation of solvent is obtained
Compound 4 is obtained after purification.
The conjunction of 6,6'- divinyl-[1,1'- dinaphthyls] -2,2'- diyls dioxygen two (tri isopropyl silane) (compound 5)
It is as follows into step, 2g compounds 2,0.90g vinyl fluoride potassium borates, 0.18g Pd (PPh3)4, 1M K2CO3Solution 15mL and
80mL tetrahydrofuran is in N2Lower backflow 12h.Room temperature is dropped to Deng reaction solution, is extracted with ether and uses MgSO4Dry, rotary evaporation
The solid that solvent is obtained obtains compound 5 after being purified with chromatographic column.
The synthesis step of 6,6'- divinyl-[1,1'- dinaphthalene] -2,2'- glycol (compound 6) is as follows, 4.6g three water
Tetrabutyl ammonium fluoride is added drop-wise to the 100mL of 4.0g compounds 5 tetrahydrofuran.Etc. after completion of dropping continuing that 4h is stirred at room temperature
Afterwards, excessive water quenching is added, is extracted with ether and uses MgSO4Dry, the solid that rotary evaporation of solvent is obtained is carried with chromatographic column
Compound 4 is obtained after pure.
The chiral phosphoramidite ligand of the BINOL bases of heretofore described vinyl functionalization is prepared by following methods and obtained
：Chemical structural formula (7) and (8) corresponding methyl substituted phosphoramidite ligand are by compound 4 (2mmol) or chemical combination in Fig. 3
Thing 6 (2mmol) is dissolved in toluene (20mL) and added after three (dimethylamino) phosphines (3mmol) to flow back under the atmosphere of 80 DEG C and nitrogen
12h.Rotary evaporation toluene, resulting solid is recrystallized to give product (Fig. 3) with petroleum ether.
The phosphoramidite ligand synthesis of other groups substitution is as follows：Compound 4 (2mmol) or compound 6 (2mmol) are dissolved in
PCl3(10mL) and add two and drip and react 1h under the atmosphere of 60 DEG C and nitrogen after 1-METHYLPYRROLIDONEs.PCl is removed under reduced pressure3Afterwards,
50mL anhydrous tetrahydro furan is added toward reaction system, excessive secondary amine is then added.Chemical structural formula (9)-(20) are right in Fig. 4
What is answered is obtained several representational phosphoramidite ligands, and this method goes for any secondary amine in principle.
The chiral phosphite ester ligand of the BINOL bases of heretofore described vinyl functionalization is prepared by following methods and obtained
：Compound 4 (2mmol) or compound 6 (2mmol) are dissolved in PCl3(10mL) and add after two drop 1-METHYLPYRROLIDONEs 60
DEG C and the atmosphere of nitrogen under react 1h.PCl is removed under reduced pressure3Afterwards, then toward reaction system 50mL anhydrous tetrahydro furan, three second are added
Amine (3mmol), and alcohol compound or phenolic compound (2.4mmol) are reacted, and obtain chiral phosphite ester ligand.Figure
It is several representational chiral phosphite ester ligands that chemical structural formula (21)-(32) are corresponding in 5, and this method can be fitted in principle
Different phosphite ester ligands are obtained for any alcohols (or phenols) compound.
Embodiment 1
1g compounds 7,20g ethyl acetate, 0.001g azodiisobutyronitriles are mixed, in heating under conditions of stirring
To 120 DEG C, 6h is reacted, solvent distillation obtains the polymer of white.The sample13C MAS NMR and31P MAS NMR scheme such as
Shown in Fig. 6 and Fig. 7, it can be seen that also occur in that one strong peak on the solid carbon nuclear-magnetism of polymer at 41.2ppm, this explanation second
Alkenyl polymerization successfully there occurs.31P MAS NMR figures show the chemical shift and the chemical shift of monomer of the P nuclear-magnetisms of polymer
It is almost identical, illustrate that the valence state of P in the course of the polymerization process does not change.N2Absorption result shows, resulting polymer
Specific surface area is in 490m2/ g or so (Fig. 8), pore-size distribution is at 0.5-150nm (Fig. 9).
Embodiment 2
By 1g compounds (8-20), 2g tetrahydrofurans, 0.01g azodiisobutyronitriles are mixed, under conditions of stirring
60 DEG C are being heated to, is being reacted 24 hours, solvent distillation, the polymer of white is being obtained.N2Absorption result shows, resulting polymerization
The specific surface area of thing is 400-780g/m2Between left and right, 1~100nm.
Embodiment 3
By 1g compounds (8-20), 40g DMFs, 0.005g azodiisobutyronitriles are mixed, and are being stirred
240 DEG C are being heated under conditions of mixing, 48h is being reacted, solvent distillation is obtaining the polymer of white.N2Absorption result shows, gained
The specific surface area of the polymer arrived is 500~1000g/m2Between left and right, 0.5~80nm.
Embodiment 4
By 1g compounds (21-32), 20g ethanol, 0.1g azodiisobutyronitriles are mixed, and are being added under conditions of stirring
Heat reacts 12h to 100 DEG C, and solvent distillation obtains the polymer of white.N2Absorption result shows, the ratio of resulting polymer
Surface area is in 400-600m2Between/g or so, 1~200nm.
Embodiment 5
By 1g compounds (21-32), 10g 1-METHYLPYRROLIDONEs, 0.01g azodiisobutyronitriles are mixed, in stirring
Under conditions of be heated to 150 DEG C, react 24h, solvent distillation obtains the polymer of white.N2Absorption result is shown, resulting
Polymer specific surface area be 460~780g/m2Left and right, aperture is between 0.3~100nm.
Embodiment 6
By 1g compounds 26,20g 1,2- dichloroethanes, 0.008g azodiisobutyronitriles are mixed, in the condition of stirring
Under be heated to 100 DEG C, react 24h, solvent distillation obtains the polymer of white.N2Absorption result shows, resulting polymerization
The specific surface area of thing is 523g/m2Between (Figure 10), 1.5~100nm (Figure 11).
Claims (6)
1. one kind is based on the poromeric method of homochiral molecule construction of 1,1'- union -2-naphthols, it is characterised in that including
Step：
According to basic framework material: porogenic solvents: the mass ratio of polymerization initiator is 1: 2~40: 0.001~0.1, by basic bone
Frame material is dissolved in porogenic solvents, then adds polymerization initiator；6~48h of stirring polymerization, is distilled to recover molten at 60~240 DEG C
Agent, is obtained by the porous polymer material of homochiral molecule construction；
The basic framework material is the chiral ligand of 1, the 1'- union -2-naphthol bases of vinyl functionalization, is by vinyl work(
Chiral phosphoramidite ligand or chiral phosphorous acid that the 1,1'- union -2-naphthols of energyization are obtained with amine, alcohol or phenolic compound reaction
Ester part.
2. according to the method described in claim 1, it is characterised in that the porogenic solvents are tetrahydrofuran, ethyl acetate, second
Any one in alcohol, N,N-dimethylformamide, 1-METHYLPYRROLIDONE or 1,2- dichloroethanes.
3. according to the method described in claim 1, it is characterised in that the polymerization initiator is azodiisobutyronitrile.
4. the method according to claims 1 to 3 any one, it is characterised in that the preparation of the basic framework material
Method is：
(1) 1, the 1'- union -2-naphthols containing 2mmol vinyl functionalization are dissolved in 20mL toluene, then add 3mmol tri-
(dimethylamino) phosphine, flow back 12h under the atmosphere of 80 DEG C and nitrogen；Toluene is spin-dried for by reaction after terminating with Rotary Evaporators, then
Recrystallized with petroleum ether, obtain methyl substituted chiral phosphoramidite ligand；Or,
(2) the 1,1'- union -2-naphthols of 2mmol vinyl functionalization are dissolved in 10mL PCl3, add two and drip 1-METHYLPYRROLIDONE
Afterwards, 1h is reacted under the atmosphere of 60 DEG C and nitrogen；PCl is removed under reduced pressure3Afterwards, 50mL anhydrous tetrahydrochysene furan is added into reaction system
Mutter, then add excessive secondary amine and proceed reaction, obtain the chiral phosphoramidite ligand of substituent substitution；Or,
(3) the 1,1'- union -2-naphthols of 2mmol vinyl functionalization are dissolved in 10mL PCl3, add two and drip 1-METHYLPYRROLIDONE
Afterwards, 1h is reacted under the atmosphere of 60 DEG C and nitrogen；PCl is removed under reduced pressure3Afterwards, the anhydrous tetrahydrochysene furans of 50mL are added into reaction system
Mutter, 3mmol triethylamines, and 2.4mmol alcohol compounds or phenolic compound reacted, and is obtained chiral phosphite ester and is matched somebody with somebody
Body.
5. method according to claim 4, it is characterised in that described secondary amine is diethylamine, diisopropylamine, N- methyl
Any one in tert-butylamine, double-(1- phenylethyls) amine, cyclohexylamine or morpholine；Described alcohols or phenolic compound be
Any one in methanol, isopropanol, phenol, 1- phenylethanols, 2-TBP or 2,6- DI-tert-butylphenol compounds.
6. method according to claim 1, it is characterised in that the poromeric aperture prepared 0.5~200nm it
Between, specific surface area is in 400~1000m2Between/g.
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