CN106939059B - The poromeric method of homochiral molecule construction based on 1,1 '-union -2-naphthols - Google Patents
The poromeric method of homochiral molecule construction based on 1,1 '-union -2-naphthols Download PDFInfo
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- CN106939059B CN106939059B CN201710135347.0A CN201710135347A CN106939059B CN 106939059 B CN106939059 B CN 106939059B CN 201710135347 A CN201710135347 A CN 201710135347A CN 106939059 B CN106939059 B CN 106939059B
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- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000010276 construction Methods 0.000 title claims abstract description 10
- 239000003446 ligand Substances 0.000 claims abstract description 29
- 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 19
- 229950011260 betanaphthol Drugs 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 12
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 7
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- 238000003756 stirring 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 32
- 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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 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
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 150000008301 phosphite esters Chemical class 0.000 claims description 9
- 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 8
- 150000002989 phenols Chemical class 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical class CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 6
- 150000003335 secondary amines Chemical class 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 5
- -1 phenolic compound Ester Chemical class 0.000 claims description 5
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 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
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 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
- ZQGJEUVBUVKZKS-UHFFFAOYSA-N n,2-dimethylpropan-2-amine Chemical compound CNC(C)(C)C ZQGJEUVBUVKZKS-UHFFFAOYSA-N 0.000 claims description 2
- KCXYZMFPZHYUFO-UHFFFAOYSA-N n-methyl-n-phosphanylmethanamine Chemical compound CN(C)P KCXYZMFPZHYUFO-UHFFFAOYSA-N 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- WAPNOHKVXSQRPX-UHFFFAOYSA-N 1-phenylethanol Chemical compound CC(O)C1=CC=CC=C1 WAPNOHKVXSQRPX-UHFFFAOYSA-N 0.000 claims 1
- XPNGNIFUDRPBFJ-UHFFFAOYSA-N alpha-methylbenzylalcohol Natural products CC1=CC=CC=C1CO XPNGNIFUDRPBFJ-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
- 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
- 229920000642 polymer Polymers 0.000 abstract description 26
- 230000015572 biosynthetic process Effects 0.000 abstract description 11
- 238000003786 synthesis reaction Methods 0.000 abstract description 11
- 239000000178 monomer Substances 0.000 abstract description 3
- 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
- 238000005516 engineering process Methods 0.000 abstract 1
- 230000006698 induction Effects 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 22
- 235000019441 ethanol Nutrition 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 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
- 238000010521 absorption reaction Methods 0.000 description 6
- 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
- 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
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000004738 31P MAS NMR Methods 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 229940125898 compound 5 Drugs 0.000 description 3
- 229910001882 dioxygen Inorganic materials 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
- 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 compound 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
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalene Chemical group C1=CC=C2C(C=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 description 2
- 238000004410 13C MAS NMR Methods 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- SPFZAUMRFKKIFC-UHFFFAOYSA-N B([O-])([O-])[O-].[K+].C(=C)F.[K+].[K+] Chemical compound 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
- 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
- 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
- 238000006555 catalytic reaction Methods 0.000 description 1
- 210000003850 cellular structure Anatomy 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
- 238000002156 mixing Methods 0.000 description 1
- 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 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 technologies of preparing of polymer, it is desirable to provide one kind is based on the poromeric method of homochiral molecule construction of 1,1'- union -2-naphthol.This method comprises: polymerization initiator is added after basic framework material is dissolved in porogenic solvents；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 free radical polymerization one-step synthesis method；Obtained chiral polymer is made to have better chiral induction environment that monomer is not additionally added again in the synthesis process；A series of chiral ligand can be obtained as basic framework by designing the BINOL molecule of vinyl functionalization；Between 0.5~200nm, specific surface area reaches as high as 1000m in obtained resin aperture2/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, in particular to a kind of poromeric synthesis side of the homochiral molecule construction based on 1,1'- union -2-naphthol (BINOL)
Method.
Background technique
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 catalyst of often has high activity and selectivity.But homogeneous chiral catalyst is difficult to repeat
It utilizes, and low utilization efficiency due to caused by poor stability further limits 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, stablizes and the catalyst being easily recycled is always to grind
The cost of enantiomer molecule is made to reduce by chiral catalysis for the hot spot studied carefully.
Porous polymer is because its designability is strong, big specific surface area, regulatable cellular structure, excellent chemistry and water
The features such as stability and be catalyzed, adsorb, ion exchange, and separation etc. 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-naphthol (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 ligand [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 [a) by the immobilized stability for being expected to improve them of orgnometallic catalyst
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 also it is able to achieve recycling.These all substantially increase their application prospect.
But the method for preparing multi-phase chiral catalyst of existing report is generally all comparatively laborious, and various preparation methods match difference
The general applicability of body is poor.
To which how synthesis multi-phase chiral catalyst that is easy and being suitable for being mass produced is still a challenge.
Summary of the invention
The technical problem to be solved by the present invention is to overcome deficiency in the prior art, provide a kind of based on 1,1'- connection -2-
The poromeric method of homochiral molecule construction of naphthols.
In order to solve the technical problem, solution of the invention is:
A kind of poromeric method of homochiral molecule construction being based on 1,1'- union -2-naphthol is provided, comprising steps of
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, and polymerization initiator is then added；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 base of vinyl functionalization, is by vinyl functionalization
The chiral phosphoramidite ligand that is reacted with amine, alcohol or phenolic compound of BINOL or chiral phosphite ester ligand.
In the present invention, the porogenic solvents are tetrahydrofuran, ethyl acetate, ethyl alcohol, n,N-Dimethylformamide, N- methyl
Any one in pyrrolidones or 1,2- dichloroethanes.
In the present invention, the polymerization initiator is azodiisobutyronitrile.
In the present invention, the basic framework material the preparation method comprises the following steps:
(1) 1, the 1'- union -2-naphthol containing 2mmol vinyl functionalization is dissolved in 20mL toluene, is then added
3mmol tri- (dimethylamino) phosphine, flow back 12h under the atmosphere of 80 DEG C and nitrogen；After reaction by toluene Rotary Evaporators
It is spin-dried for, then is recrystallized with petroleum ether, obtain methyl substituted chiral phosphoramidite ligand；Alternatively,
(2) the 1,1'- union -2-naphthol of 2mmol vinyl functionalization is dissolved in 10mL PCl3, two drop N- methyl pyrroles are added
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
Then tetrahydrofuran is added excessive secondary amine and continues to react, obtain the chiral phosphoramidite ligand of substituent group substitution；Or
Person,
(3) the 1,1'- union -2-naphthol of 2mmol vinyl functionalization is dissolved in 10mL PCl3, two drop N- methyl pyrroles are added
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 triethylamine and 2.4mmol alcohol compound or phenolic compound are reacted, and chiral phosphite ester is obtained
Ligand.
In the present invention, the secondary amine is diethylamine, diisopropylamine, N- methyl tertbutyl amine, double-(1- phenylethyl)
Any one in amine, cyclohexylamine or morpholine；The alcohols or phenolic compound is methanol, isopropanol, phenol, 1- phenyl second
Alcohol, 2-TBP or 2, any one in 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) pass through the porous chiral polymer of free radical polymerization one-step synthesis method；
(2) obtained chiral polymer is made to have better chirality to lure that monomer is not additionally added again in the synthesis process
Lead ring border；
(3) a series of chirality can be obtained as basic framework by the BINOL molecule of design vinyl functionalization to match
Body；
(4) between 0.5~200nm, specific surface area reaches as high as 1000m in obtained resin aperture2/g。
Detailed description of the invention
Fig. 1 is the synthetic route chart of the BINOL ligand of styryl functionalization.
In figure, (i) Br2, CH2Cl2；(ii) tri isopropyl chlorosilane, imidazoles, 4-dimethylaminopyridine, N, N- dimethyl methyl
Amide；(iii) 4- vinylphenylboronic acid, Pd (PPh3)4, K2CO3, tetrahydrofuran, H2O；(iv) tetrabutyl ammonium fluoride, tetrahydro furan
It mutters.
Fig. 2 is the synthetic route chart of the BINOL ligand 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 figure.
Fig. 7 is polymer samples in embodiment 131P MAS NMR figure.
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.
Specific embodiment
The present invention obtains porous chiral polymer by the one step solvent thermal polymerization of chiral molecules of vinyl functionalization.
Related 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 base of vinyl functionalization, is by vinyl functionalization
The chiral phosphoramidite ligand or chiral phosphite ester ligand that BINOL is reacted with amine, alcohol or phenolic compound.Preparation 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 the BINOL of 5.0g is molten
In the CH of 100mL2Cl2, after waiting system temperatures to drop to -10 DEG C, 2.4mL Br2With 20mL CH2Cl2It is slowly dropped to after dilution
State solution.It is added dropwise after being further continued for reaction 3h and uses NaHSO3Aqueous solution quenching.Water phase CH2Cl2It extracts and uses MgSO4It is dry
It is dry, rotary evaporation CH2Cl2Obtained white solid had both been compound 1.
The synthesis of bromo- [1,1'- the dinaphthyl] -2,2'- diyl dioxygen two (tri isopropyl silane) (compound 2) of 6,6'- bis- walks
Rapid as follows, the tri isopropyl chlorosilane (TIPSCl) of 17.4mL is added drop-wise to containing 15.8g compound 1,5.33g imidazoles, 9.56g
The DMF solution (150mL) of 4- lutidines.After being stirred at room temperature for 24 hours, 200mL NaCl solution is added to reaction above
System.Obtained reaction solution CH2Cl2It extracts and uses MgSO4It is dry, rotary evaporation CH2Cl2Obtained solid is mentioned with chromatographic column
Compound 2 is obtained after pure.
Bis- 4- ethenylphenyl of 6,6'--two (tri isopropyl silane) (compound of [1,1'- dinaphthyl] -2,2'- diyl dioxygen
3) synthesis step is as follows, 2g compound 2,0.98g 4- vinylphenylboronic acid, 0.18g Pd (PPh3)4, the K of 1M2CO3Solution
The tetrahydrofuran of 15mL and 80mL is in N2Lower reflux 12h.Equal reaction solutions drop to room temperature, are extracted with ether and use MgSO4It is dry, rotation
Turn to obtain compound 3 after the solid that evaporation solvent obtains is purified with chromatographic column.
6,6'- bis- 4- ethenylphenyls-[1,1'- dinaphthalene] -2,2'- glycol (compound 4) synthesis step 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 being added dropwise
After 4h, excessive water quenching is added, is extracted with ether and uses MgSO4It is dry, the solid chromatographic column that rotary evaporation of solvent obtains
Compound 4 is obtained after purification.
The conjunction of 6,6'- divinyl-[1,1'- dinaphthyl] -2,2'- diyl dioxygen two (tri isopropyl silane) (compound 5)
At steps are as follows, 2g compound 2,0.90g vinyl fluoride potassium borate, 0.18g Pd (PPh3)4, the K of 1M2CO3Solution 15mL and
The tetrahydrofuran of 80mL is in N2Lower reflux 12h.Equal reaction solutions drop to room temperature, are extracted with ether and use MgSO4It is dry, rotary evaporation
The solid that solvent obtains obtains compound 5 after being purified with chromatographic column.
6,6'- divinyl-[1,1'- dinaphthalene] -2,2'- glycol (compound 6) synthesis step is as follows, three water of 4.6g
Tetrabutyl ammonium fluoride is added drop-wise to the tetrahydrofuran of the 100mL of 4.0g compound 5.Etc. after being added dropwise 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 obtains is mentioned with chromatographic column
Compound 4 is obtained after pure.
The chiral phosphoramidite ligand of the BINOL base of heretofore described vinyl functionalization is obtained by following methods preparation
: chemical structural formula (7) and (8) corresponding methyl substituted phosphoramidite ligand are by compound 4 (2mmol) or chemical combination in Fig. 3
Object 6 (2mmol) is dissolved in toluene (20mL) and flows back under the atmosphere of 80 DEG C and nitrogen after three (dimethylamino) phosphines (3mmol) are added
12h.Rotary evaporation toluene, obtained solid are recrystallized to give product (Fig. 3) with petroleum ether.
The phosphoramidite ligand synthesis that other groups replace is as follows: compound 4 (2mmol) or compound 6 (2mmol) are dissolved in
PCl3(10mL) and 1h is reacted under the atmosphere of 60 DEG C and nitrogen after two drop N-Methyl pyrrolidones are added.PCl is removed under reduced pressure3Afterwards,
The anhydrous tetrahydro furan of 50mL is added toward reaction system, excessive secondary amine is then added.Chemical structural formula (9)-(20) are right in Fig. 4
Several representative phosphoramidite ligands for being answered, this method can be adapted for any secondary amine in principle.
The chiral phosphite ester ligand of the BINOL base of heretofore described vinyl functionalization is obtained by following methods preparation
: compound 4 (2mmol) or compound 6 (2mmol) are dissolved in PCl3It (10mL) and is added after two drop N-Methyl pyrrolidones 60
DEG C and the atmosphere of nitrogen under react 1h.PCl is removed under reduced pressure3Afterwards, then toward reaction system anhydrous tetrahydro furan, three second of 50mL are added
Amine (3mmol) and alcohol compound or phenolic compound (2.4mmol) are reacted, and chiral phosphite ester ligand is obtained.Figure
It is several representative chiral phosphite ester ligands that chemical structural formula (21)-(32) are corresponding in 5, and this method can fit in principle
Different phosphite ester ligands is obtained for any alcohols (or phenols) compound.
Embodiment 1
1g compound 7,20g ethyl acetate, 0.001g azodiisobutyronitrile are mixed, are heating under stirring conditions
To 120 DEG C, 6h is reacted, solvent distillation obtains the polymer of white.The sample13C MAS NMR and31P MAS NMR schemes such as
Shown in Fig. 6 and Fig. 7, it can be seen that also occur a strong peak on the solid carbon nuclear-magnetism of polymer at 41.2ppm, this illustrates second
Alkenyl polymerization successfully has occurred.31P MAS NMR figure shows the chemical shift of the P nuclear-magnetism of polymer and the chemical shift of monomer
It is almost the same, illustrate that the valence state of P in the course of the polymerization process does not change.N2Absorption result shows, obtained 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 compound (8-20), 2g tetrahydrofuran, 0.01g azodiisobutyronitrile is mixed, under stirring conditions
60 DEG C are being heated to, is being reacted 24 hours, solvent distillation, the polymer of white is obtained.N2Absorption result shows, obtained polymerization
The specific surface area of object is 400-780g/m2Or so, between 1~100nm.
Embodiment 3
By 1g compound (8-20), 40g n,N-Dimethylformamide, 0.005g azodiisobutyronitrile is mixed, and is being stirred
240 DEG C are being heated under conditions of mixing, is reacting 48h, solvent distillation obtains the polymer of white.N2Absorption result shows, gained
The specific surface area of the polymer arrived is 500~1000g/m2Or so, between 0.5~80nm.
Embodiment 4
By 1g compound (21-32), 20g ethyl alcohol, 0.1g azodiisobutyronitrile is mixed, and is being added under stirring conditions
Heat reacts 12h to 100 DEG C, and solvent distillation obtains the polymer of white.N2Absorption result shows, the ratio of obtained polymer
Surface area is in 400-600m2/ g or so, between 1~200nm.
Embodiment 5
By 1g compound (21-32), 10g N-Methyl pyrrolidone, 0.01g azodiisobutyronitrile is mixed, and is being stirred
Under conditions of be heated to 150 DEG C, for 24 hours, solvent distillation obtains the polymer of white for reaction.N2Absorption result is shown, acquired
Polymer specific surface area be 460~780g/m2Left and right, aperture is between 0.3~100nm.
Embodiment 6
By 1g compound 26,20g 1,2- dichloroethanes, 0.008g azodiisobutyronitrile is mixed, in the condition of stirring
Under be heated to 100 DEG C, for 24 hours, solvent distillation obtains the polymer of white for reaction.N2Absorption result shows, obtained polymerization
The specific surface area of object is 523g/m2(Figure 10), between 1.5~100nm (Figure 11).
Claims (5)
1. the poromeric method of homochiral molecule construction that one kind is based on 1,1'- union -2-naphthol, which is characterized 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, and polymerization initiator is then added；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 base of vinyl functionalization, is by vinyl function
The chiral phosphoramidite ligand or chiral phosphorous acid that the 1,1'- union -2-naphthol of energyization is reacted with amine, alcohol or phenolic compound
Ester ligand；
The basic framework material the preparation method comprises the following steps:
(1) 1, the 1'- union -2-naphthol containing 2mmol vinyl functionalization is dissolved in 20mL toluene, 3mmol tri- is then added
(dimethylamino) phosphine, flow back 12h under the atmosphere of 80 DEG C and nitrogen；Toluene is spin-dried for Rotary Evaporators after reaction, then
It is recrystallized with petroleum ether, obtains methyl substituted chiral phosphoramidite ligand；Alternatively,
(2) the 1,1'- union -2-naphthol of 2mmol vinyl functionalization is dissolved in 10mL PCl3, two drop N-Methyl pyrrolidones are added
Afterwards, 1h is reacted under the atmosphere of 60 DEG C and nitrogen；PCl is removed under reduced pressure3Afterwards, the anhydrous tetrahydro furan of 50mL is added into reaction system
It mutters, excessive secondary amine is then added and continues to react, obtain the chiral phosphoramidite ligand of substituent group substitution；Alternatively,
(3) the 1,1'- union -2-naphthol of 2mmol vinyl functionalization is dissolved in 10mL PCl3, two drop N-Methyl pyrrolidones are added
Afterwards, 1h is reacted under the atmosphere of 60 DEG C and nitrogen；PCl is removed under reduced pressure3Afterwards, the anhydrous tetrahydro furan of 50mL is added into reaction system
Mutter, 3mmol triethylamine and 2.4mmol alcohol compound or phenolic compound are reacted, obtain chiral phosphite ester and match
Body.
2. the method according to claim 1, wherein the porogenic solvents are tetrahydrofuran, ethyl acetate, second
Any one in alcohol, N,N-dimethylformamide, N-Methyl pyrrolidone or 1,2- dichloroethanes.
3. the method according to claim 1, wherein the polymerization initiator is azodiisobutyronitrile.
4. the method according to claim 1, wherein the secondary amine is diethylamine, diisopropylamine, N- methyl
Tert-butylamine, double-(1- phenylethyl) amine, any one in cyclohexylamine or morpholine；The alcohols or phenolic compound be
Methanol, isopropanol, phenol, 1- phenylethanol, 2-TBP or 2, any one in 6- DI-tert-butylphenol compounds.
5. the method according to claim 1, which is characterized in that the poromeric aperture prepared 0.5~200nm it
Between, specific surface area is in 400~1000m2Between/g.
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