CN103242373B - Immobilized chiral ligand of a kind of ferriferrous oxide nano-particle and preparation method thereof and application - Google Patents
Immobilized chiral ligand of a kind of ferriferrous oxide nano-particle and preparation method thereof and application Download PDFInfo
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 118
- 239000003446 ligand Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 239000002245 particle Substances 0.000 claims abstract description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 141
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 116
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 63
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 239000007787 solid Substances 0.000 claims description 26
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 17
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 14
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 11
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000005576 amination reaction Methods 0.000 claims description 7
- -1 p-dichlorobenzyl (p-dichlorobenzyl) Chemical group 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 6
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 3
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 3
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005642 Oleic acid Substances 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 3
- 238000004440 column chromatography Methods 0.000 claims description 3
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 claims description 3
- ZITKDVFRMRXIJQ-UHFFFAOYSA-N dodecane-1,2-diol Chemical group CCCCCCCCCCC(O)CO ZITKDVFRMRXIJQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 3
- 238000000197 pyrolysis Methods 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 20
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 abstract description 14
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical group CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 238000006555 catalytic reaction Methods 0.000 abstract description 11
- 150000003934 aromatic aldehydes Chemical class 0.000 abstract description 10
- 239000000047 product Substances 0.000 abstract description 6
- 238000001179 sorption measurement Methods 0.000 abstract description 6
- 238000007259 addition reaction Methods 0.000 abstract description 5
- 238000009826 distribution Methods 0.000 abstract description 2
- 239000012467 final product Substances 0.000 abstract 1
- 238000007867 post-reaction treatment Methods 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 229910052786 argon Inorganic materials 0.000 description 15
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 12
- 230000004580 weight loss Effects 0.000 description 11
- 238000011068 loading method Methods 0.000 description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 8
- 238000004809 thin layer chromatography Methods 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 7
- 229960003638 dopamine Drugs 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- 238000010907 mechanical stirring Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 239000002122 magnetic nanoparticle Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- JQIVECLQPHOSDY-QGZVFWFLSA-N [(2s)-1,2-diphenylpyrrolidin-2-yl]methanol Chemical compound C([C@@]1(CO)C=2C=CC=CC=2)CCN1C1=CC=CC=C1 JQIVECLQPHOSDY-QGZVFWFLSA-N 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 229910009112 xH2O Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 150000001414 amino alcohols Chemical class 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000004179 3-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(Cl)=C1[H] 0.000 description 2
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000819038 Chichester Species 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000011982 enantioselective catalyst Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene chloride Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 2
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 229910017135 Fe—O Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- 150000008365 aromatic ketones Chemical class 0.000 description 1
- 238000009876 asymmetric hydrogenation reaction Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010961 commercial manufacture process Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- DLAPQHBZCAAVPQ-UHFFFAOYSA-N iron;pentane-2,4-dione Chemical compound [Fe].CC(=O)CC(C)=O DLAPQHBZCAAVPQ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of Z 250 (Fe
3o
4) the immobilized chiral ligand of nanoparticle and preparation method thereof and application, this part has the structural formula shown in formula I, the present invention also provides the preparation method of this part, and this part is mainly used in the addition reaction of the addition of catalysis zinc ethyl and aromatic aldehyde, phenylacetylene and aromatic aldehyde.Part of the present invention is easily prepared, and post-reaction treatment is simple to operate, only needs simple magnet adsorption to get final product separating catalyst and product; Catalytic stability is high, recycles 20 times and still can keep high catalytic activity and stereoselectivity; There is particle size distribution range narrow, dispersed good, the not easily advantage such as reunion.
Description
Technical Field
The invention relates to ferroferric oxide (Fe)3O4) A nano particle immobilized chiral ligand, a preparation method and an application thereof belong to the technical field of chiral catalytic materials.
Background
In the field of asymmetric catalysis, homogeneous asymmetric catalytic reactions dominate. This is because homogeneous asymmetric catalytic reactions generally have high selectivity and catalytic activity, and in many reaction systems, high enantioselectivity is achieved: (>The 95% ee value, which means that one isomer is present in the enantiomeric mixture in an amount which is more than the other isomer as a percentage of the total amount), has not been particularly difficult. However, in addition to the partial asymmetric catalytic hydrogenation and the very individual carbon-carbon, carbon-heteroatom bond formation reactions, the problem of the efficiency of the use of chiral catalysts has been the major bottle that limits their practical applicationsAnd (4) a neck. On the one hand, since chiral catalysts (including chiral ligands and metals) are generally relatively expensive and are not easily recovered and recycled under homogeneous catalysis conditions, relatively high catalyst loadings (1-10%) generally render catalytic reactions impractical [ R.Noyori, Asymmetric catalysis organic Synthesis, Wiley-Interscience, New York,1994 ]];[CatalysisAsymmetricSynthesis2nded.(Ed.:I.Ojima),Wiley-VCH,NewYork,2000],[ComprehensiveAsymmetricCatalysis,(Eds.:E.N.Jacoben,A.Pfaltz,H.Yamamoto),Springer,Berlin,1999,Vol.I-III],[LewisAcidsinOrganicSynthesis,(Ed.H.Yamamoto),Wiley-VCH,NewYork,2001](ii) a On the other hand, the loss of harmful substances such as heavy metals from the catalyst during the homogeneous reaction is also a problem, especially in the preparation and production of pharmaceutical intermediates, which is absolutely unacceptable [ chirality industry: the commercial manufacture and application of optically active compounds (eds.: A.N.Collins, G.N.Sheldrake, J.Crosby), Wiley, Chichester,1992];[ChiralityinIndustryII:DevelopmentsintheCommercialManufactureandApplicationsofOpticallyActiveCompouds(Eds.:A.N.Collins,G.N.Sheldrake,J.Crosby),Wiley,Chichester,1997];[R.A.Sheldon,Chirotechnology:IndustrialSynthesisofOpticallyActiveCompounds,Dekker,NewYork,1993]. Heterogeneous catalysis provides a good technical platform for solving the problems, and through immobilization of a homogeneous catalyst, the method not only can solve the problem of recycling, but also can reduce metal pollutants in the catalyst and a separation process with a complex surface [ ChiralCatalystImmobilationRecycling, D.E.DeVos, I.F.J.Vankelecom, P.A.Jacobs, eds, Wiley-VCH: Weinheim, 2000. E.DeVos, I.F.J.Vankelecom, P.A.Jacobs, eds, Wiley-VCH]。
The magnetic nano material has the characteristics of small size, large specific surface area, easy separation and the like, and has wide application prospects in various fields (fine chemical intermediates 41 (2011) 12-119). For example, LinWenbin et al prepared phosphate-coated Fe3O4Chiral Ru catalyst [ Ru (BINAP-PO) immobilized by nano particles3)-(DPEN)Cl2]The asymmetric hydrogenation of aromatic ketones shows good catalytic effect (journal of American chemical society127(2005) 12486-12487). Catalysts prepared by such processesCan be recycled for fourteen times. Preparation of SiO by Chengjin-Pei et al2Wrapping Fe3O4The nano particle immobilized chiral primary amine ligand shows good catalytic effect on asymmetric aldol condensation and can be recycled for ten times (chem.Commun. (2008) 5719-. In 2009, the rajerrs s.varma group suggested that dopamine hydrochloride could be in Fe3O4The formation of stable complexes on the surface of nanoparticles provides a simple and efficient method for functionalizing nanoparticles (org. biomol. chem.7(2009)37-40, chem. eur. j.15(2009) 1582-1586). In the same year, StephenJ. connon group used this method in Fe3O4Functional molecules are introduced to the surface of the nano-particle and are used for asymmetric esterification reaction of alcohol for the first time, and good results are obtained (chem. Eur. J.15(2009) 5669-5673), but the solid loading of the chiral ligand is only 0.0805 mmol/g. Therefore, the functional Fe with high solid load and good asymmetric catalytic activity is developed3O4Nanomaterials remain an important problem. In addition, the catalytic activity of the existing related asymmetric catalyst is still to be mentioned, and the preparation of the asymmetric catalyst with high catalytic activity and long service life is imperative.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides ferroferric oxide (Fe)3O4) A nano particle immobilized chiral ligand and a preparation method and application thereof.
The technical scheme of the invention is as follows:
ferroferric oxide (Fe)3O4) A nanoparticle-immobilized chiral ligand having a structural formula shown in formula I:
in the formula I, A is ferroferric oxide (Fe)3O4) Nanoparticles.
Ferroferric oxide (Fe)3O4) The preparation method of the nano particle immobilized chiral ligand comprises the following steps:
(1) ferroferric oxide (Fe)3O4) Preparing nano particles:
preparation by a precipitation method: dissolving ferric salt and ferrous salt in water according to a molar ratio of 2:1, adding an alkali solution at 20-100 ℃ under the protection of inert gas, keeping for 20-30 minutes, naturally cooling to room temperature, separating solid, washing with deionized water to be neutral, and drying in vacuum at 50-60 ℃ to obtain ferroferric oxide (Fe)3O4) Nanoparticles; or,
pyrolysis preparation: dissolving an iron-containing compound in a high-boiling-point solvent, refluxing for 10-60 minutes at 200-300 ℃, naturally cooling to room temperature, separating solids, washing with acetone, and drying in vacuum at 50-60 ℃ to obtain ferroferric oxide (Fe)3O4) Nanoparticles; the high boiling point solvent is 1, 2-dodecanediol, oleic acid, oleylamine, diphenyl ether or benzyl ether;
(2) ferroferric oxide (Fe)3O4) Surface amination of nanoparticles:
the ferroferric oxide (Fe) prepared in the step (1) is added3O4) Dispersing the nano particles into water or ethanol solution, uniformly dispersing, adding dopamine hydrochloride, performing ultrasonic treatment or stirring for 0.5-24 hours, separating solid, washing with acetone, and performing vacuum drying at 50-60 ℃ to obtain ferroferric oxide (Fe) with aminated surface3O4) Nanoparticles; the dopamine hydrochloride and ferroferric oxide (Fe)3O4) The mass ratio of the nano particles is (1-1.5): 1, the surface aminated ferroferric oxide (Fe)3O4) The structural formula of the nano particle is shown as formula II:
in the formula II, A is ferroferric oxide (Fe)3O4) Nanoparticles; through element analysis, the solid loading amount of the dopamine hydrochloride is 0.03-2.20 mmol/g;
(3) preparation of (S) - (1- (4- (chloromethyl) phenyl) -2-pyrrolyl) diphenylmethanol:
p-dichlorobenzyl, (S) -diphenyl prolinol and alkali are mixed according to the mol ratio of 1: 1: (1-1.5), dissolving in a solvent, stirring and heating to 50-60 ℃, keeping the temperature for reaction for 24 hours, and stopping the reaction; distilling under reduced pressure to remove solvent, dissolving the residue with ethyl acetate, washing with saturated sodium chloride solution, drying with anhydrous sodium sulfate, distilling under reduced pressure to remove ethyl acetate, and separating by column chromatography to obtain (S) - (1- (4- (chloromethyl) phenyl) -2-pyrrolyl) diphenylmethanol; the solvent is acetone, acetonitrile or tetrahydrofuran; the structural formula of the (S) - (1- (4- (chloromethyl) phenyl) -2-pyrrolyl) diphenyl methanol is shown as a formula III:
(4) ferroferric oxide (Fe)3O4) Preparing a nano particle immobilized chiral ligand:
carrying out surface amination on ferroferric oxide (Fe) prepared in step (2)3O4) The nanoparticles, the (S) - (1- (4- (chloromethyl) phenyl) -2-pyrrolyl) diphenyl methanol prepared in the step (3) and the base are mixed according to the mass ratio of 1: (1-1.5): (1-1.5) mixing, and dissolving in a solvent; mechanically stirring and heating to 50-60 ℃ in an inert environment, keeping the temperature for reaction for 24 hours, and stopping the reaction; separating the solid, washing with methanol and acetone, and vacuum drying at 50-60 deg.C to obtain black ferroferric oxide (Fe)3O4) The nano particles are immobilized with chiral ligands, and the solvent is acetone, acetonitrile or tetrahydrofuran. By element analysis, the solid loading of the chiral ligand is 0.04-1.80 mmol/g based on (S) - (1- (4- (chloromethyl) phenyl) -2-pyrrolyl) diphenylmethanol.
According to the present invention, preferably, the ferroferric oxide (Fe) prepared in the step (1)3O4) The nano particles are magnetic nano particles;
preferably, in the preparation by precipitation: the ferric salt is Fe2(SO4)3·xH2O、FeCl3·xH2O or Fe (NO)3)3·xH2O; the ferrous salt being FeCl2·xH2O; the inert gas is nitrogen or argon, preferably argon; the temperature is preferably 30-80 ℃, the aqueous alkali is 28wt% of concentrated ammonia or 10wt% of sodium hydroxide solution, preferably 28wt% of concentrated ammonia, and the ferroferric oxide (Fe) is prepared3O4) The average particle size of the nanoparticles is 5-20 nm;
preferably, in the pyrogenic process preparation: said iron-containing compound is Fe (acac)3(iron acetylacetonate), Fe (CO)5(iron pentacarbonyl) or FeCup3Organic iron (N-nitrosohydroxyanilino hydroxylamine iron), more preferably Fe (acac)3(iron acetylacetonate) to obtain ferroferric oxide (Fe)3O4) The average particle diameter of the nanoparticles is 4-14 nm.
According to the present invention, it is preferred that the base in step (3) or (4) is triethylamine, pyridine or potassium carbonate, more preferably potassium carbonate.
According to the present invention, it is preferable that the method for separating solids in step (1), (2) or (4) is to separate solids by strong magnet adsorption or to separate solids by centrifugation.
The above-mentioned iron oxide (Fe) of the present invention3O4) The application of the nano particle immobilized chiral ligand is that ferroferric oxide (Fe)3O4) The nano particle immobilized chiral ligand is used for catalyzing addition reaction of diethyl zinc and aromatic aldehyde and addition reaction of phenylacetylene and aromatic aldehyde.
Compared with the prior art, the invention has the following advantages:
1. book (I)Inventive ferroferric oxide (Fe)3O4) The nano particle immobilized chiral ligand is easy to prepare, the treatment operation after reaction is simple, and the catalyst and the product can be separated only by simple magnet adsorption.
2. Ferroferric oxide (Fe) of the invention3O4) The nano particle immobilized chiral ligand is applied to the addition reaction of diethyl zinc and aromatic aldehyde and the addition reaction of phenylacetylene and aromatic aldehyde, and has the catalytic activity and the stereoselectivity equivalent to those of a free chiral ligand.
3. Ferroferric oxide (Fe) of the invention3O4) The nano-particle immobilized chiral ligand has higher stability, and can still maintain high catalytic activity and stereoselectivity after being recycled for 20 times.
4. The invention adopts bisphenol with active functional group and ferroferric oxide (Fe)3O4) The defect sites on the surfaces of the magnetic nanoparticles are coordinated, so that the magnetic nanoparticles are subjected to the reaction of ferroferric oxide (Fe)3O4) Active functional groups are introduced into the surface of the magnetic nano-particle, and the magnetic nano-particle and the derivatized (S) -diphenyl prolinol form covalent bonds to achieve the purpose of immobilizing the (S) -diphenyl prolinol.
5. The preparation method is simple, and the reaction operation is easy; prepared ferroferric oxide (Fe)3O4) The particle size distribution range of the nano particle supported chiral ligand is narrow, the dispersibility is good, and the nano particle supported chiral ligand is not easy to agglomerate; the catalyst shows higher reaction activity and stereoselectivity in asymmetric catalytic reaction.
6. Ferroferric oxide (Fe) prepared by the invention3O4) The immobilization of the nano-particle immobilized chiral ligand is high and can reach 1.80mmol/g according to the (S) - (1- (4- (chloromethyl) phenyl) -2-pyrrolyl) diphenyl methanol.
Drawings
FIG. 1 is a single-crystal X-ray diffraction structural analysis diagram of (S) - (1- (4- (chloromethyl) phenyl) -2-pyrrolyl) benzhydrol. HCl prepared in example 1 of the present invention.
FIG. 2 shows ferroferric oxide (Fe) prepared in example 1 of the present invention3O4) A dispersion example diagram and a separation example diagram of the nano particle immobilized chiral ligand; in the figure, (i) is ferroferric oxide (Fe)3O4) An example of dispersing a nanoparticle immobilized chiral ligand in a methanol solution; (ii) is ferroferric oxide (Fe)3O4) An example of the separation of the nano-particle immobilized chiral ligand under the adsorption action of a magnet is shown in the figure.
FIG. 3 shows ferroferric oxide (Fe) prepared in example 1 of the present invention3O4) Nanoparticles (a) and surface-aminated ferroferric oxide (Fe)3O4) Nanoparticles (b) and ferroferric oxide (Fe)3O4) An infrared spectrum of the nanoparticle-immobilized chiral ligand (d).
FIG. 4 shows ferroferric oxide (Fe) prepared in example 1 of the present invention3O4) Nanoparticles and iron oxide (Fe)3O4) An X-ray diffraction pattern of the nanoparticle-immobilized chiral ligand; in the figure, (i) is ferroferric oxide (Fe)3O4) X-ray diffraction pattern of the nanoparticles, (ii) ferroferric oxide (Fe)3O4) X-ray diffraction pattern of the nanoparticle-immobilized chiral ligand.
FIG. 5 shows ferroferric oxide (Fe) prepared in example 1 of the present invention3O4) Nanoparticles and iron oxide (Fe)3O4) Transmission electron microscope image of nano particle immobilized chiral ligand; in the figure, (i) is ferroferric oxide (Fe)3O4) Transmission electron microscope picture of nano particle, (ii) is ferroferric oxide (Fe)3O4) Transmission electron microscope image of nano particle supported chiral ligand.
FIG. 6 shows ferroferric oxide (Fe) prepared in example 1 of the present invention3O4) Nanoparticles (a) and surface-aminated ferroferric oxide (Fe)3O4) Nanoparticles (b)And ferroferric oxide (Fe)3O4) Thermogravimetric analysis of the nanoparticle-immobilized chiral ligand (d).
Detailed Description
The present invention will be further described with reference to the following detailed description of embodiments thereof, but not limited thereto, in conjunction with the accompanying drawings.
The raw materials used in the examples and the application examples are all conventional reagents, and the equipment used is conventional equipment and a commercial product. Wherein: (S) -Diphenyl Prolinanol (CAS number: 112068-01-6), available from Jinanhaohua industry responsibility, Inc.
Example 1
Ferroferric oxide (Fe)3O4) The preparation method of the nano particle immobilized chiral ligand comprises the following steps:
(1) ferroferric oxide (Fe)3O4) Preparing nano particles:
0.56g of FeCl3·6H2O and 0.20gFeCl2·4H2Dissolving O in 10ml of secondary distilled water, heating to 80 ℃ under the protection of argon, rapidly adding 5ml of 28wt% ammonia water under vigorous mechanical stirring, and keeping the reaction for 20 minutes; naturally cooling the reactant to room temperature, washing the reactant to be neutral by using secondary distilled water, adsorbing and separating the solid by using a permanent magnet, and drying the solid for 5 hours in vacuum at the temperature of 60 ℃ to obtain ferroferric oxide (Fe)3O4) Nanoparticles (numbered a). IR (KBr, cm)-1):3437,612,598；
(2) Ferroferric oxide (Fe)3O4) Surface amination of nanoparticles:
weighing 0.2g of ferroferric oxide (Fe) obtained in the step (1)3O4) Dissolving the nano particles in 25ml of secondary distilled water, carrying out ultrasonic treatment for 30 minutes, adding 0.2g of dopamine hydrochloride under the protection of argon, and carrying out ultrasonic reaction for 2 hours; transferring the reaction mixture to a centrifugal tube for centrifugal separation, washing the solid for 3 times by using acetone, and drying for 5 hours in vacuum at 60 ℃ to obtain ferroferric oxide (Fe) with aminated surface3O4) Nanoparticles (numbered b). IR (KBr, cm)-1) 3430,2925,2855,1631,1544,1429,1050,629,592; the solid loading capacity of dopamine hydrochloride is 1.5mmol/g in elemental analysis;
(3) preparation of (S) - (1- (4- (chloromethyl) phenyl) -2-pyrrolyl) diphenylmethanol:
dissolving 1mmol of p-dichlorobenzyl, 1mmol of (S) -diphenyl prolinol and 1mmol of potassium carbonate in 20ml of acetonitrile, stirring and heating to 50 ℃, preserving heat for reaction for 24 hours, and stopping the reaction; removing acetonitrile by distillation under reduced pressure, dissolving the residue with ethyl acetate, washing with saturated sodium chloride solution, drying with anhydrous sodium sulfate, removing ethyl acetate by distillation under reduced pressure, and separating by column chromatography (ethyl acetate: petroleum ether =1: 8) to obtain (S) - (1- (4- (chloromethyl) phenyl) -2-pyrrolyl) diphenylmethanol (numbered as c) with a yield of 47%; m.p.89-90 ℃; IR (KBr, cm)-1):3435,2952,1639,1490,1450,1410,1270,1101,707.1HNMR(CDCl3,400MHz):7.70(d,J=7.6Hz,2H),7.57(d,J=6.8Hz,2H),7.31-7.24(m,7H),7.18-7.14(m,1H),7.11-7.07(m,1H),7.04-7.02(m,2H),4.85(s,1H),4.54(s,2H),3.97(q,J=4.8Hz,J=14.0Hz,1H),3.21-3.18(m,1H),3.05-3.02(m,1H),2.92-2.91(m,1H),2.37-2.30(m,1H),1.99-1.92(m,1H),1.77-1.75(m,1H),1.65-1.62(m,2H)；
(4) Ferroferric oxide (Fe)3O4) Preparing a nano particle immobilized chiral ligand:
0.2g of ferroferric oxide (Fe) with aminated surface3O4) Nanoparticles, 0.2g of (S) - (1- (4- (chloromethyl) phenyl) -2-pyrrolyl) diphenylmethanol and 0.2g of potassium carbonate were mixed and dissolved in 10ml of acetonitrile; mechanically stirring and heating to 50 ℃ under the protection of argon, preserving heat and reacting for 24 hours, and stopping reaction; separating with strong magnet, washing with methanol and acetone for 2 times, vacuum drying at 60 deg.C for 5 hrThen ferroferric oxide (Fe) is obtained3O4) The nano-particles are immobilized with chiral ligand (numbered as d), and the average particle diameter is 14 nm. IR (KBr, cm)-1):3425,2925,2855,1650,1567,1420,1406,1384,1310,1100,1052,631,592. Elemental analysis the solid loading of the chiral ligand was 1.6mmol/g based on (S) - (1- (4- (chloromethyl) phenyl) -2-pyrrolyl) diphenylmethanol.
Performing infrared spectrum tests on the a, the b and the d to obtain infrared spectrograms as shown in figure 3, wherein the infrared peak graphs of the a, the b and the d are respectively (a), (b) and (d) in figure 3; 3437cm from (a)-1Is ferroferric oxide (Fe)3O4) Stretching vibration of crystal water O-H bond on nanoparticle surface, 612cm-1And 598cm-1Stretching vibration of Fe-O bond; from (b), it is found that not only Fe is present3O4And at 2925cm-1And 2855cm-1Stretching vibration of C-H bond with dopamine, 1631cm-1、1544cm-1And 1429cm-1Skeleton having C-C bond of benzene ring vibrating at 1050cm-1The stretching vibration of C-N bond of dopamine shows that ferroferric oxide (Fe) with aminated surface is obtained3O4) Nanoparticles; from (d), it is found that not only iron oxide (Fe) is present3O4) And characteristic peak of dopamine, 1310cm-1In-plane bending vibration of 1100cm having amino alcohol C-O bond and O-H bond-1Stretching vibration of the C-N bond with amino alcohol indicates that ferroferric oxide (Fe) is obtained3O4) The nanoparticles entrap chiral ligands.
FIG. 6 shows ferroferric oxide (Fe) prepared in this example3O4) Nanoparticles (a) and surface-aminated ferroferric oxide (Fe)3O4) Nanoparticles (b) and ferroferric oxide (Fe)3O4) Thermogravimetric analysis of the nanoparticle-immobilized chiral ligand (d); from (a), the weight loss reaches about 1.5% at about 120 ℃, which is attributed to the removal of water adsorbed on the surfaces of the nanoparticles, and when the temperature is higher than 150 ℃, the water adsorbed among the nanoparticles begins to volatilize, resulting in the weight loss of 0.5% -1.5%, so that ferroferric oxide (F)e3O4) The final weight loss of the nano particles at high temperature is within the range of 2-3 percent; (b) in addition, the material has obvious weight loss peak (ferroferric oxide (Fe) in the place) at the temperature of 120-150 DEG C3O4) The weight loss of water adsorbed on the surfaces of the nano particles and among the nano particles) and has an obvious weight loss peak from 170 ℃, which is ferroferric oxide (Fe)3O4) The weight loss caused by decomposition of dopamine molecules on the surface of the nano particles is realized, so that the adsorption capacity of the dopamine on the nano particles is about 8.5 percent; (d) in addition, the material has obvious weight loss peak (ferroferric oxide (Fe) in the place) at the temperature of 120-150 DEG C3O4) The surface of the nano-particle and the weight loss of water absorbed between the nano-particles) and has an obvious weight loss peak from about 170 ℃, which is ferroferric oxide (Fe)3O4) The weight loss caused by the decomposition of organic molecules on the surfaces of the nanoparticles is reduced, and the adsorption capacity of the chiral ligand of the amino alcohol is about 21.0 percent after the amount of the dopamine is deducted.
Example 2
Ferroferric oxide (Fe)3O4) The preparation method of the nano particle immobilized chiral ligand comprises the following steps:
(1) ferroferric oxide (Fe)3O4) Preparing nano particles:
mixing 1.8g of ferric acetylacetonate, 5.6g of 1, 2-dodecanediol, 4.2g of oleic acid and 4.0g of oleylamine, dissolving in 20ml of benzyl ether, and introducing argon for 30 minutes; mechanically stirring and heating to 250 ℃ under an argon environment, keeping the temperature for reaction for 3 hours, and stopping the reaction; transferring the reaction mixture to a centrifugal tube for centrifugal separation, washing with methanol and acetone until the washing liquid is colorless, and vacuum drying at 60 ℃ for 5 hours to obtain ferroferric oxide (Fe)3O4) Nanoparticles;
(2) ferroferric oxide (Fe)3O4) Surface amination of nanoparticles:
weighing 0.2g of the mixture obtained in the step (1)To ferroferric oxide (Fe)3O4) Dissolving the nano particles in 25ml of secondary distilled water, carrying out ultrasonic treatment for 30 minutes, adding 0.2g of dopamine hydrochloride under the protection of argon, and carrying out ultrasonic reaction for 2 hours; transferring the reaction mixture to a centrifugal tube for centrifugal separation, washing the reaction mixture for multiple times by acetone, and drying the reaction mixture for 5 hours in vacuum at the temperature of 60 ℃ to obtain ferroferric oxide (Fe) with aminated surface3O4) Nanoparticles; the solid loading capacity of dopamine hydrochloride in elemental analysis is 2.20 mmol/g;
(3) preparation of (S) - (1- (4- (chloromethyl) phenyl) -2-pyrrolyl) diphenylmethanol:
the same as example 1;
(4) ferroferric oxide (Fe)3O4) Preparing a nano particle immobilized chiral ligand:
0.2g of ferroferric oxide (Fe) with aminated surface3O4) Nanoparticles, 0.2g of (S) - (1- (4- (chloromethyl) phenyl) -2-pyrrolyl) diphenylmethanol and 0.2g of potassium carbonate were mixed and dissolved in 10ml of acetonitrile; mechanically stirring and heating to 50 ℃ under the protection of argon, preserving heat and reacting for 24 hours, and stopping reaction; adsorbing with strong magnet, separating, washing with methanol and acetone for several times, vacuum drying at 60 deg.C for 5 hr to obtain ferroferric oxide (Fe)3O4) The nano particles are immobilized with chiral ligands, and the average particle size is 10 nm. Elemental analysis the solid loading of the chiral ligand was 1.8mmol/g based on (S) - (1- (4- (chloromethyl) phenyl) -2-pyrrolyl) diphenylmethanol.
Example 3
Ferroferric oxide (Fe)3O4) The preparation method of the nano particle immobilized chiral ligand comprises the following steps:
(1) ferroferric oxide (Fe)3O4) Preparing nano particles:
the same as example 2;
(2) ferroferric oxide (Fe)3O4) Surface amination of nanoparticles:
the same as example 2;
(3) preparation of (S) - (1- (4- (chloromethyl) phenyl) -2-pyrrolyl) diphenylmethanol:
the same as example 2;
(4) ferroferric oxide (Fe)3O4) Preparing a nano particle immobilized chiral ligand:
0.2g of ferroferric oxide (Fe) with aminated surface3O4) Nanoparticles, 0.2g of (S) - (1- (4- (chloromethyl) phenyl) -2-pyrrolyl) benzhydrol and 0.2g of potassium carbonate were mixed and dissolved in 10ml of acetone; mechanically stirring and heating to 50 ℃ under the protection of argon, preserving heat and reacting for 24 hours, and stopping reaction; adsorbing with strong magnet, separating, washing with methanol and acetone for several times, vacuum drying at 60 deg.C for 5 hr to obtain ferroferric oxide (Fe)3O4) The nano particles are immobilized with chiral ligands, and the average particle size is 12 nm. Elemental analysis the solid loading of the chiral ligand was 1.5mmol/g based on (S) - (1- (4- (chloromethyl) phenyl) -2-pyrrolyl) diphenylmethanol.
Example 4
Ferroferric oxide (Fe)3O4) The preparation method of the nano-particle immobilized chiral ligand has the same steps as the example 1 and is different
Is to add Fe (NO) in the step (1)3）3·6H2O and FeCl2·4H2O is dissolved in 10ml of secondary distilled water according to the molar ratio of 2:1, the temperature is raised to 80 ℃ under the protection of argon, and 5ml of 10wt% sodium hydroxide solution is rapidly added under the condition of vigorous mechanical stirring. Elemental analysis the solid loading of the chiral ligand was 1.5mmol/g based on (S) - (1- (4- (chloromethyl) phenyl) -2-pyrrolyl) diphenylmethanol.
Example 5
Ferroferric oxide (Fe)3O4) The preparation method of the nanoparticle-supported chiral ligand has the same steps as example 1, except that triethylamine is used instead of potassium carbonate in steps (3) and (4).
Example 6
The preparation method of the ferroferric oxide (Fe 3O 4) nanoparticle supported chiral ligand has the same steps as the example 2, except that Fe (CO)5 (iron pentacarbonyl) is used for replacing acetylacetone iron in the step (1).
Example 7
The preparation method of the ferroferric oxide (Fe 3O 4) nanoparticle supported chiral ligand comprises the same steps as the example 1, except that dopamine hydrochloride and ferroferric oxide (Fe 3O 4) in the step (2)3O4) The mass ratio of the nano particles is 1.5: 1; the surface aminated ferroferric oxide (Fe) in the step (4)3O4) The mass ratio of the nanoparticles, (S) - (1- (4- (chloromethyl) phenyl) -2-pyrrolyl) diphenyl methanol to the base is 1: 1.5: 1.5.
application example 1
Ferroferric oxide (Fe)3O4) The nano particle immobilized chiral ligand is used for diethyl zinc-aldehyde addition catalytic reaction, and comprises the following steps: under the protection of argon, the catalyst (ferroferric oxide (Fe) prepared in example 13O4) Nano particles carry chiral ligand, 2 mol%) is dissolved in anhydrous toluene solution, and the toluene solution of diethyl zinc with the concentration of 1mol/L is slowly dropped under mechanical stirring, wherein the adding amount of diethyl zinc is 1.2 mmol; mechanically stirring for 30 minutes at room temperature, and slowly dropping 1.0mmol of aromatic aldehyde; the reaction was followed by Thin Layer Chromatography (TLC) and after completion of the reaction saturated NH was added4Quenching with Cl; the catalyst was separated with a magnet, washed with acetone, dried and ready for the next run. Reaction formula is：
Yield of the product1HNMR determination, ee value by high performance liquid chromatography, the test results are shown in Table 1:
TABLE 1
| Ar- (aryl) | Yield of | ee (enantiomeric excess percentage) (%) |
| C6H5(phenyl group) | 100 | 98 |
| p-ClC6H4(p-chlorophenyl) | 99 | 99 |
| p-BrC6H4(p-bromophenyl) | 99 | 99 |
| p-MeC6H4(p-tolyl) | 99 | 99 |
| p-MeOC6H4(p-methoxyphenyl) | 99 | 99 |
| p-NO2C6H4(p-nitrophenyl) | 99 | 99 |
| m-ClC6H4(m-chlorophenyl) | 99 | 99 |
| m-NO2C6H4(m-nitrophenyl) | 99 | 99 |
Application example 2
Ferroferric oxide (Fe)3O4) The nano particle immobilized chiral ligand is used for the addition catalytic reaction of diethyl zinc on aldehyde, and the catalyst is recycled, and the method comprises the following steps:
under the protection of argon, the catalyst used in application example 1 (ferroferric oxide (Fe) prepared in example 1) is recovered3O4) The nano particles are fixedly supported with chiral ligand, 2 mol%) and dissolved in anhydrous toluene solution, and the toluene solution of diethyl zinc with the concentration of 1mol/L is slowly dropped under mechanical stirring, wherein the adding amount of the diethyl zinc is 1.2 mmol; mechanically stirring for 30 minutes at room temperature, and slowly dropping 1.0mmol of aromatic aldehyde; the reaction was followed by Thin Layer Chromatography (TLC) and after completion of the reaction saturated NH was added4Quenching with Cl; the catalyst was separated with a magnet, washed with acetone, dried and ready for the next run. The reaction formula is as follows:
yield of the product1HNMR determination, ee value by high performance liquid chromatography, the test results are shown in Table 2:
TABLE 2
Application example 3
Ferroferric oxide (Fe)3O4) The nano particle immobilized chiral ligand is used for phenylacetylene and aldehyde addition catalytic reaction and comprises the following steps:
under the protection of argon, the catalyst (ferroferric oxide (Fe) prepared in example 13O4) Nano particle supported chiral ligand, 5 mol%) dissolved in anhydrous CH2Cl2In the solution, slowly dropping a toluene solution of diethyl zinc with the concentration of 1mol/L under mechanical stirring, wherein the addition amount of the diethyl zinc is 2.2 mmol; mechanically stirring for 30 minutes at room temperature, and slowly dropping 2.4mmol of phenylacetylene; after mechanically stirring for 1 hour at room temperature, slowly dropping 1.0mmol of aromatic aldehyde; the reaction mixture was reacted at room temperature, followed by Thin Layer Chromatography (TLC), and after completion of the reaction saturated NH was added4Quenching with Cl; the catalyst was separated with a magnet, washed with acetone, dried and ready for the next run. The reaction formula is as follows:
yield of the product1HNMR was measured, ee value was measured by high performance liquid chromatography, and the results are shown in Table 3:
TABLE 3
| Ar- (aryl) | Yield of | ee (enantiomeric excess percentage) (%) |
| C6H5(phenyl group) | 100 | 98 |
| p-ClC6H4(p-chlorophenyl) | 99 | 99 |
| p-BrC6H4(p-bromophenyl) | 99 | 99 |
| p-MeC6H4(p-tolyl) | 99 | 99 |
| p-MeOC6H4(p-methoxyphenyl) | 99 | 99 |
| p-NO2C6H4(p-nitrophenyl) | 99 | 99 |
| m-ClC6H4(m-chlorophenyl) | 99 | 99 |
| m-NO2C6H4(m-nitrophenyl) | 99 | 99 |
Application example 4
Ferroferric oxide (Fe)3O4) The nano particle immobilized chiral ligand is used for phenylacetylene and aldehyde addition catalytic reaction, and the catalyst is recycled, and comprises the following steps:
under the protection of argon, the catalyst used in application example 3 (ferroferric oxide (Fe) prepared in example 1) is recovered3O4) Nano particle supported chiral ligand, 5 mol%) dissolved in anhydrous CH2Cl2In the solution, slowly dropping a toluene solution of diethyl zinc with the concentration of 1mol/L under mechanical stirring, wherein the addition amount of the diethyl zinc is 2.2 mmol; mechanically stirring for 30 minutes at room temperature, and slowly dropping 2.4mmol of phenylacetylene; after mechanically stirring for 1 hour at room temperature, slowly dropping 1.0mmol of aromatic aldehyde; the reaction mixture was reacted at room temperature, followed by Thin Layer Chromatography (TLC), and after completion of the reaction saturated NH was added4Quenching with Cl; the catalyst was separated with a magnet, washed with acetone, dried and ready for the next run. The reaction formula is as follows:
yield of the product1HNMR was measured, ee value was measured by high performance liquid chromatography, and the results are shown in Table 4:
TABLE 4
Claims (6)
1. Ferroferric oxide (Fe)3O4) A process for preparing a nanoparticle-immobilized chiral ligand having the formulaIThe structural formula shown in the specification:
formula (II)I
Formula (II)IIn the formula, A is ferroferric oxide (Fe)3O4) Nanoparticles;
the method comprises the following steps:
(1) ferroferric oxide (Fe)3O4) Preparing nano particles:
preparation by a precipitation method: dissolving ferric salt and ferrous salt in water according to a molar ratio of 2:1, adding an alkali solution at 20-100 ℃ under the protection of inert gas, keeping for 20-30 minutes, naturally cooling to room temperature, separating solid, washing with deionized water to be neutral, and drying in vacuum at 50-60 ℃ to obtain ferroferric oxide (Fe)3O4) Nanoparticles; or,
pyrolysis preparation: dissolving an iron-containing compound in a high-boiling-point solvent, refluxing for 10-60 minutes at 200-300 ℃, naturally cooling to room temperature, separating solids, washing with acetone, and drying in vacuum at 50-60 ℃ to obtain ferroferric oxide (Fe)3O4) Nanoparticles; the high boiling point solvent is 1, 2-dodecanediol, oleic acid, oleylamine, diphenyl ether or benzyl ether;
(2) ferroferric oxide (Fe)3O4) Surface amination of nanoparticles:
the ferroferric oxide (Fe) prepared in the step (1) is added3O4) Dispersing the nano particles into water or ethanol solution, uniformly dispersing, adding dopamine hydrochloride, performing ultrasonic treatment or stirring for 0.5-24 hours, separating solid, washing with acetone, and performing vacuum drying at 50-60 ℃ to obtain ferroferric oxide (Fe) with aminated surface3O4) Nanoparticles; the dopamine hydrochloride and ferroferric oxide (Fe)3O4) The mass ratio of the nano particles is (1-1.5): 1;
（3）(S) Preparation of- (1- (4- (chloromethyl) phenyl) -2-pyrrolyl) benzhydrol:
p-dichlorobenzyl (p-dichlorobenzyl)S) -diphenylprolinol, base in a molar ratio of 1: 1: (1-1.5), dissolving in a solvent, stirring and heating to 50-60 ℃, keeping the temperature for reaction for 24 hours, and stopping the reaction; distilling under reduced pressure to remove solvent, dissolving the residue with ethyl acetate, washing with saturated sodium chloride solution, drying with anhydrous sodium sulfate, distilling under reduced pressure to remove ethyl acetate, and separating by column chromatography to obtainS) - (1- (4- (chloromethyl) phenyl) -2-pyrrolyl) diphenylmethanol; the solvent is acetone, acetonitrile or tetrahydrofuran;
(4) ferroferric oxide (Fe)3O4) Preparing a nano particle immobilized chiral ligand:
carrying out surface amination on ferroferric oxide (Fe) prepared in step (2)3O4) Nanoparticles, the preparation of step (3) (ii)S) - (1- (4- (chloromethyl) phenyl) -2-pyrrolyl) diphenylmethanol and a base in a mass ratio of 1: (1-1.5): (1-1.5) mixing, and dissolving in a solvent; mechanically stirring and heating to 50-60 ℃ in an inert environment, keeping the temperature for reaction for 24 hours, and stopping the reaction; separating the solid, washing with methanol and acetone, and vacuum drying at 50-60 deg.C to obtain black ferroferric oxide (Fe)3O4) The nano particles are immobilized with chiral ligands, and the solvent is acetone, acetonitrile or tetrahydrofuran.
2. Ferroferric oxide (Fe) according to claim 13O4) The preparation method of the nano particle immobilized chiral ligand is characterized in that in the preparation of the nano particle immobilized chiral ligand by the precipitation method in the step (1), the ferric salt is FeCl3·6H2O or Fe (NO)3）3·6H2O; the ferrous salt being FeCl2·4H2O。
3. Ferroferric oxide (Fe) according to claim 13O4) The preparation method of the nano particle immobilized chiral ligand is characterized in that in the preparation of the nano particle immobilized chiral ligand by the precipitation method in the step (1), the alkali solution is 28wt% of concentrated ammonia water or 10wt% of sodium hydroxide solution to prepare ferroferric oxide (Fe)3O4) The average particle diameter of the nanoparticles is 5-20 nm.
4. Ferroferric oxide (Fe) according to claim 13O4) The preparation method of the nanoparticle-immobilized chiral ligand is characterized in that in the step (1) of pyrolysis preparation, the iron-containing compound is Fe (acac)3(iron acetylacetonate), Fe (CO)5(iron pentacarbonyl) or FeCup3Organic iron (N-nitrosohydroxybenzene)Iron amine) to obtain ferroferric oxide (Fe)3O4) The average particle diameter of the nanoparticles is 4-14 nm.
5. Ferroferric oxide (Fe) according to claim 13O4) The preparation method of the nanoparticle-immobilized chiral ligand is characterized in that the base in the step (3) or (4) is triethylamine, pyridine or potassium carbonate.
6. Ferroferric oxide (Fe) according to claim 13O4) The preparation method of the nano particle immobilized chiral ligand is characterized in that the solid separation method in the step (1), (2) or (4) is centrifugal solid separation.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1232462A (en) * | 1996-08-08 | 1999-10-20 | 先灵公司 | Muscarinic antagonists |
| WO2009069959A2 (en) * | 2007-11-30 | 2009-06-04 | Korea University Industrial & Academic Collaboration Foundation | A nanoparticle for separating peptide, method for preparing the same, and method for separating peptide using the same |
| CN102579336A (en) * | 2012-03-07 | 2012-07-18 | 华东师范大学 | MRI(magnetic resonance imaging)-visible hyperstable doxorubicin nanomicelle medicine transmission system, preparation method thereof and use thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1232462A (en) * | 1996-08-08 | 1999-10-20 | 先灵公司 | Muscarinic antagonists |
| WO2009069959A2 (en) * | 2007-11-30 | 2009-06-04 | Korea University Industrial & Academic Collaboration Foundation | A nanoparticle for separating peptide, method for preparing the same, and method for separating peptide using the same |
| CN102579336A (en) * | 2012-03-07 | 2012-07-18 | 华东师范大学 | MRI(magnetic resonance imaging)-visible hyperstable doxorubicin nanomicelle medicine transmission system, preparation method thereof and use thereof |
Non-Patent Citations (3)
| Title |
|---|
| Nanoparticle-supported and magnetically recoverable palladium (Pd) catalyst: a selective and sustainable oxidation protocol with high turnover number;Vivek Polshettiwar等，;《Org. Biomol. Chem.》;20081113;第7卷;第37-40页 * |
| Nanoparticle-Supported and Magnetically Recoverable Ruthenium Hydroxide Catalyst: Efficient Hydration of Nitriles to Amides in Aqueous Medium;Vivek Polshettiwar等，;《Chem. Eur. J.》;20091231;第15卷;第1582-1586页 * |
| The First Magnetic Nanoparticle-Supported Chiral DMAP Analogue: Highly Enantioselective Acylation and Excellent Recyclability;Oliver Gleeson等，;《Chem. Eur. J.》;20091231;第15卷;第5669-5673页，尤其是第5670页方案1 * |
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