CN112808316B - 一种壳聚糖/聚乙烯醇复合膜负载纳米铜催化剂及其应用 - Google Patents
一种壳聚糖/聚乙烯醇复合膜负载纳米铜催化剂及其应用 Download PDFInfo
- Publication number
- CN112808316B CN112808316B CN202110029822.2A CN202110029822A CN112808316B CN 112808316 B CN112808316 B CN 112808316B CN 202110029822 A CN202110029822 A CN 202110029822A CN 112808316 B CN112808316 B CN 112808316B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- reaction
- chitosan
- composite membrane
- copper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 229920001661 Chitosan Polymers 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 239000010949 copper Substances 0.000 title claims abstract description 37
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 35
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 29
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 91
- 239000012528 membrane Substances 0.000 claims abstract description 31
- 239000002904 solvent Substances 0.000 claims abstract description 28
- 239000000758 substrate Substances 0.000 claims abstract description 18
- 150000001639 boron compounds Chemical class 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical class CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 105
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 238000004440 column chromatography Methods 0.000 claims description 21
- 239000012074 organic phase Substances 0.000 claims description 20
- 239000000706 filtrate Substances 0.000 claims description 18
- BMIBJCFFZPYJHF-UHFFFAOYSA-N 2-methoxy-5-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Chemical compound COC1=NC=C(C)C=C1B1OC(C)(C)C(C)(C)O1 BMIBJCFFZPYJHF-UHFFFAOYSA-N 0.000 claims description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 16
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 239000012071 phase Substances 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 9
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 claims description 8
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 8
- 229910001431 copper ion Inorganic materials 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 8
- -1 4-chlorphenyl Chemical group 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000012418 sodium perborate tetrahydrate Substances 0.000 claims description 5
- IBDSNZLUHYKHQP-UHFFFAOYSA-N sodium;3-oxidodioxaborirane;tetrahydrate Chemical compound O.O.O.O.[Na+].[O-]B1OO1 IBDSNZLUHYKHQP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 claims description 4
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 claims description 4
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- 230000005526 G1 to G0 transition Effects 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- IPWKHHSGDUIRAH-UHFFFAOYSA-N bis(pinacolato)diboron Chemical compound O1C(C)(C)C(C)(C)OB1B1OC(C)(C)C(C)(C)O1 IPWKHHSGDUIRAH-UHFFFAOYSA-N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000000741 silica gel Substances 0.000 claims description 4
- 229910002027 silica gel Inorganic materials 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- VBXDEEVJTYBRJJ-UHFFFAOYSA-N diboronic acid Chemical compound OBOBO VBXDEEVJTYBRJJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 claims description 2
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000002390 rotary evaporation Methods 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims 4
- 239000002184 metal Substances 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 26
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 26
- 150000001875 compounds Chemical class 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 15
- 238000000605 extraction Methods 0.000 description 14
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 13
- 238000005160 1H NMR spectroscopy Methods 0.000 description 13
- ZOCHARZZJNPSEU-UHFFFAOYSA-N diboron Chemical compound B#B ZOCHARZZJNPSEU-UHFFFAOYSA-N 0.000 description 13
- 239000003208 petroleum Substances 0.000 description 13
- 238000010898 silica gel chromatography Methods 0.000 description 13
- 239000007858 starting material Substances 0.000 description 13
- 239000013256 coordination polymer Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000036772 blood pressure Effects 0.000 description 1
- UNXISIRQWPTTSN-UHFFFAOYSA-N boron;2,3-dimethylbutane-2,3-diol Chemical compound [B].[B].CC(C)(O)C(C)(C)O UNXISIRQWPTTSN-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
- B01J35/59—Membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
-
- 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/323—Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
-
- 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
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
-
- 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
- C08J2429/00—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 at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- 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
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
Abstract
本发明公布了一种壳聚糖/聚乙烯醇复合膜负载纳米铜催化剂及其应用,该催化剂应用于制备含有α‑取代丙酸酯结构的有机硼化合物,包括以下步骤:在反应容器中加入壳聚糖/聚乙烯醇复合膜负载纳米铜催化剂CP@Cu、溶剂、底物I、碱、联硼酸频那醇酯B2(pin)2,在室温下搅拌反应,反应时间为6~24h,反应结束后,分离提纯,即得含有α‑取代丙酸酯结构的有机硼化合物II。催化剂用量低且可回收使用,反应结束后易于分离,无金属残留,反应条件温和,后处理简单,适合大规模生产。
Description
技术领域
本发明涉及化合物合成领域,具体涉及一种壳聚糖/聚乙烯醇复合膜负载纳米铜催化剂及其应用。
背景技术
含有α-取代丙烯酯结构的分子在药物分子中广泛存在于药物分子中,在降血压和抗病毒方面都取得了显著重大进展。然而这类分子的合成方法步骤繁琐,且成本高,限制了其在实际生产中的进一步应用。近年来,有文献(Angew.Chem.Int.Ed.2017,56,13314–13318)报道利用Cu催化烯烃、芳基化合物和联硼酸频那醇酯三组分化合物合成了含有α-取代丙烯酯结构的硼化物,或者以CO参与反应,采用铜、钯进行催化(Angew.Chem.Int.Ed.2020,59,17055–17061),进一步实现了碳-硼键的转化。但是上述反应在均相体系中进行,金属催化剂难以回收,容易造成在药物合成中有金属残留,严重危害人体健康,且使用纯有机溶剂,对环境污染较大。
随着人们环保意识的日益提高,如何在保证化学反应绿色高效进行的情况下回收和重复利用催化剂已成为一个迫切和备受关注的问题。因此,负载金属催化剂成为了提高效率和回收利用的最好办法之一。目前为止,各种有机和无机材料,如氧化铝、沸石,聚合物以及磁性材料都已经被作为非均相载体研究。壳聚糖作为一种来源广泛的天然聚合物,具有廉价无毒,来源广泛,生物可降解,可再生和环境友好等特点,且含有大量的可供金属配位的氨基(-NH2)和羟基(-OH),但是作为非均相催化剂载体的研究还很少,若能将金属固定在壳聚糖上实现催化含有α-取代丙烯酯结构的硼化物高效合成,将能进一步减少金属离子对环境的污染,并实现催化剂的回收和重复利用,同时使用对壳聚糖亲和力好的水作为溶剂,绿色环保,并能以高产率实现克级反应,在简化实验步骤的基础上进一步提高产率,将进一步为药物合成的工业化生产提高效率。
发明内容
本发明的目的是在于提供了复合壳聚糖膜负载纳米铜催化制备含有α-取代丙烯酯结构的有机硼化物的新方法,以温和的条件实现底物的硼加成反应,制备出含有不同取代基的α-取代丙烯酯有机硼化合物。方法易行,操作简便,该制备方法以复合壳聚糖膜负载纳米铜为催化剂,联硼酸频那醇酯(B2(pin)2)为反应试剂,在水相中反应即可达到很高的反应活性。催化剂用量低且可回收使用,反应结束后易于分离,无金属残留,反应条件温和,后处理简单,适合大规模生产。
其技术方案是:一种壳聚糖/聚乙烯醇复合膜负载纳米铜催化剂,所述催化剂是由壳聚糖与聚乙烯醇通过交联反应后形成水溶性复合薄膜,再洗涤至中性并烘干后,该水溶性复合薄膜加入铜离子水中浸泡至完全变色,再经烘干,再加入硼氢化钠溶液还原铜离子,再洗涤烘干,进而获得壳聚糖/聚乙烯醇复合膜负载纳米铜催化剂,该催化剂以壳聚糖为载体、零价纳米铜粒子为活性组分,其中铜在催化剂中的负载量为催化剂质量的2.6%。
进一步地,所述的壳聚糖/聚乙烯醇复合膜负载纳米铜催化剂应用于制备含有α-取代丙酸酯结构的有机硼化合物,包括以下步骤:
在反应容器中加入壳聚糖/聚乙烯醇复合膜负载纳米铜催化剂CP@Cu、溶剂、底物I、碱、联硼酸频那醇酯B2(pin)2,在室温下搅拌反应,反应时间为6~24h,反应结束后,分离提纯,即得含有α-取代丙酸酯结构的有机硼化合物II;
化学反应方程式如下:
其中,R1基团为苯基、4-甲基苯基、4-氟苯基,R2基团为甲基、苯基、4-甲基苯基、4-甲氧基苯基、4-氟苯基、4-氯苯基、4-溴苯基、2-萘基;
所述溶剂为去离子水,所述碱包括三乙胺,苯胺,吡啶,4-甲基苯胺,4-甲氧基苯胺,4-硝基苯胺中的一种;
所述底物I与溶剂的添加比为0.2mol:2~3ml,所述的联硼酸频那醇酯B2(pin)2与底物I的物质的量之比为1.0-2.0:1,所述壳聚糖/聚乙烯醇复合膜负载纳米铜催化剂中铜离子的摩尔量为底物I摩尔量的1%,所述碱的摩尔量为底物I摩尔量的3%。
进一步地,所述碱为4-甲基苯胺。
优选地,所述的联硼酸频那醇酯B2(pin)2与底物I的物质的量之比为1:1。
优选地,所述的反应时间为12h。
进一步地,所述分离提纯包括以下步骤:过滤整个反应体系,滤液转入分液漏斗并加入饱和食盐水,再用乙酸乙酯萃取,将得到的有机相除去多余溶剂后利用柱层析法,通过控制流动相的比例分离提纯得到含有α-取代丙酸酯结构的有机硼化合物II,柱层析采用硅胶为固定相。
进一步地,所述催化剂应用于制备β-羟基化合物的反应,所述分离提纯还包括以下步骤:过滤整个反应体系,滤液转入分液漏斗并加入饱和食盐水,再用乙酸乙酯萃取,将得到的有机相除去多余溶剂后直接加入过硼酸钠四水合物、四氢呋喃和水,在室温下搅拌3-5小时,再加入乙酸乙酯稀释,以乙酸乙酯萃取,分离出有机相后,用无水硫酸钠干燥,过滤,旋转蒸发除去溶剂,残留物经柱层析纯化,得到β-羟基化合物III,柱层析采用硅胶为固定相,所述过硼酸钠四水合物与底物I的摩尔比为4:1,化学反应方程式如下:
其中,R1基团为苯基、4-甲基苯基、4-氟苯基,R2基团为甲基、苯基、4-甲基苯基、4-甲氧基苯基、4-氟苯基、4-氯苯基、4-溴苯基、2-萘基。
有利地,上述反应中在壳聚糖/聚乙烯醇复合膜负载纳米铜催化剂的催化下,底物I和联硼酸频那醇酯(B2(pin)2(结构如化学反应方程式所示)吸附于催化剂表面而彼此相互靠近。零价铜与4-甲基苯胺、联硼酸频那醇酯与形成复合金属络合物,通过氧化环金属化,金属转移和还原消除完成直接硼加成的过程,制备得到有机硼化合物。反应结束后,通过简单的过滤操作回收催化剂,向残留反应体系中加入过硼酸钠,将有机硼化合物直接氧化为β-羟基化合物III。
该壳聚糖/聚乙烯醇复合膜负载纳米铜催化剂与CN106892935B和CN107573370A所使用的壳聚糖微球负载的二价铜离子相比,本发明所述催化剂负载的为零价铜,首次使用负载零价铜纳米粒子的壳聚糖/聚乙烯醇复合膜实现α-取代丙烯酸酯的硼加成反应,使用负载二价铜离子的催化剂催化目标产物产率不足30%,反应活性非常低,且需要使用有机溶剂,无法实现回收利用。相比而言,铜在催化剂中以纳米粒子形态存在,分散均匀,负载量小,非均相零价铜相比于二价铜在反应过程中不易脱落,催化剂寿命长,多次重复回收利用后依然具有很高的活性。
以I为原料经过氧化生成产物III为例,在反应结束后,通过过滤回收催化剂,直接用于下一轮反应,重复该步骤五次得到目标产物的产率分别为92%,90%,90%,92%,91%,证明催化剂活性几乎没有任何损失,可循环利用。
壳聚糖/聚乙烯醇复合薄膜可通过商业购买,廉价易得,壳聚糖的高比表面积使得载体上的金属铜分散度高,聚乙烯醇亲水性强,与壳聚糖共混交联后,一方面提高了共混后形成的膜的强度和韧性,另一方面也增加了共混后膜的亲水性,使得该复合膜能运用于纯水中参与硼加成反应,因此反应不用使用有机溶剂,反应绿色环保,因而大大降低了生产成本,和减少污染,同时反应完成后可方便的过滤回收复合膜。
本发明于现有技术相比,具有以下优点和效果
1.方法易行,操作简便,原料来源丰富,成本较低,如功能化壳聚糖,氯化铜等,利于该方法在实际生产中的应用;
2.该方法仅需要使用较低的催化剂用量,即可实现反应物较高的转化数;
3.该方法反应条件温和,在室温下进行反应,简便易操作;
4.该方法应用性广,可适用于各种不同类型的底物,成功制备出相应的目标化合物;
5.该方法中整个反应体系为非均相,催化剂在反应结束后可以很方便的借由过滤除去;
6.该方法在克级反应中仍能保证高产率,具有实际应用的前景。
附图说明
图1为本发明的壳聚糖/聚乙烯醇复合膜负载纳米铜催化剂的红外图谱;
图2为本发明的壳聚糖/聚乙烯醇复合膜负载纳米铜催化剂的扫描电镜图。
具体实施方式
以下对本发明的原理和特征进行描述,所举实施例只用于解释本发明,并非用于限定本发明的范围。
下面通过实施例,进一步阐明本发明的突出特点,仅在于说明本发明而决不限制本发明。当起始原料为α-取代丙烯酸化合物I时,制备得到α-取代有机硼化合物II,进而转化为β-羟基化合物III;
一种壳聚糖/聚乙烯醇复合膜负载纳米铜催化剂,详细制备过程如下:
将300mg壳聚糖粉末加入50mL的反应烧瓶中,加入20mL乙酸溶液(1v/v-%),在室温条件下搅拌12小时;将200mg聚乙烯醇和10mL的蒸馏水加入到50mL的烧瓶中,然后密封,在60℃加热条件下搅拌至完全溶解;在室温条件下,将壳聚糖溶液和聚乙烯醇溶液混合搅拌半小时至均匀,然后边搅拌边逐滴添加50μL质量分数为35w/w%的戊二醛溶液,5分钟后,将混合溶液倒入培养皿中,在40℃的烘箱中放置24小时至水分全部蒸发,得到;将壳聚糖/聚乙烯醇膜(CP膜)从培养皿上剥离,浸泡在100mL的氢氧化钠溶液(0.3mol/L)中5分钟,然后用蒸馏水洗涤几次直至pH试纸检测为中性,最后,继续将CP膜在40℃烘箱中烘干24小时(黄色膜),将CP膜浸泡在25mL的CuCl2·2H2O溶液(0.2mol/L)中2.5小时,然后收集吸附Cu2+离子的膜(表示为CP@Cu2+),放入40℃烘箱干燥24小时(绿色膜);将CP@Cu2+膜浸泡在新鲜制备的100mL硼氢化钠溶液(50mmol/L)中15分钟,然后取出膜,使用蒸馏水中洗涤几次,继续放入40℃烤箱干燥24小时,得到负载铜纳米颗粒的CP膜即为CP@Cu NPs(黑色膜)。电感耦合等离子体原子发射光谱测试结果表明材料中铜的质量百分含量为2.6%。如图1将CP@CuNPs和壳聚糖进行红外测试,发现CP@Cu NPs的红外图谱中壳聚糖的N-H和O-H带有些偏移,还观察到了交联剂的乙烯基带,证明了戊二醛与壳聚糖的交联反应(如图1的IR表征);如图2,CP@Cu NPs的扫描电镜(SEM)图中,显示出光滑的表面,没有大的聚集体,说明CP膜对纳米铜颗粒具有很好的稳定作用;
实施例1:
化合物II-1的制备方法,其步骤是:
A、在3mL反应瓶中加入起始原料I-1:(0.2mmol)、联硼酸频那醇酯(B2(pin2))(0.2mmol)、CP@Cu(5mg)、4-甲基苯胺(3mmol%)、磁子、去离子水(3mL),在室温(20-25℃,以下相同)下搅拌12小时。
B、反应结束后,过滤整个反应体系,滤液转入分液漏斗并加入15mL饱和食盐水,用15mL乙酸乙酯萃取,将得到的有机相除去多余溶剂后利用柱层析法,通过控制流动相的比例分离(乙酸乙酯:石油醚=1:10),利用硅胶柱层析法提纯得到硼化物II-1 61.9mg,产率92%。
1H NMR(400MHz,Chloroform-d);δ=8.00–7.85(m,2H),7.48–7.40(m,1H),7.34(t,J=7.5Hz,2H),7.30–7.21(m,4H),7.18–7.11(m,1H),4.85–4.69(m,1H),1.58(dd,J=15.9,9.2Hz,1H),1.34(dd,J=15.9,6.7Hz,1H),1.19(s,6H),1.12(s,6H).
13C NMR(101MHz,Chloroform-d);δ=200.74,142.00,136.65,132.48,128.89,128.86,128.30,128.00,126.69,83.23,50.17,24.80,24.59.
通过过滤回收催化剂,直接重复以上步骤用于下一轮反应,重复该步骤五次得到目标产物的产率分别为92%,90%,90%,92%,91%,证明催化剂活性几乎没有任何损失,可循环利用。
实施例2:
化合物II-2的制备方法,其步骤是:
A、在3mL反应瓶中加入起始原料I-2:(0.2mmol)、联硼酸频那醇酯(B2(pin2))(0.2mmol)、CP@Cu(5mg)、4-甲基苯胺(3mmol%)、磁子、去离子水(3mL),在室温(20-25℃,以下相同)下搅拌12小时。
B、反应结束后,过滤整个反应体系,滤液转入分液漏斗并加入15mL饱和食盐水,用15mL乙酸乙酯萃取,将得到的有机相除去多余溶剂后利用柱层析法,通过控制流动相的比例分离(乙酸乙酯:石油醚=1:10),利用硅胶柱层析法提纯得到硼化物II-2 66.5mg,产率95%。
1H NMR(400MHz,Chloroform-d);δ=7.97–7.87(m,2H),7.47–7.39(m,1H),7.38–7.29(m,2H),7.15(d,J=8.1Hz,2H),7.05(d,J=7.9Hz,2H),4.81–4.71(m,1H),2.25(s,3H),1.57(dd,J=15.9,9.5Hz,1H),1.30(dd,J=15.9,6.5Hz,1H),1.19(s,6H),1.13(s,6H).
13C NMR(101MHz,Chloroform-d);δ=200.88,139.03,136.68,136.25,132.42,129.59,128.91,128.28,127.81,83.21,49.81,24.81,24.60,21.05.
实施例3:
化合物II-3的制备方法,其步骤是:
A、在3mL反应瓶中加入起始原料I-3:(0.2mmol)、联硼酸频那醇酯(B2(pin2))(0.2mmol)、CP@Cu(5mg)、4-甲基苯胺(3mmol%)、磁子、去离子水(3mL),在室温(20-25℃,以下相同)下搅拌12小时。
B、反应结束后,过滤整个反应体系,滤液转入分液漏斗并加入15mL饱和食盐水,用15mL乙酸乙酯萃取,将得到的有机相除去多余溶剂后利用柱层析法,通过控制流动相的比例分离(乙酸乙酯:石油醚=1:10),利用硅胶柱层析法提纯得到硼化物II-3 75.4mg,产率91%。
1H NMR(400MHz,Chloroform-d);δ=7.96–7.83(m,2H),7.61–7.53(m,1H),7.48–7.42(m,1H),7.39–7.32(m,2H),7.17–7.11(m,1H),7.08–6.98(m,2H),5.25–5.06(m,1H),1.40(dd,J=15.8,10.2Hz,1H),1.29(dd,J=15.8,5.6Hz,1H),1.22(s,6H),1.16(s,6H).
13C NMR(101MHz,Chloroform-d);δ=200.53,141.83,136.15,133.20,132.73,129.00,128.85,128.42,128.30,128.12,123.81,83.25,49.64,24.85,24.55.
实施例4:
化合物II-4的制备方法,其步骤是:
A、在3mL反应瓶中加入起始原料I-4:(0.2mmol)、联硼酸频那醇酯(B2(pin2))(0.2mmol)、CP@Cu(5mg)、4-甲基苯胺(3mmol%)、磁子、去离子水(3mL),在室温(20-25℃,以下相同)下搅拌12小时。
B、反应结束后,过滤整个反应体系,滤液转入分液漏斗并加入15mL饱和食盐水,用15mL乙酸乙酯萃取,将得到的有机相除去多余溶剂后利用柱层析法,通过控制流动相的比例分离(乙酸乙酯:石油醚=1:10),利用硅胶柱层析法提纯得到硼化物II-4 63.8mg,产率90%。
1H NMR(400MHz,Chloroform-d);δ=7.96–7.88(m,2H),7.50–7.43(m,1H),7.41–7.33(m,2H),7.28–7.20(m,2H),6.99–6.89(m,2H),4.84–4.75(m,1H),1.55(dd,J=16.0,8.8Hz,1H),1.34(dd,J=15.9,7.2Hz,1H),1.18(s,6H),1.13(s,6H).
13C NMR(101MHz,Chloroform-d);δ=200.64,162.86,160.43,137.59,137.56,136.42,132.66,129.60,129.52,128.84,128.40,115.80,115.58,83.31,49.12,24.76,24.61.
实施例5:
化合物II-5的制备方法,其步骤是:
A、在3mL反应瓶中加入起始原料I-5:(0.2mmol)、联硼酸频那醇酯(B2(pin2))(0.2mmol)、CP@Cu(5mg)、4-甲基苯胺(3mmol%)、磁子、去离子水(3mL),在室温(20-25℃,以下相同)下搅拌12小时。
B、反应结束后,过滤整个反应体系,滤液转入分液漏斗并加入15mL饱和食盐水,用15mL乙酸乙酯萃取,将得到的有机相除去多余溶剂后利用柱层析法,通过控制流动相的比例分离(乙酸乙酯:石油醚=1:10),利用硅胶柱层析法提纯得到硼化物II-5 71.4mg,产率96%。
1H NMR(400MHz,Chloroform-d);δ=7.90(d,J=7.1Hz,2H),7.50–7.43(m,1H),7.40–7.32(m,2H),7.22(d,J=1.3Hz,4H),4.83–4.74(m,1H),1.55(dd,J=16.0,8.9Hz,1H),1.32(dd,J=16.0,6.9Hz,1H),1.18(s,6H),1.13(s,6H).
13C NMR(101MHz,Chloroform-d);δ=200.38,140.43,136.35,132.73,132.55,129.39,129.01,128.84,128.42,83.35,49.33,24.77,24.62.
实施例6:
化合物II-6的制备方法,其步骤是:
A、在3mL反应瓶中加入起始原料I-6:(0.2mmol)、联硼酸频那醇酯(B2(pin2))(0.2mmol)、CP@Cu(5mg)、4-甲基苯胺(3mmol%)、磁子、去离子水(3mL),在室温(20-25℃,以下相同)下搅拌12小时。
B、反应结束后,过滤整个反应体系,滤液转入分液漏斗并加入15mL饱和食盐水,用15mL乙酸乙酯萃取,将得到的有机相除去多余溶剂后利用柱层析法,通过控制流动相的比例分离(乙酸乙酯:石油醚=1:10),利用硅胶柱层析法提纯得到硼化物II-6 77.2mg,产率93%。
1H NMR(400MHz,Chloroform-d);δ=7.95–7.84(m,2H),7.46(d,J=7.3Hz,1H),7.42–7.33(m,4H),7.21–7.10(m,2H),4.82–4.68(m,1H),1.55(dd,J=16.0,9.0Hz,1H),1.31(dd,J=16.0,6.9Hz,1H),1.18(s,6H),1.13(s,6H).
13C NMR(101MHz,Chloroform-d);δ=200.29,140.97,136.33,132.75,131.96,129.76,128.85,128.43,120.67,83.35,49.41,24.77,24.63.
实施例7:
化合物II-7的制备方法,其步骤是:
A、在3mL反应瓶中加入起始原料I-7:(0.2mmol)、联硼酸频那醇酯(B2(pin2))(0.2mmol)、CP@Cu(5mg)、4-甲基苯胺(3mmol%)、磁子、去离子水(3mL),在室温(20-25℃,以下相同)下搅拌12小时。
B、反应结束后,过滤整个反应体系,滤液转入分液漏斗并加入15mL饱和食盐水,用15mL乙酸乙酯萃取,将得到的有机相除去多余溶剂后利用柱层析法,通过控制流动相的比例分离(乙酸乙酯:石油醚=1:10),利用硅胶柱层析法提纯得到硼化物II-7 72.2mg,产率99%。
1H NMR(400MHz,Chloroform-d);δ=7.93–7.87(m,2H),7.44–7.38(m,1H),7.30(t,J=7.5Hz,2H),7.17–7.07(m,2H),6.86–6.75(m,2H),5.16–5.04(m,1H),3.82(s,3H),1.48(dd,J=15.7,10.0Hz,1H),1.28–1.24(m,1H),1.22(s,6H),1.15(s,6H).
13C NMR(101MHz,Chloroform-d);δ=201.64,155.70,136.66,132.23,130.99,128.67,128.63,128.10,127.84,121.01,110.72,83.06,55.29,43.66,24.87,24.55.
实施例8:
化合物II-8的制备方法,其步骤是
A、在3mL反应瓶中加入起始原料I-8:(0.2mmol)、联硼酸频那醇酯(B2(pin2))(0.2mmol)、CP@Cu(5mg)、4-甲基苯胺(3mmol%)、磁子、去离子水(3mL),在室温(20-25℃,以下相同)下搅拌12小时。
B、反应结束后,过滤整个反应体系,滤液转入分液漏斗并加入15mL饱和食盐水,用15mL乙酸乙酯萃取,将得到的有机相除去多余溶剂后利用柱层析法,通过控制流动相的比例分离(乙酸乙酯:石油醚=1:10),利用硅胶柱层析法提纯得到硼化物II-8 70.2mg,产率96%。
1H NMR(400MHz,Chloroform-d);δ=7.97–7.89(m,2H),7.48–7.41(m,1H),7.35(t,J=7.5Hz,2H),7.17(t,J=7.9Hz,1H),6.86(d,J=7.7Hz,1H),6.80(t,J=2.1Hz,1H),6.73–6.63(m,1H),4.80–4.71(m,1H),3.74(s,3H),1.58(dd,J=15.9,9.5Hz,1H),1.32(dd,J=15.9,6.4Hz,1H),1.20(s,6H),1.14(s,6H).
13C NMR(101MHz,Chloroform-d);δ=200.60,159.84,143.62,136.59,132.53,129.88,128.90,128.32,120.39,113.37,112.19,83.25,55.16,50.30,24.83,24.59.
实施例9:
化合物II-9的制备方法,其步骤是
A、在3mL反应瓶中加入起始原料I-9:(0.2mmol)、联硼酸频那醇酯(B2(pin2))(0.2mmol)、CP@Cu(5mg)、4-甲基苯胺(3mmol%)、磁子、去离子水(3mL),在室温(20-25℃,以下相同)下搅拌12小时。
B、反应结束后,过滤整个反应体系,滤液转入分液漏斗并加入15mL饱和食盐水,用15mL乙酸乙酯萃取,将得到的有机相除去多余溶剂后利用柱层析法,通过控制流动相的比例分离(乙酸乙酯:石油醚=1:10),利用硅胶柱层析法提纯得到硼化物II-9 67.2mg,产率92%。
1H NMR(400MHz,Chloroform-d);δ=7.97–7.88(m,2H),7.48–7.40(m,1H),7.38–7.31(m,2H),7.23–7.12(m,2H),6.83–6.71(m,2H),4.79–4.70(m,1H),3.73(s,3H),1.55(dd,J=15.9,9.1Hz,1H),1.32(dd,J=15.9,6.9Hz,1H),1.19(s,6H),1.13(s,6H).
13C NMR(101MHz,Chloroform-d);δ=200.93,158.28,136.66,134.01,132.43,129.03,128.88,128.30,114.23,83.21,55.19,49.22,24.80,24.62.
实施例10:
化合物II-10的制备方法,其步骤是
A、在3mL反应瓶中加入起始原料I-10:(0.2mmol)、联硼酸频那醇酯(B2(pin2))(0.2mmol)、CP@Cu(5mg)、4-甲基苯胺(3mmol%)、磁子、去离子水(3mL),在室温(20-25℃,以下相同)下搅拌12小时。
B、反应结束后,过滤整个反应体系,滤液转入分液漏斗并加入15mL饱和食盐水,用15mL乙酸乙酯萃取,将得到的有机相除去多余溶剂后利用柱层析法,通过控制流动相的比例分离(乙酸乙酯:石油醚=1:10),利用硅胶柱层析法提纯得到硼化物II-10 72.6mg,产率99%。
1H NMR(400MHz,Chloroform-d);δ=7.99–7.92(m,2H),7.78–7.68(m,4H),7.44–7.36(m,4H),7.34–7.26(m,2H),5.04–4.86(m,1H),1.68(dd,J=16.0,9.2Hz,1H),1.42(dd,J=16.0,6.7Hz,1H),1.19(s,6H),1.12(s,6H).
13C NMR(101MHz,Chloroform-d);δ=200.69,139.65,136.62,133.67,132.56,132.28,128.96,128.73,128.36,127.75,127.64,126.70,126.16,126.09,125.69,83.30,50.35,24.81,24.67.
实施例11:
化合物II-11的制备方法,其步骤是
A、在3mL反应瓶中加入起始原料I-11:(0.2mmol)、联硼酸频那醇酯(B2(pin2))(0.2mmol)、CP@Cu(5mg)、4-甲基苯胺(3mmol%)、磁子、去离子水(3mL),在室温(20-25℃,以下相同)下搅拌12小时。
B、反应结束后,过滤整个反应体系,滤液转入分液漏斗并加入15mL饱和食盐水,用15mL乙酸乙酯萃取,将得到的有机相除去多余溶剂后利用柱层析法,通过控制流动相的比例分离(乙酸乙酯:石油醚=1:10),利用硅胶柱层析法提纯得到硼化物II-11 69.6mg,产率96%。
1H NMR(400MHz,Chloroform-d);δ=7.83(d,J=8.3Hz,2H),7.18–7.10(m,4H),7.05(d,J=7.8Hz,2H),4.78–4.68(m,1H),2.32(s,3H),2.25(s,3H),1.55(dd,J=15.9,9.4Hz,1H),1.29(dd,J=15.9,6.5Hz,1H),1.19(s,6H),1.13(s,6H).
13C NMR(101MHz,Chloroform-d);δ=200.39,143.11,139.32,136.14,134.04,129.56,129.06,129.00,127.77,83.17,49.68,24.82,24.59,21.62,21.07.
实施例12:
化合物II-12的制备方法,其步骤是
A、在3mL反应瓶中加入起始原料I-12:(0.2mmol)、联硼酸频那醇酯(B2(pin2))(0.2mmol)、CP@Cu(5mg)、4-甲基苯胺(3mmol%)、磁子、去离子水(3mL),在室温(20-25℃,以下相同)下搅拌12小时。
B、反应结束后,过滤整个反应体系,滤液转入分液漏斗并加入15mL饱和食盐水,用15mL乙酸乙酯萃取,将得到的有机相除去多余溶剂后利用柱层析法,通过控制流动相的比例分离(乙酸乙酯:石油醚=1:10),利用硅胶柱层析法提纯得到硼化物II-12 70.7mg,产率96%。
1H NMR(400MHz,Chloroform-d);δ=7.83(d,J=8.3Hz,2H),7.29–7.20(m,2H),7.16(d,J=8.0Hz,2H),6.93(t,J=8.7Hz,2H),4.82–4.70(m,1H),2.34(s,3H),1.53(dd,J=15.9,8.7Hz,1H),1.33(dd,J=15.9,7.2Hz,1H),1.18(s,6H),1.12(s,6H).
13C NMR(101MHz,Chloroform-d);δ=200.15,162.81,160.38,143.43,137.85,137.82,133.79,129.56,129.48,129.10,129.01,115.75,115.54,83.27,48.97,24.77,24.61,21.63.
实施例13:
化合物II-13的制备方法,其步骤是:
A、在3mL反应瓶中加入起始原料I-1:(0.2mmol)、联硼酸频那醇酯(B2(pin2))(0.2mmol)、CP@Cu(5mg)、4-甲基苯胺(3mmol%)、磁子、去离子水(3mL),在室温(20-25℃,以下相同)下搅拌12小时。
B、反应结束后,过滤整个反应体系,滤液转入分液漏斗并加入15mL饱和食盐水,用15mL乙酸乙酯萃取,将得到的有机相除去多余溶剂后转入烧瓶,加入四氢呋喃(2mL)和水(1.5mL),并加入244mg四水合过硼酸钠,在室温下搅拌4小时。
C、反应结束后,过滤整个反应体系,滤液转入分液漏斗并加入15mL饱和食盐水,用15mL乙酸乙酯萃取,将得到的有机相除去多余溶剂后利用柱层析法,通过控制流动相的比例分离(乙酸乙酯:石油醚=1:4),利用硅胶柱层析法提纯得到硼化物III-1 42.9mg,产率95%。
1H NMR(400MHz,Chloroform-d);δ=7.98–7.87(m,2H),7.47(t,J=7.4Hz,1H),7.40– 7.19(m,7H),4.80(dd,J=8.5,4.8Hz,1H),4.28(dd,J=11.4,8.5Hz,1H),3.87(dd,J=11.4,4.7Hz,1H),2.62(s,1H).
13C NMR(101MHz,Chloroform-d);δ=199.98,136.21,136.17,133.30,129.24,128.93,128.58,128.45,127.64,65.19,56.44.
以上所述仅为本发明的较佳实施例,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (6)
1.一种壳聚糖/聚乙烯醇复合膜负载纳米铜催化剂的应用,其特征在于,所述催化剂是由壳聚糖与聚乙烯醇通过交联反应后形成水溶性复合薄膜,再洗涤至中性并烘干后,该水溶性复合薄膜加入铜离子水中浸泡至完全变色,再经烘干,再加入硼氢化钠溶液还原铜离子,再洗涤烘干,进而获得壳聚糖/聚乙烯醇复合膜负载纳米铜催化剂,该催化剂以壳聚糖为载体、零价纳米铜粒子为活性组分,其中铜在催化剂中的负载量为催化剂质量的2.6%,所述催化剂应用于制备含有α-取代丙烯酯结构的有机硼化合物的反应,包括以下步骤:
在反应容器中加入壳聚糖/聚乙烯醇复合膜负载纳米铜催化剂CP@Cu、溶剂、底物I、碱、联硼酸频那醇酯B2(pin)2,在室温下搅拌反应,反应时间为6~24h,反应结束后,分离提纯,即得含有α-取代丙酸酯结构的有机硼化合物II;
化学反应方程式如下:
其中,R1基团为苯基、4-甲基苯基、4-氟苯基,R2基团为甲基、苯基、4-甲基苯基、4-甲氧基苯基、4-氟苯基、4-氯苯基、4-溴苯基、2-萘基;
所述溶剂为去离子水,所述碱包括三乙胺,苯胺,吡啶,4-甲基苯胺,4-甲氧基苯胺,4-硝基苯胺中的一种;
所述底物I与溶剂的添加比为0.2mol:2~3ml,所述的联硼酸频那醇酯B2(pin)2与底物I的物质的量之比为1.0-2.0:1,所述壳聚糖/聚乙烯醇复合膜负载纳米铜催化剂中铜离子的摩尔量为底物I摩尔量的1%,所述碱的摩尔量为底物I摩尔量的3%。
2.根据权利要求1所述的应用,其特征在于,所述碱为4-甲基苯胺。
3.根据权利要求1所述的应用,其特征在于,所述的联硼酸频那醇酯B2(pin)2与底物I的物质的量之比为1:1。
4.根据权利要求1所述的应用,其特征在于,所述的反应时间为12h。
5.根据权利要求1所述的应用,其特征在于,所述分离提纯包括以下步骤:过滤整个反应体系,滤液转入分液漏斗并加入饱和食盐水,再用乙酸乙酯萃取,将得到的有机相除去多余溶剂后利用柱层析法,通过控制流动相的比例分离提纯得到含有α-取代丙酸酯结构的有机硼化合物II,柱层析采用硅胶为固定相。
6.根据权利要求1所述的应用,其特征在于,所述催化剂应用于制备β-羟基化合物的反应,所述分离提纯还包括以下步骤:过滤整个反应体系,滤液转入分液漏斗并加入饱和食盐水,再用乙酸乙酯萃取,将得到的有机相除去多余溶剂后直接加入过硼酸钠四水合物、四氢呋喃和水,在室温下搅拌3-5小时,再加入乙酸乙酯稀释,以乙酸乙酯萃取,分离出有机相后,用无水硫酸钠干燥,过滤,旋转蒸发除去溶剂,残留物经柱层析纯化,得到β-羟基化合物III,柱层析采用硅胶为固定相,所述过硼酸钠四水合物与底物I的摩尔比为4:1,化学反应方程式如下:
其中,R1基团为苯基、4-甲基苯基、4-氟苯基,R2基团为甲基、苯基、4-甲基苯基、4-甲氧基苯基、4-氟苯基、4-氯苯基、4-溴苯基、2-萘基。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110029822.2A CN112808316B (zh) | 2021-01-11 | 2021-01-11 | 一种壳聚糖/聚乙烯醇复合膜负载纳米铜催化剂及其应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110029822.2A CN112808316B (zh) | 2021-01-11 | 2021-01-11 | 一种壳聚糖/聚乙烯醇复合膜负载纳米铜催化剂及其应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN112808316A CN112808316A (zh) | 2021-05-18 |
CN112808316B true CN112808316B (zh) | 2022-05-20 |
Family
ID=75868573
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110029822.2A Active CN112808316B (zh) | 2021-01-11 | 2021-01-11 | 一种壳聚糖/聚乙烯醇复合膜负载纳米铜催化剂及其应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN112808316B (zh) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107691969A (zh) * | 2017-09-21 | 2018-02-16 | 华南协同创新研究院 | 一种低分子壳聚糖@银纳米颗粒复合膜及制备方法和应用 |
CN110590819A (zh) * | 2019-08-28 | 2019-12-20 | 湖北工程学院 | 有机硼化合物的制备方法以及β-羟基有机硼化合物的制备方法 |
CN111995635A (zh) * | 2020-09-09 | 2020-11-27 | 湖北工程学院 | 壳聚糖负载铜膜材料催化制备有机硅化合物的方法 |
-
2021
- 2021-01-11 CN CN202110029822.2A patent/CN112808316B/zh active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107691969A (zh) * | 2017-09-21 | 2018-02-16 | 华南协同创新研究院 | 一种低分子壳聚糖@银纳米颗粒复合膜及制备方法和应用 |
CN110590819A (zh) * | 2019-08-28 | 2019-12-20 | 湖北工程学院 | 有机硼化合物的制备方法以及β-羟基有机硼化合物的制备方法 |
CN111995635A (zh) * | 2020-09-09 | 2020-11-27 | 湖北工程学院 | 壳聚糖负载铜膜材料催化制备有机硅化合物的方法 |
Non-Patent Citations (1)
Title |
---|
Zeus H. Pinedo-Guerrero et al..Cu Nanoparticles in Hydrogels of Chitosan-PVA Affects the Characteristics of Post-Harvest and Bioactive Compounds of Jalapeño Pepper.《Molecules》.2017,第22卷第926页. * |
Also Published As
Publication number | Publication date |
---|---|
CN112808316A (zh) | 2021-05-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN111995635B (zh) | 壳聚糖负载铜膜材料催化制备有机硅化合物的方法 | |
AU687014B2 (en) | Metal-mediated cross-coupling with ring-metalated porphyrins | |
Hajipour et al. | Proline-functionalized chitosan–palladium (ii) complex, a novel nanocatalyst for C–C bond formation in water | |
CN108329194B (zh) | 一种香茅醛制备异胡薄荷醇的方法及其催化剂的回收方法 | |
CN110590820B (zh) | 手性有机硼化合物的制备方法 | |
JP5217457B2 (ja) | アジド−アルキン付加環化反応触媒及びそれを用いたトリアゾール化合物の製造方法 | |
CN112778218A (zh) | 一种壳聚糖负载铜催化剂制备喹唑酮及其衍生物的方法 | |
Deng et al. | Optically active microspheres from helical substituted polyacetylene with pendent ferrocenyl amino-acid derivative. Preparation and recycling use for direct asymmetric aldol reaction in water | |
CN105964306B (zh) | 一种基于聚离子液体磁性纳米粒子、制备方法及其在三组分反应中的应用 | |
CN112321628B (zh) | β-二甲基苯基硅取代有机腈类化合物的制备方法 | |
CN103408756A (zh) | 可回收利用的负载型一价铜催化剂催化的制备聚三唑的方法以及制得的聚三唑 | |
CN112808316B (zh) | 一种壳聚糖/聚乙烯醇复合膜负载纳米铜催化剂及其应用 | |
CN113061145A (zh) | 纤维素负载铜催化制备手性有机硼化合物的方法及应用 | |
CN115160634B (zh) | 一种阳离子型多孔材料及其制备方法和应用 | |
CN112778351B (zh) | β-二甲基苯基硅取代芳香硝基化合物的制备方法 | |
CN112898326A (zh) | 有机硼化合物的制备方法及应用、β-羟基化合物的制备方法及应用 | |
CN101279292A (zh) | 一种用于含氟烯烃硅氢加成反应的催化剂及制备方法 | |
CN107880220B (zh) | 聚合手性氨基酸配体的合成方法及其产品和应用 | |
CN115350724B (zh) | 一种用于合成恶唑烷酮的双功能聚离子液体催化剂的制备方法 | |
Yang et al. | An efficient silica-grafted poly-(L)-leucine catalyst for asymmetric epoxidation of α, β-unsaturated ketone | |
CN110845291A (zh) | 一种可见光诱导催化还原炔烃为烯烃的方法 | |
JP2009028645A (ja) | パラジウム不均一系触媒 | |
CN112517007B (zh) | 一种高岭土负载纳米铁催化剂及其在交叉脱氢偶联反应中的应用 | |
CN115057996B (zh) | 4CzIPN型多孔有机聚合物的制备方法及其应用 | |
CN113387852B (zh) | 一种亚砜类化合物的制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20210518 Assignee: HUBEI HENDRY MEDICAL APPLIANCE Co.,Ltd. Assignor: HUBEI ENGINEERING University Contract record no.: X2023980048823 Denomination of invention: A Chitosan/Polyvinyl Alcohol Composite Membrane Supported Nanocopper Catalyst and Its Application Granted publication date: 20220520 License type: Common License Record date: 20231130 |
|
EE01 | Entry into force of recordation of patent licensing contract |