CN116693816A - Palladium-nitrogen heterocyclic carbene skeleton organic porous polymer, and preparation method and application thereof - Google Patents
Palladium-nitrogen heterocyclic carbene skeleton organic porous polymer, and preparation method and application thereof Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims abstract description 58
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- -1 1, 3-di (4-benzhydryl-2, 6-diisopropylphenyl) imidazolium salt Chemical class 0.000 claims abstract description 51
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 claims abstract description 12
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 229920006389 polyphenyl polymer Polymers 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 78
- 238000003756 stirring Methods 0.000 claims description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 239000003513 alkali Substances 0.000 claims description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 229910000071 diazene Inorganic materials 0.000 claims description 14
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 12
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 11
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- PWRBCZZQRRPXAB-UHFFFAOYSA-N 3-chloropyridine Chemical compound ClC1=CC=CN=C1 PWRBCZZQRRPXAB-UHFFFAOYSA-N 0.000 claims description 7
- 238000000944 Soxhlet extraction Methods 0.000 claims description 7
- 239000007810 chemical reaction solvent Chemical class 0.000 claims description 7
- 229940015043 glyoxal Drugs 0.000 claims description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 150000001543 aryl boronic acids Chemical class 0.000 claims description 6
- 239000011968 lewis acid catalyst Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 5
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 5
- 239000004305 biphenyl Substances 0.000 claims description 5
- 235000010290 biphenyl Nutrition 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 5
- 235000019253 formic acid Nutrition 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- 229920002866 paraformaldehyde Polymers 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- QAQRHTYPYQPBSX-UHFFFAOYSA-N 4-bromo-2,6-di(propan-2-yl)aniline Chemical compound CC(C)C1=CC(Br)=CC(C(C)C)=C1N QAQRHTYPYQPBSX-UHFFFAOYSA-N 0.000 claims description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 4
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 239000012265 solid product Substances 0.000 claims description 4
- 239000005051 trimethylchlorosilane Substances 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- SXWIAEOZZQADEY-UHFFFAOYSA-N 1,3,5-triphenylbenzene Chemical compound C1=CC=CC=C1C1=CC(C=2C=CC=CC=2)=CC(C=2C=CC=CC=2)=C1 SXWIAEOZZQADEY-UHFFFAOYSA-N 0.000 claims description 3
- PEQHIRFAKIASBK-UHFFFAOYSA-N tetraphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 PEQHIRFAKIASBK-UHFFFAOYSA-N 0.000 claims description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 2
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- 239000000758 substrate Substances 0.000 abstract description 12
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 abstract description 10
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 239000011148 porous material Substances 0.000 abstract description 5
- 238000009826 distribution Methods 0.000 abstract description 3
- 238000005727 Friedel-Crafts reaction Methods 0.000 abstract 1
- 101150003085 Pdcl gene Proteins 0.000 abstract 1
- 239000003431 cross linking reagent Substances 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 33
- 239000003054 catalyst Substances 0.000 description 24
- 229910052763 palladium Inorganic materials 0.000 description 18
- 239000007787 solid Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 239000003446 ligand Substances 0.000 description 8
- ADLVDYMTBOSDFE-UHFFFAOYSA-N 5-chloro-6-nitroisoindole-1,3-dione Chemical group C1=C(Cl)C([N+](=O)[O-])=CC2=C1C(=O)NC2=O ADLVDYMTBOSDFE-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 238000006880 cross-coupling reaction Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000012041 precatalyst Substances 0.000 description 6
- 238000005859 coupling reaction Methods 0.000 description 5
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 4
- 238000007210 heterogeneous catalysis Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000006069 Suzuki reaction reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000002073 nanorod Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 description 1
- ZDWNQEZRSIFFMM-UHFFFAOYSA-N 4-benzhydryl-2,6-di(propan-2-yl)aniline Chemical compound CC(C)C1=CC(=CC(C(C)C)=C1N)C(C1=CC=CC=C1)C1=CC=CC=C1 ZDWNQEZRSIFFMM-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000012039 electrophile Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical compound C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2265—Carbenes or carbynes, i.e.(image)
- B01J31/2269—Heterocyclic carbenes
- B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
- C08G2261/124—Copolymers alternating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/37—Metal complexes
- C08G2261/374—Metal complexes of Os, Ir, Pt, Ru, Rh, Pd
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/70—Post-treatment
- C08G2261/78—Complexation
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
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- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
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- Catalysts (AREA)
Abstract
The invention belongs to the technical field of catalysis, and particularly relates to a palladium-nitrogen heterocyclic carbene skeleton organic porous polymer, and a preparation method and application thereof. The structural unit of the palladium-nitrogen heterocyclic carbene skeleton organic porous polymer is shown as a formula I, a formula II or a formula III, and the preparation method comprises the following steps: by using dimethanol formal as a cross-linking agent, passing 1, 3-di (4-benzhydryl-2, 6-diisopropylphenyl) imidazolium salt and a polyphenyl compound through FeCl 3 Catalytic friedel-crafts alkylSynthesizing by chemical reaction to obtain an organic porous polymer; mixing organic porous polymer with PdCl under alkaline condition 2 And (3) carrying out coordination to obtain the palladium-nitrogen heterocyclic carbene skeleton organic porous polymer. The organic porous polymer has the characteristics of high stability, large specific surface area, wide pore size distribution and the like, and can efficiently catalyze the Suzuki-Miyaura coupling reaction taking chlorobenzene as a substrate; the preparation method is simple, convenient and feasible, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of catalysis, and particularly relates to a palladium-nitrogen heterocyclic carbene skeleton organic porous polymer, and a preparation method and application thereof.
Background
The disclosure of this background section is only intended to increase the understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.
The palladium-catalyzed Suzuki-Miyaura (SM) cross-coupling reaction is one of the most commonly used reactions for building C-C bonds, which is widely used in the fields of organic chemistry and materials science. The homogeneous palladium pre-catalyst has excellent catalytic efficiency on the cross coupling of aryl halide and aryl boric acid, but the palladium catalyst has high cost and great recovery difficulty, which restricts the further industrial application. In addition, in the case of synthetic drugs and intermediates thereof, the leaching amount of palladium must be strictly controlled. Therefore, heterogeneous catalysis is considered as a green chemical process, and the pollution of reaction products by heavy metal palladium can be avoided.
The organic porous material has the advantages of large specific surface area, adjustable aperture, light weight, high stability, easy functionalization and the like, and is widely applied to the fields of gas adsorption, sensing, organic photoelectricity, heterogeneous catalysis and the like. In particular, in recent years, the application of organic porous materials as supported palladium catalysts to heterogeneous catalytic C-C bond coupling has been greatly developed. However, in these heterogeneous catalytic systems, aromatic iodides and bromides remain the best choice for reactant electrophiles, but less expensive and readily available aromatic chlorides are reported as reaction substrates. From these studies based on palladium-supported organic porous polymers, it was found that palladium-supported organic porous polymers are subject to a smaller volume or lack of electron-rich supported ligands, resulting in much lower efficiency for aromatic chlorides.
Research on homogeneous palladium catalyzed SM cross-coupling reactions shows that the structure of the ligand and the pre-catalyst plays a key role, wherein the bulky, electron-rich ligand is generally beneficial to conversion, providing a hint for modification of palladium-supported organic porous polymers. Since Arduengo in 1991 reported for the first time that free stable aza-heterocyclic carbenes (NHCs), NHC ligands have been identified as reliable replacement ligands for phosphine ligands traditionally used in palladium catalyzed coupling reactions, resulting in Pd-NHC precatalysts with high catalytic activity due to the strong sigma-electron donor and the steric bulk of the NHC ligand. Among the Pd-NHC complexes described in all documents, the Pd-PEPPSI precatalyst (Pyridine Enhanced Precatalyst Preparation, stabilization and Initiation) is considered a widely used, simple to prepare, highly active, user friendly catalyst, widely used in many cross-coupling reactions. The Pd-PEPSI precatalyst still has the defects of less coordination points of palladium and ligand, easy loss of palladium ions and weaker adsorption capacity of the catalyst on reactants during heterogeneous catalysis SMSM cross-coupling reaction.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide a palladium-nitrogen heterocyclic carbene skeleton organic porous polymer, and a preparation method and application thereof. The N-heterocyclic carbene units in the palladium-N-heterocyclic carbene skeleton organic porous polymer are uniformly distributed in the organic polymer skeleton, coordination sites capable of being coordinated with metal ions are provided, palladium ions are combined with the N-heterocyclic carbene skeleton through coordination and chemical bonds, loss of palladium ions is reduced, heterogeneous catalysis recycling effect of the organic porous polymer catalyst is enhanced, and SM cross-coupling reaction taking chlorinated aromatic hydrocarbon with low activity as a substrate is efficiently catalyzed.
In order to achieve the above object, the present invention is realized by the following technical scheme:
in a first aspect, the invention provides a palladium-nitrogen heterocyclic carbene skeleton organic porous polymer, wherein a structural unit of the palladium-nitrogen heterocyclic carbene skeleton organic porous polymer is shown as a formula I, a formula II or a formula III;
in a second aspect, the invention provides a method for preparing the palladium-nitrogen heterocyclic carbene framework organic porous polymer according to the first aspect, which comprises the following steps:
s1, uniformly mixing 1, 3-bis (4-benzhydryl-2, 6-diisopropylphenyl) imidazolium salt, a polyphenyl compound, dimethanol formal and an organic solvent, adding a Lewis acid catalyst, placing a reaction system in an oil bath under the protection of nitrogen atmosphere, stirring for reaction, and filtering, washing, soxhlet extracting and drying an obtained solid product to obtain an organic porous polymer;
s2, adding an organic porous polymer and alkali into 3-chloropyridine, adding palladium dichloride, placing a reaction system into an oil bath, stirring for reaction, filtering, washing, soxhlet extracting and drying an obtained solid product to obtain the palladium-nitrogen heterocyclic carbene skeleton organic porous polymer;
the polyphenyl compound is one of 1,3, 5-triphenylbenzene, tetraphenylmethane or biphenyl.
In the preparation method, the preparation method of the 1, 3-bis (4-benzhydryl-2, 6-diisopropylphenyl) imidazolium salt comprises the following steps:
mixing 4-bromo-2, 6-diisopropylaniline and glyoxal, dissolving in methanol, dropwise adding formic acid, reacting to obtain a diimine compound, mixing the diimine compound and paraformaldehyde, dissolving in ethyl acetate, adding trimethylchlorosilane, placing a reaction system in an oil bath, stirring for reacting, filtering, washing and drying a product after the reaction is finished to obtain 1, 3-bis (4-benzhydryl-2, 6-diisopropylphenyl) imidazolium salt;
preferably, the mole ratio of the 4-bromo-2, 6-diisopropylaniline to glyoxal is 2-3: 1, the dropping amount of formic acid is 2-3 drops;
preferably, the ratio of glyoxal to methanol is 1 mmol:4-6 mL;
preferably, the condition for obtaining the diimine compound by reaction is that the diimine compound is reacted for 6 to 8 hours at room temperature;
preferably, the molar ratio of the diimine compound to the paraformaldehyde to the trimethylchlorosilane is 1:2-3:2-3;
preferably, the ratio of the diimine compound to ethyl acetate is 1 mmol:4-6 mL;
preferably, the condition of stirring reaction in the oil bath is 75-85 ℃ for 11-13 h.
In the preparation method, in the step S1, the molar ratio of the 1, 3-bis (4-benzhydryl-2, 6-diisopropylphenyl) imidazolium salt, the polyphenyl compound, the dimethanol formal and the Lewis acid catalyst is 1:1:10-25:10-25;
the ratio of the 1, 3-bis (4-benzhydryl-2, 6-diisopropylphenyl) imidazolium salt to the organic solvent is 1 mmol:16-17 mL
Preferably, the lewis acid catalyst is one or a combination of a plurality of anhydrous ferric trichloride, anhydrous aluminum trichloride and anhydrous zinc chloride.
Preferably, the organic solvent is chloroform or 1, 2-dichloroethane.
In the preparation method, in the step S1, the reaction system is placed in an oil bath at 60-80 ℃ to be stirred and reacted for 11-13 hours.
In the preparation method, in the step S2, the molar ratio of the organic porous polymer to the palladium chloride to the alkali is 1:2-3:3-5;
the ratio of the organic porous polymer to the 3-chloropyridine is 1g:9-11mL;
preferably, the alkali is one or a combination of several of potassium carbonate, sodium carbonate or cesium carbonate.
In the preparation method, in the step S2, the reaction system is placed in an oil bath at 75-85 ℃ to be stirred and reacted for 11-13 hours.
In the preparation method, the washing is to wash back and forth with methanol, chloroform, water and acetone for 3-5 times; the Soxhlet extraction is carried out for 11 to 13 hours by methanol Soxhlet extraction; the drying is vacuum drying for 11-13 hours at 75-85 ℃.
In a third aspect, the invention provides the use of a palladium-nitrogen heterocyclic carbene skeleton organic porous polymer according to the first aspect for catalyzing a Suzuki-Miyaura coupling reaction of chlorinated aromatic hydrocarbons and aryl boronic acids.
In a fourth aspect, the invention provides a Suzuki-Miyaura coupling reaction method of chlorinated aromatic hydrocarbon and aryl boric acid, which is characterized by comprising the following steps:
adding the palladium-nitrogen heterocyclic carbene skeleton organic porous polymer, chlorinated aromatic hydrocarbon, arylboronic acid, alkali and reaction solvent into a pressure-resistant reaction tube, and then placing a reaction system in the reaction system into an oil bath for stirring reaction under the protection of nitrogen atmosphere to obtain a product biphenyl compound;
preferably, the molar ratio of the palladium-nitrogen heterocyclic carbene framework organic porous polymer to the chlorinated aromatic hydrocarbon to the arylboronic acid to the alkali is 1:20-40:40-60:40-60;
preferably, the structural formula of the chloro-aromatic compound isWherein R is H, me, OMe, F, CF 3 ,CN,CHO,COCH 3 And NO 2 One of the following;
preferably, the aryl boric acid has the structural formula ofWherein R is 1 Is H, me, OMe, F, CF 3 ,CN,COOMe,COCH 3 And NO 2 One of the following;
preferably, the alkali is one or more of potassium carbonate, potassium phosphate, sodium carbonate, potassium tert-butoxide, cesium carbonate and sodium hydroxide;
preferably, the reaction solvent is one of methanol, ethanol, a mixed solvent of methanol and water, and a mixed solvent of ethanol and water.
The beneficial effects obtained by one or more of the technical schemes of the invention are as follows:
the invention obtains the functional N-heterocyclic carbene precursor molecule with large steric hindrance and a connecting site through molecular design, and then utilizes a high-efficiency and simple synthesis strategy to synthesize the organic porous polymer carrier rich in the N-heterocyclic carbene precursor in a large scale. The N-heterocyclic carbene units are uniformly distributed in the organic polymer framework, and provide coordination sites capable of coordinating with metal ions. The organic porous polymer skeleton has a large number of micropores and mesopores, has a large specific surface area, and enhances the adsorption effect on the catalytic substrate. The coordination of the large-steric-hindrance N-heterocyclic carbene and the metal palladium ions can inhibit the aggregation of palladium, so that the catalytic activity of palladium is improved. Meanwhile, palladium is combined with the N-heterocyclic carbene skeleton through a chemical bond, so that loss of palladium ions can be reduced, and the heterogeneous catalytic recycling effect of the organic porous polymer catalyst is enhanced.
The Pd-PEPPI-HCP of the palladium-nitrogen heterocyclic carbene skeleton organic porous polymer prepared by the invention can efficiently catalyze SM coupling with low-activity chlorinated aromatic hydrocarbon as a substrate, and the conversion rate of chlorobenzene is more than 99%. Compared with the reported heterogeneous catalyst loaded by palladium, the Pd-PEPSI-HCP has the advantages of good stability, high catalytic efficiency, wide substrate applicability and the like.
The preparation method is efficient and simple, is suitable for large-scale preparation, and has industrial application prospect.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of 1, 3-bis (4-benzhydryl-2, 6-diisopropylphenyl) imidazolium salt in example 1;
FIG. 2 is a nuclear magnetic resonance spectrum of 1, 3-bis (4-benzhydryl-2, 6-diisopropylphenyl) imidazolium salt in example 1;
FIG. 3 is a solid core magnetic representation of the organic porous polymer NHC-HCP-1 of example 1 13 C, spectrogram;
FIG. 4 is a graph of Pd 3-d X-ray photoelectron spectrum of Pd-PEPPI-HCP-1, an organic porous polymer having a palladium-nitrogen heterocyclic carbene skeleton in example 1;
FIG. 5 is a scanning electron microscope image of the Pd-PEPPI-HCP-1 organic porous polymer having a palladium-nitrogen heterocyclic carbene skeleton in example 1;
FIG. 6 is a graph showing the nitrogen adsorption profile of Pd-PEPPI-HCP-1, an organic porous polymer having a palladium-nitrogen heterocyclic carbene backbone, in example 1;
FIG. 7 is a pore size distribution diagram of Pd-PEPPI-HCP-1, an organic porous polymer having a palladium-nitrogen heterocyclic carbene skeleton, in example 1.
Detailed Description
In order to enable those skilled in the art to more clearly understand the technical scheme of the present invention, the technical scheme of the present invention will be described in detail below with reference to specific examples and comparative examples.
Example 1
In this example, a palladium-nitrogen heterocyclic carbene skeleton organic porous polymer with a structural unit shown in the following formula is provided, and is named as Pd-PEPSI-HCP-1:
the preparation method comprises the following steps:
into a 100mL round bottom flask was charged 1.37g (4.0 mmol,2.0 eq) of 4-benzhydryl-2, 6-diisopropylaniline, 290mg (2.0 mmol,40% water) glyoxal and 10mL methanol. A few drops of formic acid were added as catalyst. The color of the reaction mixture immediately changed from colorless to yellow, and after a few hours a yellow precipitate appeared. The reaction system was stirred for 24 hours, and the yellow solid was collected by filtration and washed with cold methanol to obtain an intermediate diimine compound. Yield 1.06g (75%). A100 mL two-necked flask was further charged with magneton, and the corresponding diimine compound (780 mg,1.1 mmol) and paraformaldehyde (60 mg,2.0 mmol) were added thereto and poured into 5.0mL ethyl acetate, and TMSCl (216 mg,2.0 mmol) was added to the round-bottomed flask via syringe at room temperature. The reaction mixture was stirred at 70 ℃ for 12h, after the reaction was completed, the white precipitate was filtered off, washed with ethyl acetate and dried in vacuo to give 1, 3-bis (4-benzhydryl-2, 6-diisopropylphenyl) imidazolium salt as a white powdery solid. Yield 599mg (72%).
In a dry and clean 50mL round bottom flask under the protection of nitrogen atmosphere, a magnetic stirrer is added, 1, 3-bis (4-benzhydryl-2, 6-diisopropylphenyl) imidazolium salt (227.2 mg,0.3 mmol), 1,3, 5-triphenylbenzene (91.8 mg,0.3 mmol) and dimethanol formal (304 mg,4.0 mmol) are dispersed in 5mL of 1, 2-dichloroethane, anhydrous ferric trichloride (649 mg,4.0 mmol) is added as a catalyst at room temperature, the reaction system is stirred at 60 ℃ for reaction for 12 hours, heating and stirring are stopped, the solid obtained by the reaction is filtered after cooling, the solid is washed by methanol, chloroform, water and acetone for a plurality of times, finally the solid is Soxhlet extracted in methanol solution, and then dried under vacuum at 80 ℃ to obtain a yellow powder, so as to obtain an organic porous polymer which is named NHC-HCP-1.
In a dry and clean 50mL round bottom flask under nitrogen atmosphere, adding a magnetic stirrer, dispersing NHC-HCP-1 (100 mg), palladium chloride (25 mg) and potassium carbonate (69 mg) in 1.0mL of 3-chloropyridine, magnetically stirring at 80 ℃ for 12h, stopping heating and stirring, and cooling to room temperature; filtering the obtained mixture, and respectively washing the obtained solid with dichloromethane, methanol, water and acetone back and forth for several times to wash away unreacted palladium chloride; and then soxhlet extraction is carried out by methanol, and then the brown yellow powder is obtained by vacuum drying at 80 ℃ to obtain the palladium-nitrogen heterocyclic carbene skeleton organic porous polymer which is named Pd-PEPPI-HCP-1.
The content of metallic palladium in the synthesized product was measured to be 4.31wt% by an ICP test instrument, indicating successful loading of palladium chloride into NHC-HCP-1, resulting in Pd-PEPPI-HCP-1 organic porous catalyst.
As shown in FIG. 1, 3-bis (4-benzhydryl-2, 6-diisopropylphenyl) imidazolium salt 1 The assignment of each signal in the H NMR spectrum corresponds to the theoretical hydrogen assignment signal peak. As shown in FIG. 2, the nuclear magnetic resonance spectrum further demonstrates that the monomer structure is the target monomer 1, 3-bis (4-benzhydryl-2, 6-diisopropylphenyl) imidazolium salt of the present invention.
As shown in FIG. 3, the solid core magnet of NHC-HCP-1 13 The C spectrum shows that the broad signal in the range of 120-150ppm is related to carbon atoms in the benzene ring, and the signal in the range of 15-30ppm belongs to the aliphatic carbon of the functionalized monomer imidazole salt. The 56ppm signal peak is attributed to the tertiary carbon atom of the functionalized monomeric imidazole. The 37ppm signal peak was attributed to the methylene carbon in the linker, indicating that the organic polymer NHC-HCP-1 was successfully synthesized by Friedel-Crafts alkylation.
As shown in FIG. 4, the Pd3d XPS spectrum of Pd-PEPPI-HCP-1 shows a Binding Energy (BE) of the Pd3d5/2 orbital of 337.70eV, indicating that the Pd species in Pd-PEPPI-HCP-1 exist in the +2 valence state.
As shown in FIG. 5, pd-PEPPI-HCP-1 has a structure in which a large number of nanorods and a small number of nanosheets are stacked, and the size of the nanorods is between 20 and 50 microns.
As shown in FIG. 6, the Pd-PEPPI-HCP-1 has a specific surface area of 568m 2 And/g. As shown in fig. 7, the pore size distribution curve indicates that a large number of micropores and mesopores exist in the HCP material.
Pd-PEPSI-HCP-1 is applied to catalyze the SM coupling reaction, and the specific steps are as follows:
taking p-chlorotoluene (0.5 mmol) and phenylboronic acid (0.75 mmol) as reaction substrates, adding 8mg of polymer Pd-PEPPI-HCP-1 as a catalyst under the protection of nitrogen, and magnetically stirring in an oil bath at 80 ℃ for reaction for 12h; the reaction condition alkali and solvent are screened, the catalyst dosage is the same as the substrate dosage, and the yield is the separation yield. As shown in Table 1, the experimental results indicate that the reaction was performed with EtOH/H 2 O (1/1, v/v) as reaction solvent, K 2 CO 3 The catalyst has the best catalytic reaction effect and the yield can reach about 95 percent.
TABLE 1 Pd-PEPSI-HCP-1 catalytic SM coupling reaction experimental condition screening
Under the same experimental conditions, catalytic experiments are carried out on other commonly used homogeneous catalysts and reported heterogeneous catalysts, and the catalytic effect is compared with that of Pd-PEPPI-HCP-1. As shown in Table 2, the results show that compared with other catalysts Pd-PEPPI-HCP-1, the catalyst has excellent catalytic activity on a substrate of low-activity chlorobenzene, and the nitrogen heterocyclic carbene monomer in the material has important effect on stabilizing palladium ions. The catalyst can be recycled for more than 5 times, and still has excellent catalytic effect on chlorobenzene.
TABLE 2 comparison of the effects of Suzuki coupling reactions with different catalysts catalyzing chlorobenzene as a substrate
Example 2
In this example, a palladium-nitrogen heterocyclic carbene skeleton organic porous polymer with a structural unit shown in the following formula is provided, and is named Pd-PEPSI-HCP-2:
the preparation method comprises the following steps:
synthesis of 1, 3-bis (4-benzhydryl-2, 6-diisopropylphenyl) imidazolium salt was performed as in example 1.
In a dry and clean 50mL round bottom flask under the protection of nitrogen atmosphere, adding a magnetic stirrer, dispersing 1, 3-bis (4-benzhydryl-2, 6-diisopropylphenyl) imidazolium salt (227.2 mg,0.3 mmol), tetraphenyl methane (96.0 mg,0.3 mmol) and dimethanol formal (304 mg,4.0 mmol) into 5mL of 1, 2-dichloroethane, adding anhydrous ferric trichloride (649 mg,4.0 mmol) as a catalyst at room temperature, stirring the reaction system at 60 ℃ for reaction for 12 hours, stopping heating and stirring, cooling, filtering out a solid obtained by the reaction, washing the solid for a plurality of times by methanol, chloroform, water and acetone, finally Soxhlet extracting the solid in a methanol solution, and drying in vacuum at 80 ℃ to obtain yellow powder, thus obtaining the organic porous polymer NHC-HCP-2.
In a dry and clean 50mL round bottom flask under nitrogen atmosphere, adding a magnetic stirrer, dispersing NHC-HCP-2 (100 mg), palladium chloride (25 mg) and potassium carbonate (69 mg) in 1.0mL of 3-chloropyridine, magnetically stirring at 80 ℃ for 12h, stopping heating and stirring, and cooling to room temperature; filtering the obtained mixture, and respectively washing the obtained solid with dichloromethane, methanol, water and acetone back and forth for several times to wash away unreacted palladium chloride; and then soxhlet extraction is carried out by methanol, and then the brown yellow powder is obtained by vacuum drying at 80 ℃ to obtain the Pd-PEPPI-HCP-2 organic porous polymer with palladium-nitrogen heterocyclic carbene skeleton.
Pd-PEPSI-HCP-2 is applied to catalyzing Suzuki coupling reaction, and specifically comprises the following steps:
using p-nitrochlorobenzene (0.5 mmol) and phenylboronic acid (0.75 mmol) as reaction substrates, adding 10mg of polymer Pd-PEPPI-HCP-2 as a catalyst under the protection of nitrogen, and magnetically stirring in an oil bath at 80 ℃ for reaction for 12h; screening reaction condition alkali and solvent, and experiment result shows that EtOH/H is adopted 2 O (1/1, v/v) as reaction solvent, K 2 CO 3 The catalyst has the best catalytic reaction effect and the yield can reach about 95 percent. The catalyst can be recycled for more than 5 times and still has excellent catalytic effect on the paranitrochlorobenzene.
Example 3
In this example, a palladium-nitrogen heterocyclic carbene skeleton organic porous polymer with a structural unit shown in the following formula is provided, and is named Pd-PEPSI-HCP-3:
the preparation method comprises the following steps:
synthesis of 1, 3-bis (4-benzhydryl-2, 6-diisopropylphenyl) imidazolium salt was performed as in example 1.
In a dry and clean 50mL round bottom flask under the protection of nitrogen atmosphere, adding a magnetic stirrer, dispersing 1, 3-bis (4-benzhydryl-2, 6-diisopropylphenyl) imidazolium salt (227.2 mg,0.3 mmol), biphenyl (46.2 mg,0.3 mmol) and dimethanol formal (304 mg,4.0 mmol) into 5mL of 1, 2-dichloroethane, adding anhydrous ferric trichloride (649 mg,4.0 mmol) as a catalyst at room temperature, stirring the reaction system at 60 ℃ for reaction for 12 hours, stopping heating and stirring, cooling, filtering out a solid obtained by the reaction, washing the solid for a plurality of times by methanol, chloroform, water and acetone, finally Soxhlet extracting the solid in methanol solution, and drying in vacuum at 80 ℃ to obtain yellow powder, thus obtaining the organic porous polymer NHC-HCP-3.
In a dry and clean 50mL round bottom flask under nitrogen atmosphere, adding a magnetic stirrer, dispersing NHC-HCP-3 (100 mg), palladium chloride (25 mg) and potassium carbonate (69 mg) in 1.0mL 3-chloropyridine, magnetically stirring at 80 ℃ for 12h, stopping heating and stirring, and cooling to room temperature; filtering the obtained mixture, and respectively washing the obtained solid with dichloromethane, methanol, water and acetone back and forth for several times to wash away unreacted palladium chloride; and then soxhlet extraction is carried out by methanol, and then the brown yellow powder is obtained by vacuum drying at 80 ℃ to obtain the Pd-PEPPI-HCP-3 organic porous polymer with palladium-nitrogen heterocyclic carbene skeleton.
Pd-PEPSI-HCP-3 is applied to catalyzing Suzuki coupling reaction, and specifically comprises the following steps:
using p-nitrochlorobenzene (0.5 mmol) and phenylboronic acid (0.75 mmol) as reaction substrates, adding 10mg of polymer Pd-PEPPI-HCP-3 as a catalyst under the protection of nitrogen, and magnetically stirring in an oil bath at 80 ℃ for reaction for 12h; screening reaction condition alkali and solvent, and experiment result shows that EtOH/H is adopted 2 O (1/1, v/v) as reaction solvent, K 2 CO 3 The catalyst has the best catalytic reaction effect and the yield can reach about 94 percent. The catalyst can be recycled for more than 5 times and still has excellent catalytic effect on the paranitrochlorobenzene.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The palladium-nitrogen heterocyclic carbene skeleton organic porous polymer is characterized in that a structural unit of the palladium-nitrogen heterocyclic carbene skeleton organic porous polymer is shown as a formula I or a formula II or a formula III;
2. a method for preparing the palladium-nitrogen heterocyclic carbene skeleton organic porous polymer according to claim 1, comprising the following steps:
s1, uniformly mixing 1, 3-bis (4-benzhydryl-2, 6-diisopropylphenyl) imidazolium salt, a polyphenyl compound, dimethanol formal and an organic solvent, adding a Lewis acid catalyst, placing a reaction system in an oil bath under the protection of nitrogen atmosphere, stirring for reaction, and filtering, washing, soxhlet extracting and drying an obtained solid product to obtain an organic porous polymer;
s2, adding an organic porous polymer and alkali into 3-chloropyridine, adding palladium dichloride, placing a reaction system into an oil bath, stirring for reaction, filtering, washing, soxhlet extracting and drying an obtained solid product to obtain the palladium-nitrogen heterocyclic carbene skeleton organic porous polymer;
the polyphenyl compound is one of 1,3, 5-triphenylbenzene, tetraphenylmethane or biphenyl.
3. The process according to claim 2, wherein the process for preparing 1, 3-bis (4-benzhydryl-2, 6-diisopropylphenyl) imidazolium salt comprises the steps of:
mixing 4-bromo-2, 6-diisopropylaniline and glyoxal, dissolving in methanol, dropwise adding formic acid, reacting to obtain a diimine compound, mixing the diimine compound and paraformaldehyde, dissolving in ethyl acetate, adding trimethylchlorosilane, placing a reaction system in an oil bath, stirring for reacting, filtering, washing and drying a product after the reaction is finished to obtain 1, 3-bis (4-benzhydryl-2, 6-diisopropylphenyl) imidazolium salt;
preferably, the mole ratio of the 4-bromo-2, 6-diisopropylaniline to glyoxal is 2-3: 1, the dropping amount of formic acid is 2-3 drops;
preferably, the ratio of glyoxal to methanol is 1 mmol:4-6 mL;
preferably, the condition for obtaining the diimine compound by reaction is that the diimine compound is reacted for 6 to 8 hours at room temperature;
preferably, the molar ratio of the diimine compound to the paraformaldehyde to the trimethylchlorosilane is 1:2-3:2-3;
preferably, the ratio of the diimine compound to ethyl acetate is 1 mmol:4-6 mL;
preferably, the condition of stirring reaction in the oil bath is 75-85 ℃ for 11-13 h.
4. The preparation method according to claim 2, wherein in the step S1, the molar ratio of the 1, 3-bis (4-benzhydryl-2, 6-diisopropylphenyl) imidazolium salt, the polyphenyl compound, the dimethanol formal and the lewis acid catalyst is 1:1:10 to 25:10 to 25;
the ratio of the 1, 3-bis (4-benzhydryl-2, 6-diisopropylphenyl) imidazolium salt to the organic solvent is 1 mmol:16-17 mL
Preferably, the lewis acid catalyst is one or a combination of a plurality of anhydrous ferric trichloride, anhydrous aluminum trichloride and anhydrous zinc chloride.
Preferably, the organic solvent is chloroform or 1, 2-dichloroethane.
5. The process according to claim 2, wherein in step S1, the reaction system is stirred in an oil bath at 60 to 80℃for 11 to 13 hours.
6. The preparation method according to claim 2, wherein in the step S2, the molar ratio of the organic porous polymer to palladium chloride and alkali is 1:2-3:3-5;
the ratio of the organic porous polymer to the 3-chloropyridine is 1g:9-11mL;
preferably, the alkali is one or a combination of several of potassium carbonate, sodium carbonate or cesium carbonate.
7. The process according to claim 2, wherein in step S2, the reaction system is stirred in an oil bath at 75 to 85℃for 11 to 13 hours.
8. A method according to claim 2 or 3, wherein the washing is performed 3-5 times with methanol, chloroform, water, acetone; the Soxhlet extraction is carried out for 11 to 13 hours by methanol Soxhlet extraction; the drying is vacuum drying for 11-13 hours at 75-85 ℃.
9. Use of a palladium-nitrogen heterocyclic carbene backbone organic porous polymer according to claim 1 for catalyzing a Suzuki-Miyaura coupling reaction of chlorinated aromatic hydrocarbons and aryl boronic acids.
10. A Suzuki-Miyaura coupling reaction method of chlorinated aromatic hydrocarbon and aryl boric acid, which is characterized by comprising the following steps:
adding the palladium-nitrogen heterocyclic carbene skeleton organic porous polymer, chlorinated aromatic hydrocarbon, arylboronic acid, alkali and reaction solvent into a pressure-resistant reaction tube, and then placing a reaction system in the reaction system into an oil bath for stirring reaction under the protection of nitrogen atmosphere to obtain a product biphenyl compound;
preferably, the molar ratio of the palladium-nitrogen heterocyclic carbene framework organic porous polymer to the chlorinated aromatic hydrocarbon to the arylboronic acid to the alkali is 1:20-40:40-60:40-60;
preferably, the structural formula of the chloro-aromatic compound isWherein R is H, me, OMe, F, CF 3 ,CN,CHO,COCH 3 And NO 2 One of the following;
preferably, the aryl boric acid has the structural formula ofWherein R is 1 Is H, me, OMe, F, CF 3 ,CN,COOMe,COCH 3 And NO 2 One of the following;
preferably, the alkali is one or more of potassium carbonate, potassium phosphate, sodium carbonate, potassium tert-butoxide, cesium carbonate and sodium hydroxide;
preferably, the reaction solvent is one of methanol, ethanol, a mixed solvent of methanol and water, and a mixed solvent of ethanol and water.
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