CN113117754A - Flower-shaped core-shell type magnetic mesoporous microsphere immobilized N-heterocyclic carbene cyclic palladium catalyst and preparation method and application thereof - Google Patents
Flower-shaped core-shell type magnetic mesoporous microsphere immobilized N-heterocyclic carbene cyclic palladium catalyst and preparation method and application thereof Download PDFInfo
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- CN113117754A CN113117754A CN202110398134.3A CN202110398134A CN113117754A CN 113117754 A CN113117754 A CN 113117754A CN 202110398134 A CN202110398134 A CN 202110398134A CN 113117754 A CN113117754 A CN 113117754A
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- flower
- magnetic mesoporous
- heterocyclic carbene
- shaped core
- shell
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 239000004005 microsphere Substances 0.000 title claims abstract description 92
- 239000011258 core-shell material Substances 0.000 title claims abstract description 69
- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- ADLVDYMTBOSDFE-UHFFFAOYSA-N 5-chloro-6-nitroisoindole-1,3-dione Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC2=C1C(=O)NC2=O ADLVDYMTBOSDFE-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 125000004122 cyclic group Chemical group 0.000 title claims abstract description 16
- 239000003446 ligand Substances 0.000 claims abstract description 21
- 238000005576 amination reaction Methods 0.000 claims abstract description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 27
- 239000000047 product Substances 0.000 claims description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
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- 239000000203 mixture Substances 0.000 claims description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
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- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical group CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
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- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 125000004103 aminoalkyl group Chemical group 0.000 claims description 3
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 2
- 101150003085 Pdcl gene Proteins 0.000 claims description 2
- DVARTQFDIMZBAA-UHFFFAOYSA-O ammonium nitrate Chemical class [NH4+].[O-][N+]([O-])=O DVARTQFDIMZBAA-UHFFFAOYSA-O 0.000 claims description 2
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- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
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- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
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- -1 aryl phenylboronic acid Chemical compound 0.000 abstract description 14
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- 150000001500 aryl chlorides Chemical class 0.000 abstract 1
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 1
- RHDYQUZYHZWTCI-UHFFFAOYSA-N 1-methoxy-4-phenylbenzene Chemical group C1=CC(OC)=CC=C1C1=CC=CC=C1 RHDYQUZYHZWTCI-UHFFFAOYSA-N 0.000 description 7
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- 238000006555 catalytic reaction Methods 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
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- AOTQLPVPRARTRF-UHFFFAOYSA-N 4-(12-bromododecoxy)benzaldehyde Chemical compound BrCCCCCCCCCCCCOC1=CC=C(C=O)C=C1 AOTQLPVPRARTRF-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
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- 238000003917 TEM image Methods 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
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- 150000002460 imidazoles Chemical class 0.000 description 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 2
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- VOAAEKKFGLPLLU-UHFFFAOYSA-N (4-methoxyphenyl)boronic acid Chemical compound COC1=CC=C(B(O)O)C=C1 VOAAEKKFGLPLLU-UHFFFAOYSA-N 0.000 description 1
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- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
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- 238000005349 anion exchange Methods 0.000 description 1
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
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- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
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- 239000002105 nanoparticle Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
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- 150000002941 palladium compounds Chemical class 0.000 description 1
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- 159000000000 sodium salts Chemical class 0.000 description 1
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- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
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- 238000012546 transfer Methods 0.000 description 1
- PKDCQJMRWCHQOH-UHFFFAOYSA-N triethoxysilicon Chemical group CCO[Si](OCC)OCC PKDCQJMRWCHQOH-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- 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
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
- B01J31/1625—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups
- B01J31/1633—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups covalent linkages via silicon containing groups
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- B01J31/2269—Heterocyclic carbenes
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
- B01J2231/4211—Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group
- B01J2231/4227—Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group with Y= Cl
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
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- 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
Abstract
The invention discloses a flower-shaped core-shell magnetic mesoporous microsphere immobilized N-heterocyclic carbene ring palladium catalyst and a preparation method and application thereof. The preparation method comprises the following steps: firstly, preparing flower-shaped core-shell type magnetic mesoporous microspheres, and then carrying out amination to load active amino target spots capable of reacting with N-heterocyclic carbene ligands on the magnetic mesoporous microspheres; then preparing a magnetic mesoporous microsphere immobilized N-heterocyclic carbene ligand, and finally reacting the ligand with palladium chloride to prepare the flower-shaped core-shell magnetic mesoporous microsphere immobilized N-heterocyclic carbene cyclic palladium catalyst. The flower-shaped core-shell magnetic mesoporous microsphere immobilized N-heterocyclic carbene cyclic palladium catalyst has high load and high catalytic activity, and can catalyze the cross-coupling reaction between aryl chloride and aryl phenylboronic acid with high difficulty by using a catalytic amount of 1 mol%. The catalyst is a superparamagnetic catalyst, can be separated magnetically and recycled, and has high economic value and wide application prospect.
Description
Technical Field
The invention relates to a flower-shaped core-shell magnetic mesoporous microsphere immobilized N-heterocyclic carbene ring palladium catalyst, and a preparation method and application thereof, and belongs to the technical field of organic catalysis.
Background
Since Aduengo first isolated free N-heterocyclic carbenes in 1991, various metal complexes of N-heterocyclic carbenes have been reported. N-heterocyclic carbene (NHC) ligands have attracted considerable attention in transition metal catalysis due to their ease of preparation, strong sigma-donor capability and effective binding strength to transition metals. The types of the azacyclo-carbenes are few, and the azacyclo-carbenes found so far mainly have the following four structures: structural formulas 1-4. As homogeneous catalysts, particularly N-heterocyclic carbene cyclic palladium catalyst complexes have been widely used in organic catalysis, particularly in Suzuki-Miyaura cross-coupling reactions. Although a large number of homogeneous catalysts exhibit excellent catalytic activity, the homogeneous catalysts still have problems such as product contamination, complicated separation processes, and high operation costs. Various materials have been used to support azacyclo-carbene catalysts, including silica, carbon, magnetic nanoparticles, and the like. The use of recoverable heterogeneous catalysts is a necessary trend for green chemistry development.
The synthesis routes for the currently used aza-carbene target compounds in Suzuki-Miyaura coupling reactions are mainly: route one synthetic route disclosed in patent document CN 107880079 a: the N-heterocyclic bis-carbene palladium complex which takes 1, 4-bis (N-ethyl-benzimidazolium methyl) -2,3,5, 6-tetramethylbenzene aromatic hydrocarbon salt as a precursor is applied to the field of catalysis. Particularly, the catalyst is used for Suzuki-Miyaura coupling reaction of para-brominated aromatic hydrocarbon and phenylboronic acid, and the synthetic route of the route I is as follows:
route two is a synthetic route disclosed in patent document CN 108586345 a: 1,8-2[3- (N-ethylimidazolyl) propoxy ] anthraquinone halide is generated mainly by the reaction of 1, 8-bis (3-bromopropoxy) anthraquinone and N-ethyl-imidazole, and 1,8-2[3- (N-ethylimidazolyl) propoxy ] anthraquinone hexafluorophosphate can be obtained by carrying out anion exchange reaction on ammonium hexafluorophosphate. Wherein, 1,8-2[3- (N-ethylimidazolyl) propoxy ] anthraquinone hexafluorophosphate reacts with a palladium compound to generate the N-heterocyclic carbene-palladium complex, and the synthesis route of the second route is as follows:
route three is a synthetic route disclosed in patent document CN 108579809 a: mainly dissolving an N-heterocyclic carbene palladium compound and an amphiphilic polymer DSPE-PEG2000 in a small amount of dimethyl sulfoxide solution, then slowly dripping the dimethyl sulfoxide solution into deionized water under the ultrasonic condition, and forming the nano-particle catalyst wrapping the N-heterocyclic carbene palladium compound through self-assembly of the amphiphilic polymer.
Route four is represented by a document published in ChemComm, 2017, 53, 13063: the cheap aza carbene ligand is synthesized by taking 10-undecene-1-alcohol as a raw material through simple reactions such as bromination, etherification, ammoniation, hydrosilylation and the like. Then preparing the aza carbene nanometer particle by corresponding triethoxy silicon group functionalization, wherein the synthesis route of the fourth route is as follows:
the above synthetic routes all have certain disadvantages:
1) the homogeneous nitrogen heterocyclic carbene palladium compound is not easy to separate in the product, causes secondary pollution and does not accord with the concept of green environmental protection;
2) the central palladium of the N-heterocyclic carbene ring palladium catalyst is easily lost in the catalysis process, thereby causing the inactivation of the catalyst.
3) The prepared magnetic microspheres are easy to agglomerate, so that the heterogeneous N-heterocyclic carbene-palladium catalyst is too low in load, the utilization rate of the catalyst is reduced, and the TOF (amount of converted reactants in unit time) of the catalyst is reduced.
These disadvantages limit the industrial application of the existing synthetic routes to a certain extent. Therefore, the existing method for synthesizing the N-heterocyclic carbene ring palladium magnetic microsphere catalyst needs further improvement.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the N-heterocyclic carbene ring palladium magnetic microsphere synthesized in the prior art is easy to agglomerate, so that the heterogeneous N-heterocyclic carbene ring palladium catalyst has too low load, the utilization rate of the catalyst is reduced, and the TOF of the catalyst is reduced.
In order to solve the technical problem, the invention provides a flower-shaped core-shell magnetic mesoporous microsphere immobilized N-heterocyclic carbene ring palladium catalyst, wherein the flower-shaped core-shell magnetic mesoporous microsphere is loaded with the N-heterocyclic carbene ring palladium catalyst shown as a formula I:
preferably, the flower-shaped core-shell magnetic mesoporous microsphere comprises magnetic Fe in a core shell3O4SiO outside the particle and core-shell2And (4) mesoporous.
The invention also provides a preparation method of the flower-shaped core-shell magnetic mesoporous microsphere immobilized N-heterocyclic carbene cyclic palladium catalyst, which comprises the following steps:
step 1: with iron and silicon sourcesTo obtain Fe3O4@SiO2Magnetic microspheres;
step 2: mixing Fe3O4@SiO2Dispersing magnetic microspheres in water to obtain magnetic microsphere dispersion, and treating the magnetic microsphere dispersion with a template agent to obtain flower-shaped core-shell magnetic mesoporous microspheres Fe3O4@mSiO2；
And step 3: flower-shaped core-shell type magnetic mesoporous microsphere Fe3O4@mSiO2Amination of (a);
and 4, step 4: reacting the aminated flower-shaped core-shell magnetic mesoporous microsphere with an N-heterocyclic carbene ligand to prepare a flower-shaped core-shell magnetic mesoporous microsphere immobilized N-heterocyclic carbene ligand;
and 5: immobilizing the flower-shaped core-shell magnetic mesoporous microspheres with N-heterocyclic carbene ligands and PdCl in an inert gas atmosphere2Adding the mixture into a solvent, stirring to obtain a mixed solution, adding carbonate into the mixed solution, performing reflux reaction, washing and drying a product after the reaction is finished, and preparing the flower-shaped core-shell magnetic mesoporous microsphere immobilized N-heterocyclic carbene cyclic palladium catalyst.
Preferably, the iron source in the step 1 is at least one of ferric chloride and ferric sulfate; the silicon source is organic siloxane; the template agent in the step 2 comprises cetyl trimethyl ammonium bromide and fluorine surfactant FS-66.
Preferably, the step 2 specifically comprises: cetyl trimethylammonium bromide, triethanolamine and ultrapure water were mixed at a ratio of 0.6 g: 0.1 mL: 30 mL-0.7 g: 0.2 mL: mixing the components in a proportion of 40mL, and stirring the mixture for 15 to 30 minutes at a temperature of between 60 and 70 ℃ to prepare a CTAB template solution; then weighing a template agent FS-66 according to the mass ratio of FS-66 to hexadecyl trimethyl ammonium bromide being 0.1-0.25: 1, dissolving the template agent FS-66 in isopropyl acetone to prepare a solution with the concentration of 0.0375-0.15 g/mL, adding the solution into the CTAB template solution, continuously stirring for 1-2 hours, adding TEOS according to the ratio of 6-10 mL TEOS/g hexadecyl trimethyl ammonium bromide, and stirring for 60-80 seconds to obtain a double-template solution; mixing the double-template solution and the magnetic microsphere dispersion in a ratio of 2-3: 1, carrying out ultrasonic treatment for 2-3 minutes, and then carrying out ultrasonic treatment on the mixture on a circumference oscillator in an r-600-700 r-Oscillating for 30-40 minutes at the speed of min, and then shaking for 6 hours at the speed of r being 200-300 r/min; finally, separating the product, removing the template solution, adding an ethanol solution of saturated ammonium nitrate, oscillating and washing for 10-15 h, washing the washed solid product with absolute ethanol and water for 2-3 times respectively, and drying to obtain the flower-shaped core-shell magnetic mesoporous microspheres; in the magnetic microsphere dispersion, Fe3O4@SiO2The concentration of the magnetic microspheres is 0.005-0.01 g/mL.
Preferably, the amination in step 3 is specifically: and (3) adding the flower-shaped core-shell magnetic mesoporous microspheres prepared in the step (2), amino alkyl siloxane and a cation trapping agent into cyclohexane, carrying out ultrasonic treatment to obtain a dispersion liquid, stirring the obtained dispersion liquid at room temperature for reaction, washing a product with n-hexane and ethanol after the reaction is finished, and drying to obtain the aminated flower-shaped core-shell magnetic mesoporous microspheres.
More preferably, the aminoalkyl siloxane is 3-aminopropyltrimethoxysilane; the cation trapping agent is dodecylamine; in the dispersion, the concentration of the flower-shaped core-shell magnetic mesoporous microspheres is 0.005-0.01 g/mL, the concentration of 3-aminopropyltrimethoxysilane is 1-3 v/v%, and the concentration of dodecylamine is 1-5 v/v%; the ultrasonic treatment time is 5-10 min, and the stirring reaction time is 4-6 h.
Preferably, the mass ratio of the aminated flower-shaped core-shell magnetic mesoporous microsphere in the step 4 to the azacyclo-carbene ligand is 1: 1-1: 1.2, and the reaction conditions are as follows: methanol is used as a solvent, the reaction temperature is 50-60 ℃, and the reaction time is 2-3 days; the mole ratio of the carbonate to the flower-shaped core-shell magnetic mesoporous microsphere immobilized N-heterocyclic carbene ligand to the palladium chloride in the step 5 is 0.4:1: 1-0.7: 1.2: 1; in the mixed solution, the concentration of the flower-shaped core-shell magnetic mesoporous microsphere immobilized N-heterocyclic carbene ligand is 0.02-0.03 mol/L; the solvent is acetonitrile, and the carbonate is potassium carbonate; the time of the reflux reaction is 20-30 h.
The invention also provides application of the flower-shaped core-shell magnetic mesoporous microsphere immobilized N-heterocyclic carbene cyclic palladium catalyst.
Preferably, the use comprises use in a Suzuki-Miyaura coupling reaction.
Compared with the prior art, the invention has the beneficial effects that:
1. the magnetic mesoporous silica is prepared by two templates, namely hexadecyl trimethyl ammonium bromide and FS-66 (fluorinated surfactant), and the pore diameter is adjustable, so that the magnetic mesoporous silica with larger specific surface area can be prepared to be used as a carrier, which is more favorable for mass transfer of reactant molecules; in the amination process of the core-shell magnetic mesoporous microspheres, dodecylamine forms micelles on the surfaces of the core-shell magnetic mesoporous microspheres, so that the prepared aminated core-shell magnetic mesoporous microspheres are more uniformly dispersed;
2. the load of palladium in the magnetic mesoporous palladium catalyst prepared by the invention is very high and reaches 0.20mmol/g, the prepared magnetic microspheres are not easy to agglomerate, and the catalytic efficiency of the catalyst is greatly improved;
3. the center palladium of the N-heterocyclic carbene cyclic palladium catalyst is connected with a structure of two independent groups, one end of the catalyst is introduced with an aliphatic long chain at an N atom, and the N-heterocyclic carbene is connected to a cyclic palladium ligand in a molecule; in order to coordinate and ring-palladate, groups at two ends of palladium need to be pulled by virtue of the stability of long-chain palladium molecules, so that the loss of a catalytic center in the catalytic process is avoided, therefore, the flower-shaped core-shell N-heterocyclic carbene ring target catalyst has higher stability, and two ends of a ligand are anchored on the palladium by virtue of a flexible aliphatic long chain; the catalyst can be recycled through magnetic separation and recovery, and the catalytic activity of the catalyst is basically kept unchanged after 12 times of recycling, so that the catalyst has higher economic value and wide application prospect.
Drawings
FIG. 1 is a schematic diagram of a preparation process of a flower-shaped core-shell magnetic mesoporous microsphere immobilized N-heterocyclic carbene ring palladium catalyst;
FIG. 2 is a transmission electron microscope image of flower-like core-shell magnetic mesoporous microspheres prepared by different amounts of template agent FS-66 (a: FS-66 is 0.075g, b: FS-66 is 0.10g, c: FS-66 is 0.125g, d: FS-66 is 0.15 g);
fig. 3 is a transmission electron microscope image of a flower-shaped core-shell magnetic mesoporous microsphere immobilized N-heterocyclic carbene ring palladium catalyst, wherein a and b are transmission electron microscope images of the flower-shaped core-shell magnetic mesoporous microsphere immobilized N-heterocyclic carbene ring palladium catalyst freshly prepared in example 1 at low times and high times, respectively, and c and d are transmission electron microscope images of the last recovered magnetic mesoporous microsphere immobilized N-heterocyclic carbene ring palladium catalyst in application example 1 at low times and high times, respectively;
FIG. 4 is a nuclear magnetic hydrogen spectrum of 4-methoxybiphenyl prepared by application example 1;
FIG. 5 is a nuclear magnetic carbon spectrum of 4-methoxybiphenyl prepared in application example 1;
FIG. 6 is a result chart of the verification of the recycling performance of the flower-shaped core-shell magnetic mesoporous microsphere immobilized aza-ring captivity palladium catalyst.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below with reference to the accompanying drawings.
Example 1
The preparation process of the flower-shaped core-shell magnetic mesoporous microsphere immobilized N-heterocyclic carbene ring palladium catalyst is shown in figure 1, and comprises the following steps:
s1, preparing flower-shaped core-shell magnetic mesoporous microspheres (a1-a 3):
1) 1.3g of ferric chloride hexahydrate and 60mL of ethylene glycol are used as reducing agents, and 4.5g of anhydrous sodium acetate, 1.5g of poly (4-styrenesulfonic acid-co-maleic acid) sodium salt and 0.5g of calcium fluoride are added simultaneously to prepare Fe with uniform appearance3O4Magnetic microspheres.
2) 0.50g of Fe was taken3O4Magnetic microspheres were sonicated in 60mL of ultrapure water for 2 minutes, 4.5mL of a 1% NaF solution was added, and the mixture was stirred on a stirrer (r ═ 500 r/min). A mixture of TEOS (tetraethylorthosilicate), 1.98mL, and ethanol (1.8mL EtOH +0.18mL TEOS) was added dropwise every 30 minutes, 10 times in total. After all additions were complete, rapid stirring was continued for 15 hours. Washing the product with absolute ethyl alcohol twice, washing with water twice, drying at 60 deg.C for 24 hr to obtain Fe3O4@SiO2。
3) 0.64g of cetyltrimethylammonium bromide (CTAB) was weighed by an electronic balance, mixed with 0.12mL of Triethanolamine (TEA) and 33.3mL of ultrapure water, and stirred in a magnetic stirrer at 60 ℃ for 15 minutes to prepare a CTAB template solution. Then, template FS-66 (a: FS-66 ═ 0.075g, b: FS-66 ═ 0.10g, c: FS-66 ═ 0.125g, and d: FS-66 ═ 0.15g) was weighed out and dissolved in 1 to 2mL of isopropyl alcohol, and the above CTAB template solution was added, and after stirring was continued for 1 hour, 5mL of TEOS was added, and after stirring was continued for 70 seconds, stirring was stopped, whereby a bimodal solution was obtained. 20mL of the dual template solution was added to 10mL of ultrasonically dispersed 0.08g Fe3O4@SiO2In aqueous solution, then sonicated for 2 minutes, then rapidly shaken (r 700r/min) on a peripheral shaker for 30 minutes, then slowly shaken (r 250r/min) for 6 hours. After 6 hours, the product was isolated and the template solution was removed. Then, a saturated ethanol solution of ammonium nitrate was added thereto, and the mixture was washed with shaking for 12 hours. Washing the product twice with absolute ethyl alcohol and twice with water, and then drying the product for 24 hours at 60 ℃ to obtain the flower-shaped core-shell magnetic mesoporous microspheres (Fe) with different apertures and specific surface areas3O4@mSiO2) FIG. 2 shows a transmission electron micrograph thereof.
S2, aminated magnetic mesoporous microsphere Fe3O4@mSiO2-NH2Synthesis of (a 4):
the amount of the template FS-66 prepared in S1 was 0.15g of Fe3O4@mSiO2(0.5g), 2% v/v APTMS (3-aminopropyl trimethoxy silane) and 3% v/v dodecylamine are added into 20ml cyclohexane, ultrasonic treatment is carried out for 5min, after stirring for 5h at room temperature, the product is washed once by n-hexane and once by ethanol, and vacuum drying is carried out for 24 h at 50 ℃ to obtain aminated magnetic mesoporous microsphere Fe3O4@mSiO2-NH2。
S3 preparation of (2, 6-diisopropyl) imidazole (a 5):
50mmol of 2, 6-diisopropylaniline and 50mmol of glyoxal are dissolved in 20mL of MeOH and stirred at 20 ℃ for 12 hours. Then 100mmol of ammonium dichloride and 10mmol of formaldehyde (37% formaldehyde aqueous solution) were added to the systemThe system was diluted 10 times with MeOH. The system was placed at 65 ℃, heated to reflux for 1 hour, and 7mL of 86% H was added dropwise3PO4Reflux for 8 hours. At the end of the reaction, the system was rotary evaporated to 30-40mL, transferred to a beaker, ice was added and the pH was adjusted to 9 with 8M NaOH solution. The solution was extracted with EA, washed with water, and then with saturated brine. The pure product was then isolated by silica gel chromatography. The product was collected, dried and weighed. Nuclear magnetic analysis of the product:1H NMR(400MHz，CDCl3，298K)：δ＝7.50-7.42(m，2H)，7.28(s，3H)，6.96(s，1H)，2.42(dt，J＝13.7，6.9Hz，2H)，1.15(d，J＝6.8Hz，12H)；13C NMR(101MHz，CDCl3，298K)：δ＝146.51，138.44，132.81，129.77，129.32，123.71，121.52，28.06，24.39，24.31。
s4.preparation of 4- (12-bromododecyloxy) benzaldehyde (a 6):
adding 5mmol of p-hydroxybenzaldehyde into 11mmol of 1, 12-dibromododecane dissolved in 75mL of acetone, adding 20mmol of anhydrous potassium carbonate into the system, condensing and refluxing at 65 ℃, stirring for 3 hours, adding 3mmol of p-hydroxybenzaldehyde into the system, continuing to react for 3 hours, finally adding 2mmol of p-hydroxybenzaldehyde into the reaction system, and continuing to react for 15 hours. The pure product was then isolated by silica gel chromatography. The product was collected, dried by removing the solvent by rotary evaporation, cooled and weighed. Nuclear magnetic analysis of the product:1H NMR(400MHz，CDCl3，298K)：δ＝9.88(s，1H)，7.83(d，J＝8.0Hz，2H)，6.99(d，J＝8.0Hz，2H)，4.04(t，J＝6.5Hz，2H)，3.41(t，J＝6.8Hz，2H)，1.90-1.76(m，4H)，1.44(dt，J＝15.3，7.5Hz，4H)，1.29(s，12H)；13C NMR(101MHz，CDCl3，298K)：δ＝190.80，164.29，131.99，129.79，114.77，68.44，34.02，32.84，29.51，29.42，29.32，29.06，28.76，28.17，25.96。
s5, preparing imidazole salt (a 7):
3mmol of 4- (12-bromododecyloxy) benzaldehyde and 3.5mmol of 2, 6-diisopropyl) imidazole are dissolved in 8mL of 1, 4-dioxane, the reaction system is put in an oil bath at 100 ℃, concentrated and refluxed,and the reaction was stirred for 18 hours. After the reaction was complete, the pure product was isolated by silica gel chromatography. Nuclear magnetic analysis of the product:1H NMR(400MHz，CDCl3，298K)：δ＝10.24(s，1H)，9.84(s，1H)，8.19(s，1H)，7.81(d，J＝8.6Hz，2H)，7.52(t，J＝7.8Hz，1H)，7.33-7.27(m，3H)，6.99(d，J＝8.6Hz，2H)，4.71(t，J＝6.8Hz，2H)，4.04(t，J＝6.4Hz，2H)，2.32-2.22(m，2H)，1.99(s，2H)，1.87-1.75(m，2H)，1.45(d，J＝7.2Hz，3H)，1.33(s，6H)，1.25(s，7H)，1.19(d，J＝6.8Hz，6H)，1.15(d，J＝6.7Hz，6H)；13C NMR(101MHz，CDCl3，298K)：δ＝160.18，145.27，138.09，132.59，131.80，130.08，124.56，124.25，123.15，115.04，67.99，55.45，50.36，45.99，30.53，29.38，29.25，28.97，28.88，28.64，25.99，25.76，24.35，24.04，8.84。
s6, immobilizing an N-heterocyclic carbene ligand (a8) by using the magnetic mesoporous microsphere:
aminated magnetic mesoporous microspheres a4(0.40g) prepared in S2 were added to dry methanol (20ml) for sonication for 15 minutes, followed by addition of imidazole salt a7(0.044g) prepared in S5 and heating at 50 ℃ for 2 days. After the reaction, separating the product by magnetic separation, washing the product for 3 times by methanol, and drying the product for 24 hours at 50 ℃ in vacuum to obtain the magnetic mesoporous microsphere of the immobilized N-heterocyclic carbene ligand.
S7, preparation of flower-shaped core-shell magnetic mesoporous microsphere immobilized N-heterocyclic carbene cyclic palladium catalyst (a9 ═ Fe)3O4@mSiO2@NHC-Pd)：
Under nitrogen, 0.24mmol of imidazolium salt and 0.21mmol of PdCl2Added to 10ml of acetonitrile solvent and stirred at 80 ℃ for 0.5 hour under nitrogen protection. Then adding K2CO3(0.12mmol), cooling and refluxing for 24 hours, washing the product twice with water, washing 2 times with ethanol, and vacuum-drying at 50 ℃ for 24 hours to obtain flower-shaped core-shell magnetic mesoporous microsphere immobilized N-heterocyclic carbene cyclic palladium catalyst Fe3O4@mSiO2@ NHC-Pd, its transmission electron micrograph is shown in figure 3a and 3b, the palladium loading in the catalyst prepared is 0.2 mmol/g.
And (3) verification of catalytic performance:
in order to verify the catalytic activity and the recycling performance of the catalyst prepared in example 1 in the coupling reaction, the flower-shaped core-shell type magnetic mesoporous microsphere immobilized N-heterocyclic carbene ring palladium catalyst Fe prepared in example 1 is applied3O4@mSiO2The @ NHC-Pd is used as a catalyst to prepare 4-methoxybiphenyl, and the catalyst is recovered through magnetic separation to verify the recycling performance of the catalyst.
Application example 1
In the nitrogen atmosphere, 4-methoxyphenylboronic acid (0.75mmol) and the flower-shaped core-shell magnetic mesoporous microsphere immobilized N-heterocyclic carbene cyclic palladium catalyst (1 mol%) prepared in the step 1 are added, and K2CO3(1.5 equiv.) and EtOH/H in a volume ratio of 2:12O (2.0mL) was added to the Schlenk reaction tube followed by chlorobenzene (0.5 mmol). The mixture was stirred at 60 ℃ for 12h, then extracted with EtOAc, the organic phase collected over anhydrous Na2SO4Drying, filtration and purification by flash column chromatography gave the pure product in 95% yield. 4-methoxybiphenyl nuclear magnetic analysis:1H NMR(400MHz，CDCl3，298K)：δ＝7.59-7.52(m，4H)，7.42(dd，J＝10.8，4.5Hz，2H)，7.34-7.28(m，1H)，6.99(d，J＝8.8Hz，2H)，3.86(s，3H)；13C NMR(101MHz，CDCl3，298K)：δ＝159.12，140.81，133.77，128.70，128.13，126.72,126.63，114.18，55.33)。
to verify Fe3O4@mSiO2The reusability of the @ NHC-Pd catalyst. After the catalytic reaction is completed, Fe is recovered by magnetic separation3O4@mSiO2The reaction was continued with ethanol and water to prepare 4-methoxybiphenyl (the reaction conditions were the same) using the catalyst of @ NHC-Pd and continuously washing with ethanol and water, and the yield of the obtained 4-methoxybiphenyl was as shown in FIG. 5, and after 12 cycles of use, Fe3O4@mSiO2The @ NHC-Pd still has high catalytic activity, the yield of 4-methoxybiphenyl can still reach 90%, and the transmission electron microscope images of the catalyst obtained by the last recovery are shown in FIGS. 3c and 3 d.
The above-described embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way and substantially, it should be noted that those skilled in the art may make several modifications and additions without departing from the scope of the present invention, which should also be construed as a protection scope of the present invention.
Claims (10)
1. A flower-shaped core-shell magnetic mesoporous microsphere immobilized N-heterocyclic carbene ring palladium catalyst is characterized in that the flower-shaped core-shell magnetic mesoporous microsphere is loaded with the N-heterocyclic carbene ring palladium catalyst shown as a formula I:
2. the flower-like core-shell magnetic mesoporous microsphere immobilized N-heterocyclic carbene ring palladium catalyst according to claim 1, wherein the flower-like core-shell magnetic mesoporous microsphere comprises magnetic Fe in a core shell3O4SiO outside the particle and core-shell2And (4) mesoporous.
3. The preparation method of the flower-like core-shell magnetic mesoporous microsphere immobilized N-heterocyclic carbene ring palladium catalyst according to claim 1 or 2, comprising the following steps:
step 1: fe preparation from iron source and silicon source3O4@SiO2Magnetic microspheres;
step 2: mixing Fe3O4@SiO2Dispersing magnetic microspheres in water to obtain magnetic microsphere dispersion, and treating the magnetic microsphere dispersion with a template agent to obtain flower-shaped core-shell magnetic mesoporous microspheres Fe3O4@mSiO2；
And step 3: flower-shaped core-shell type magnetic mesoporous microsphere Fe3O4@mSiO2Amination of (a);
and 4, step 4: reacting the aminated flower-shaped core-shell magnetic mesoporous microsphere with an N-heterocyclic carbene ligand to prepare a flower-shaped core-shell magnetic mesoporous microsphere immobilized N-heterocyclic carbene ligand;
and 5: immobilizing the flower-shaped core-shell magnetic mesoporous microspheres with N-heterocyclic carbene ligands and PdCl in an inert gas atmosphere2Adding the mixture into a solvent, stirring to obtain a mixed solution, adding carbonate into the mixed solution, performing reflux reaction, washing and drying a product after the reaction is finished, and preparing the flower-shaped core-shell magnetic mesoporous microsphere immobilized N-heterocyclic carbene cyclic palladium catalyst.
4. The method for preparing the flower-like core-shell magnetic mesoporous microsphere immobilized N-heterocyclic carbene cyclopalladated catalyst according to claim 3, wherein the iron source in the step 1 is at least one of ferric chloride and ferric sulfate; the silicon source is organic siloxane; the template agent in the step 2 comprises cetyl trimethyl ammonium bromide and fluorine surfactant FS-66.
5. The preparation method of the flower-like core-shell magnetic mesoporous microsphere immobilized N-heterocyclic carbene ring palladium catalyst according to claim 4, wherein the step 2 specifically comprises the following steps: cetyl trimethylammonium bromide, triethanolamine and ultrapure water were mixed at a ratio of 0.6 g: 0.1 mL: 30 mL-0.7 g: 0.2 mL: mixing the components in a proportion of 40mL, and stirring the mixture for 15 to 30 minutes at a temperature of between 60 and 70 ℃ to prepare a CTAB template solution; then weighing a template agent FS-66 according to the mass ratio of FS-66 to hexadecyl trimethyl ammonium bromide being 0.1-0.25: 1, dissolving the template agent FS-66 in isopropyl acetone to prepare a solution with the concentration of 0.0375-0.15 g/mL, adding the solution into the CTAB template solution, continuously stirring for 1-2 hours, adding TEOS according to the ratio of 6-10 mL TEOS/g hexadecyl trimethyl ammonium bromide, and stirring for 60-80 seconds to obtain a double-template solution; mixing the double-template solution and the magnetic microsphere dispersion liquid in a ratio of 2-3: 1, carrying out ultrasonic treatment for 2-3 minutes, then oscillating for 30-40 minutes on a circumferential oscillator at a speed of r being 600-700 r/min, and then shaking for 6 hours at a speed of r being 200-300 r/min; finally, separating the product, removing the template solution, adding an ethanol solution of saturated ammonium nitrate, oscillating and washing for 10-15 h, washing the washed solid product for 2-3 times by using absolute ethanol and water respectively, and drying to obtain the productTo flower-shaped core-shell type magnetic mesoporous microspheres; in the magnetic microsphere dispersion, Fe3O4@SiO2The concentration of the magnetic microspheres is 0.005-0.01 g/mL.
6. The preparation method of the flower-like core-shell magnetic mesoporous microsphere immobilized N-heterocyclic carbene cyclic palladium catalyst according to claim 3, wherein the amination in the step 3 specifically comprises: adding the flower-shaped core-shell magnetic mesoporous microspheres prepared in the step 1, amino alkyl siloxane and a cation trapping agent into cyclohexane, performing ultrasonic treatment to obtain a dispersion liquid, stirring the obtained dispersion liquid at room temperature for reaction, washing a product with n-hexane and ethanol after the reaction is finished, and drying to obtain the aminated flower-shaped core-shell magnetic mesoporous microspheres.
7. The preparation method of the flower-like core-shell magnetic mesoporous microsphere immobilized N-heterocyclic carbene ring palladium catalyst according to claim 6, wherein the amino alkyl siloxane is 3-aminopropyl trimethoxysilane; the cation trapping agent is dodecylamine; in the dispersion, the concentration of the flower-shaped core-shell magnetic mesoporous microspheres is 0.005-0.01 g/mL, the concentration of 3-aminopropyltrimethoxysilane is 1-3 v/v%, and the concentration of dodecylamine is 1-5 v/v%; the ultrasonic treatment time is 5-10 min, and the stirring reaction time is 4-6 h.
8. The preparation method of the flower-shaped core-shell magnetic mesoporous microsphere immobilized N-heterocyclic carbene ring palladium catalyst according to claim 3, wherein the mass ratio of the aminated flower-shaped core-shell magnetic mesoporous microsphere to the N-heterocyclic carbene ligand in the step 4 is 1: 1-1: 1.2, and the reaction conditions are as follows: methanol is used as a solvent, the reaction temperature is 50-60 ℃, and the reaction time is 2-3 days; the mole ratio of the carbonate to the flower-shaped core-shell magnetic mesoporous microsphere immobilized N-heterocyclic carbene ligand to the palladium chloride in the step 5 is 0.4:1: 1-0.7: 1.2: 1; in the mixed solution, the concentration of the flower-shaped core-shell magnetic mesoporous microsphere immobilized N-heterocyclic carbene ligand is 0.02-0.03 mol/L; the solvent is acetonitrile, and the carbonate is potassium carbonate; the time of the reflux reaction is 20-30 h.
9. The application of the flower-shaped core-shell magnetic mesoporous microsphere immobilized N-heterocyclic carbene cyclic palladium catalyst of claim 1 or 2.
10. Use according to claim 9, comprising use in a Suzuki-Miyaura coupling reaction.
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