CN113117754B - 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
- Publication number
- CN113117754B CN113117754B CN202110398134.3A CN202110398134A CN113117754B CN 113117754 B CN113117754 B CN 113117754B CN 202110398134 A CN202110398134 A CN 202110398134A CN 113117754 B CN113117754 B CN 113117754B
- Authority
- CN
- China
- Prior art keywords
- flower
- shaped core
- magnetic mesoporous
- heterocyclic carbene
- shell
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 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 102
- 239000011258 core-shell material Substances 0.000 title claims abstract description 75
- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 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 62
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 125000004122 cyclic group Chemical group 0.000 title claims abstract description 17
- 239000003446 ligand Substances 0.000 claims abstract description 24
- 238000005576 amination reaction Methods 0.000 claims abstract description 7
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical class CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 239000000047 product Substances 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 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 16
- 239000006185 dispersion Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 11
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical group CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical group CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 101150003085 Pdcl gene Proteins 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 4
- 239000012498 ultrapure water Substances 0.000 claims description 4
- 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
- 239000012298 atmosphere Substances 0.000 claims description 3
- 230000003100 immobilizing effect Effects 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- 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
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims 2
- 239000011261 inert gas Substances 0.000 claims 2
- 244000282866 Euchlaena mexicana Species 0.000 claims 1
- -1 aryl phenylboronic acid Chemical compound 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- HXITXNWTGFUOAU-UHFFFAOYSA-N dihydroxy-phenylborane Natural products OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 abstract description 3
- 150000001500 aryl chlorides Chemical class 0.000 abstract 1
- 238000006880 cross-coupling reaction Methods 0.000 abstract 1
- 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000007885 magnetic separation Methods 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 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
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 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
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000004693 imidazolium salts Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- VOAAEKKFGLPLLU-UHFFFAOYSA-N (4-methoxyphenyl)boronic acid Chemical compound COC1=CC=C(B(O)O)C=C1 VOAAEKKFGLPLLU-UHFFFAOYSA-N 0.000 description 1
- ZJJATABWMGVVRZ-UHFFFAOYSA-N 1,12-dibromododecane Chemical compound BrCCCCCCCCCCCCBr ZJJATABWMGVVRZ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ZFJSAAXAPRFPNQ-UHFFFAOYSA-N 1,8-bis(3-bromopropoxy)anthracene-9,10-dione Chemical compound BrCCCOC1=CC=CC=2C(C3=CC=CC(=C3C(C1=2)=O)OCCCBr)=O ZFJSAAXAPRFPNQ-UHFFFAOYSA-N 0.000 description 1
- IWDFHWZHHOSSGR-UHFFFAOYSA-N 1-ethylimidazole Chemical compound CCN1C=CN=C1 IWDFHWZHHOSSGR-UHFFFAOYSA-N 0.000 description 1
- HXVNBWAKAOHACI-UHFFFAOYSA-N 2,4-dimethyl-3-pentanone Chemical compound CC(C)C(=O)C(C)C HXVNBWAKAOHACI-UHFFFAOYSA-N 0.000 description 1
- WKBALTUBRZPIPZ-UHFFFAOYSA-N 2,6-di(propan-2-yl)aniline Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N WKBALTUBRZPIPZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 208000034809 Product contamination Diseases 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- NJSVDVPGINTNGX-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethanamine Chemical compound CCC[Si](OC)(OC)OCN NJSVDVPGINTNGX-UHFFFAOYSA-N 0.000 description 1
- DVARTQFDIMZBAA-UHFFFAOYSA-O ammonium nitrate Chemical class [NH4+].[O-][N+]([O-])=O DVARTQFDIMZBAA-UHFFFAOYSA-O 0.000 description 1
- 229940040526 anhydrous sodium acetate Drugs 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- FLNKWZNWHZDGRT-UHFFFAOYSA-N azane;dihydrochloride Chemical compound [NH4+].[NH4+].[Cl-].[Cl-] FLNKWZNWHZDGRT-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 229940032296 ferric chloride Drugs 0.000 description 1
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000003818 flash chromatography Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 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
- 239000002122 magnetic nanoparticle Substances 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- PKDCQJMRWCHQOH-UHFFFAOYSA-N triethoxysilicon Chemical compound CCO[Si](OCC)OCC PKDCQJMRWCHQOH-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—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
-
- 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
- B01J31/18—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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—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
-
- 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
- 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
- B01J2531/824—Palladium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
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 N-heterocyclic carbene metal complexes 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 N-heterocyclic carbenes are few, and the found N-heterocyclic carbenes 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 synthesis route disclosed in patent document CN 107880079A: the N-heterocyclic bis-carbene-palladium complex which takes 1, 4-bis (N-ethyl-benzimidazolium methyl) -2,3,5, 6-tetramethylbenzene arene salt as a precursor is mainly 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 108586345A: the 1,8-2[3- (N-ethylimidazolyl) propoxy ] anthraquinone hexafluorophosphate is mainly prepared by the reaction of 1, 8-bis (3-bromopropoxy) anthraquinone and N-ethyl-imidazole to generate 1,8-2[3- (N-ethylimidazolyl) propoxy ] anthraquinone halide and can also be prepared by the anion exchange reaction of 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:
the third synthetic route is disclosed in patent document CN 108579809A: mainly dissolving a N-heterocyclic carbene palladium compound and an amphiphilic polymer DSPE-PEG2000 in a small amount of dimethyl sulfoxide solution, 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-based functionalization, wherein the synthesis route of the fourth route is as follows:
the above synthetic routes all have certain disadvantages:
1) The homogeneous N-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 cyclic palladium catalyst is easily lost in the catalysis process, so that the catalyst is inactivated.
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 shell 3 O 4 SiO outside the particle and core-shell 2 And (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: preparation of Fe from iron source and silicon source 3 O 4 @SiO 2 Magnetic microspheres;
and 2, step: mixing Fe 3 O 4 @SiO 2 Dispersing 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 Fe 3 O 4 @mSiO 2 ；
And step 3: flower-shaped core-shell type magnetic mesoporous microsphere Fe 3 O 4 @mSiO 2 Amination 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: atmosphere of inert gasThen, flower-shaped core-shell magnetic mesoporous microspheres are immobilized with N-heterocyclic carbene ligands and PdCl 2 Adding 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 0.6g:0.1mL:30 mL-0.7 g:0.2mL: 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 CTAB template solution; then weighing template agent FS-66 according to the mass ratio of FS-66 to hexadecyl trimethyl ammonium bromide being 0.1-0.25, dissolving the template agent FS-66 in isopropyl ketone 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 according to the ratio of 2-3 to 1, then carrying out ultrasonic treatment for 2-3 minutes, then oscillating for 30-40 minutes on a circumferential oscillator at the r = 600-700 r/min, and then shaking for 6 hours at the r = 200-300 r/min; finally, separating the product and 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 flower-shaped core-shell magnetic mesoporous microspheres; in the magnetic microsphere dispersion, fe 3 O 4 @SiO 2 The concentration of the magnetic microspheres is 0.005-0.01 g/mL.
Preferably, the amination in the 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, 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.
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: methanol is used as a solvent, the reaction temperature is 50-60 ℃, and the reaction time is 2-3 days; the molar ratio of the carbonate to the flower-shaped core-shell type magnetic mesoporous microsphere immobilized N-heterocyclic carbene ligand to the palladium chloride in the step 5 is (1.4); in the mixed solution, the concentration of the flower-shaped core-shell type 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 to 30 hours.
The invention also provides application of the flower-shaped core-shell type 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 aperture is adjustable, so that the magnetic mesoporous silica with larger specific surface area can be prepared to be used as a carrier, and the mass transfer of reactant molecules is more facilitated; 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, the catalytic activity of the catalyst is basically kept unchanged after 12 times of recycling, and 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 type magnetic mesoporous microsphere immobilized N-heterocyclic carbene cyclic palladium catalyst;
FIG. 2 is a transmission electron micrograph of flower-like core-shell magnetic mesoporous microspheres prepared with different amounts of templating agent FS-66 (a: FS-66=0.075g, b FS-66=0.10g, c FS-66=0.125g, d FS-66= 0.15g);
fig. 3 is a transmission electron microscope image of flower-shaped core-shell type magnetic mesoporous microsphere immobilized N-heterocyclic carbene annular palladium catalyst, wherein, a and b are transmission electron microscope images of flower-shaped core-shell type magnetic mesoporous microsphere immobilized N-heterocyclic carbene annular palladium catalyst freshly prepared in example 1 under low multiple and high multiple respectively, and c and d are transmission electron microscope images of magnetic mesoporous microsphere immobilized N-heterocyclic carbene annular palladium catalyst recovered last time in application example 1 under low multiple and high multiple 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, preparation of flower-shaped core-shell magnetic mesoporous microspheres (a 1-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 appearance 3 O 4 Magnetic microspheres.
2) 0.50g of Fe was taken 3 O 4 Magnetic microspheres, sonicated in 60mL of ultrapure water for 2 minutes, added with 4.5ml of 1% naf solution, and then stirred on a stirrer (r =500 r/min). A mixture of 1.98mL TEOS (tetraethylorthosilicate) and ethanol (1.8mL EtOH +0.18mL TEOS) was added dropwise every 30 minutes for a total of 10 additions. After all additions were complete, rapid stirring was continued for 15 hours. Washing the product twice with absolute ethyl alcohol and twice with water, drying for 24 hours at 60 ℃ to obtain Fe 3 O 4 @SiO 2 。
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. 20mL of the dual template solution was added to 10mL of ultrasonically dispersed 0.08g Fe 3 O 4 @SiO 2 In aqueous solution, then sonicated for 2 minutes, then rapidly shaken (r =700 r/min) on a circular shaker for 30 minutes, then slowly shaken (r =250 r/min) for 6 hoursWhen the user wants to use the device. 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 areas 3 O 4 @mSiO 2 ) FIG. 2 shows a transmission electron micrograph of the compound.
S2, aminated magnetic mesoporous microsphere Fe 3 O 4 @mSiO 2 -NH 2 Synthesis of (a 4):
the amount of the template FS-66 prepared from S1 above was 0.15g of Fe 3 O 4 @mSiO 2 (0.5 g), 2% v/v APTMS (3-aminopropyltrimethoxysilane) and 3% v/v dodecylamine to 20ml cyclohexane, sonicated for 5min, stirred at room temperature for 5h, then the product washed once with n-hexane, once with ethanol and dried under vacuum at 50 ℃ for 24 hours to give aminated magnetic mesoporous microspheres Fe 3 O 4 @mSiO 2 -NH 2 。
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% aqueous formaldehyde) were added to the system and the system was diluted with 10 times of MeOH. Heating the system at 65 deg.C under reflux for 1 hr, and adding dropwise 7mL 86% 3 PO 4 Reflux 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: 1 H NMR(400MHz，CDCl 3 ，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)； 13 C NMR(101MHz，CDCl 3 ，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 is then isolated by chromatography on silica gel. The product was collected, dried by cooling by removing the solvent by rotary evaporation and weighed. Nuclear magnetic analysis of the product: 1 H NMR(400MHz，CDCl 3 ，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)； 13 C NMR(101MHz，CDCl 3 ，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 an imidazole salt (a 7):
3mmol of 4- (12-bromododecyloxy) benzaldehyde and 3.5mmol of 2, 6-diisopropyl) imidazole were dissolved in 8mL of 1, 4-dioxane, the reaction system was placed 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: 1 H NMR(400MHz，CDCl 3 ，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)； 13 C NMR(101MHz，CDCl 3 ，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 (a 8) by using the magnetic mesoporous microsphere:
aminated magnetic mesoporous microspheres a4 (0.40 g) prepared in S2 were added to dry methanol (20 ml) for sonication for 15 minutes, followed by addition of imidazolium salt a7 (0.044 g) prepared in S5 and heating at 50 ℃ for 2 days. After the reaction, separating the product by magnetic separation, washing the product with methanol for 3 times, and drying the product in vacuum at 50 ℃ for 24 hours 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 ring palladium catalyst (a 9= Fe) 3 O 4 @mSiO 2 @NHC-Pd)：
Under nitrogen, 0.24mmol of imidazolium salt and 0.21mmol of PdCl 2 Added to 10ml of acetonitrile solvent and stirred at 80 ℃ for 0.5 hour under nitrogen protection. Then adding K 2 CO 3 (0.12 mmol), cooling and refluxing for 24 hours, washing the product twice with water, washing with ethanol for 2 times, and vacuum drying at 50 ℃ for 24 hours to obtain flower-shaped core-shell type magnetic mesoporous microsphere immobilized N-heterocyclic carbene cyclic palladium catalyst Fe 3 O 4 @mSiO 2 @ NHC-Pd, its transmission electron micrograph is shown in figure 3a and 3b, the palladium loading in the catalyst prepared is 0.2mmol/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 applied 3 O 4 @mSiO 2 The @ 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 (0.75 mmol) and the flower-shaped core-shell type magnetic mesoporous microsphere immobilized N-heterocyclic carbene cyclic palladium catalyst (1 mol%) prepared in the step 1 are added, and K 2 CO 3 (1.5 equivalents) and EtOH/H in a volume ratio of 2 2 O (2.0 mL) 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, and the organic phase was collected and purified over anhydrous Na 2 SO 4 Drying, filtration and purification by flash column chromatography gave the pure product in 95% yield. 4-methoxybiphenyl nuclear magnetic analysis: 1 H NMR(400MHz，CDCl 3 ，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)； 13 C NMR(101MHz，CDCl 3 ，298K)：δ＝159.12，140.81，133.77，128.70，128.13，126.72,126.63，114.18，55.33)。
to verify Fe 3 O 4 @mSiO 2 The reusability of the @ NHC-Pd catalyst. After the catalytic reaction is completed, fe is recovered by magnetic separation 3 O 4 @mSiO 2 The 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, fe 3 O 4 @mSiO 2 The @ 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 figures 3c and 3 d.
The above-described embodiments are intended to be preferred embodiments of the present invention only, and not to limit the invention in any way and in any way, it being noted that those skilled in the art will be able to make modifications and additions without departing from the scope of the invention, which shall be deemed to also encompass the scope of the invention.
Claims (9)
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:
formula I;
the flower-shaped core-shell type magnetic mesoporous microsphere consists of magnetic Fe in a core shell 3 O 4 SiO outside the particle and core-shell 2 Mesoporous composition;
the preparation method of the flower-shaped core-shell magnetic mesoporous microsphere immobilized N-heterocyclic carbene ring palladium catalyst comprises the following steps:
step 1: fe preparation from iron source and silicon source 3 O 4 @SiO 2 Magnetic microspheres;
and 2, step: mixing Fe 3 O 4 @SiO 2 Dispersing 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 Fe 3 O 4 @mSiO 2 ；
And 3, step 3: flower-shaped core-shell type magnetic mesoporous microsphere Fe 3 O 4 @mSiO 2 Amination 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 atmosphere 2 Adding 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.
2. The preparation method of the flower-like core-shell magnetic mesoporous microsphere immobilized N-heterocyclic carbene ring palladium catalyst according to claim 1 comprises the following steps:
step 1: preparation of Fe from iron source and silicon source 3 O 4 @SiO 2 Magnetic microspheres;
step 2: mixing Fe 3 O 4 @SiO 2 Dispersing magnetic microsphere in water to obtain magnetic microsphere dispersion, and using templateTreating the magnetic microsphere dispersion with an agent to obtain flower-shaped core-shell magnetic mesoporous microspheres Fe 3 O 4 @mSiO 2 ；
And step 3: flower-shaped core-shell type magnetic mesoporous microsphere Fe 3 O 4 @mSiO 2 Amination of (2);
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 atmosphere 2 Adding 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.
3. The method for preparing the flower-like core-shell magnetic mesoporous microsphere immobilized N-heterocyclic carbene cyclopalladated catalyst according to claim 2, 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 hexadecyl trimethyl ammonium bromide and a fluorine surfactant FS-66.
4. The preparation method of the flower-like core-shell magnetic mesoporous microsphere immobilized N-heterocyclic carbene ring palladium catalyst according to claim 3, wherein the step 2 specifically comprises the following steps: cetyl trimethylammonium bromide, triethanolamine and ultrapure water were mixed at a ratio of 0.6g:0.1mL:30 mL-0.7 g:0.2mL:40 mixing the components in a ratio of mL, and stirring the mixture for 15 to 30 minutes at a temperature of between 60 and 70 ℃ to prepare a hexadecyl trimethyl ammonium bromide 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 to 0.25, dissolving the template agent FS-66 in isopropanol to prepare a solution with the concentration being 0.0375 to 0.15g/mL, adding the solution into the hexadecyl trimethyl ammonium bromide template solution, continuously stirring for 1 to 2 hours, then adding TEOS according to the ratio of 6 to 10mL TEOS/g hexadecyl trimethyl ammonium bromide, stirring for 60 to 80 seconds, and then, adding the TEOS into the mixtureObtaining a double-template solution; mixing the double-template solution and the magnetic microsphere dispersion liquid according to the proportion of 2-3, carrying out ultrasonic treatment for 2-3 minutes, then oscillating for 30-40 minutes at the speed of r = 600-700 r/min on a circumferential oscillator, and then shaking for 6 hours at the speed of r = 200-300 r/min; finally separating the product, removing the template solution, adding a saturated ethanol solution of ammonium nitrate, oscillating and washing for 10-15h, washing the washed solid product for 2-3 times respectively by using absolute ethanol and water, and drying to obtain the flower-shaped core-shell magnetic mesoporous microspheres; in the magnetic microsphere dispersion, fe 3 O 4 @SiO 2 The concentration of the magnetic microspheres is 0.005 to 0.01g/mL.
5. The preparation method of the flower-like core-shell magnetic mesoporous microsphere immobilized N-heterocyclic carbene cyclic palladium catalyst according to claim 2, 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.
6. The preparation method of the flower-like core-shell magnetic mesoporous microsphere immobilized N-heterocyclic carbene ring palladium catalyst according to claim 5, wherein the amino alkyl siloxane is 3-aminopropyl trimethoxysilane; the cation trapping agent is dodecyl amine; in the dispersion liquid, the concentration of the flower-shaped core-shell type magnetic mesoporous microspheres is 0.005 to 0.01g/mL, the concentration of 3-aminopropyltrimethoxysilane is 1 to 3v/v%, and the concentration of dodecylamine is 1 to 5v/v%; the ultrasonic treatment time is 5 to 10min, and the stirring reaction time is 4 to 6h.
7. The method for preparing the flower-shaped core-shell magnetic mesoporous microsphere immobilized N-heterocyclic carbene cyclopalladated catalyst according to claim 2, 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 to 1.2, and the reaction conditions are as follows: methanol is used as a solvent, the reaction temperature is 50 to 60 ℃, and the reaction time is 2 to 3 days; the molar 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 (1.4); in the mixed solution, the concentration of the immobilized N-heterocyclic carbene ligand of the flower-shaped core-shell type magnetic mesoporous microsphere is 0.02 to 0.03mol/L; the solvent is acetonitrile, and the carbonate is potassium carbonate; the time of the reflux reaction is 20 to 30 hours.
8. The application of the flower-shaped core-shell magnetic mesoporous microsphere immobilized N-heterocyclic carbene ring palladium catalyst of claim 1.
9. Use according to claim 8, comprising use in a Suzuki-Miyaura coupling reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110398134.3A CN113117754B (en) | 2021-04-14 | 2021-04-14 | Flower-shaped core-shell type magnetic mesoporous microsphere immobilized N-heterocyclic carbene cyclic palladium catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110398134.3A CN113117754B (en) | 2021-04-14 | 2021-04-14 | Flower-shaped core-shell type magnetic mesoporous microsphere immobilized N-heterocyclic carbene cyclic palladium catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113117754A CN113117754A (en) | 2021-07-16 |
| CN113117754B true CN113117754B (en) | 2022-10-11 |
Family
ID=76776272
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110398134.3A Active CN113117754B (en) | 2021-04-14 | 2021-04-14 | Flower-shaped core-shell type magnetic mesoporous microsphere immobilized N-heterocyclic carbene cyclic palladium catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113117754B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115672290B (en) * | 2022-10-21 | 2024-01-26 | 浙江海洋大学 | Copper ion imprinting magnetic mesoporous silica composite material, preparation method and adsorption catalysis application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2555613A1 (en) * | 2014-06-26 | 2016-01-05 | Universidad De Alcalá | Nhl palladium heterogeneous complexes and their uses as recoverable catalysts (Machine-translation by Google Translate, not legally binding) |
| CN105771904A (en) * | 2016-03-09 | 2016-07-20 | 清华大学 | Magnetic adsorbent as well as preparation method thereof, and recycling of palladium in nitric acid medium |
| EP3339313A1 (en) * | 2016-12-22 | 2018-06-27 | Umicore Ag & Co. Kg | Metal organic compounds |
| CN108465472A (en) * | 2018-03-26 | 2018-08-31 | 北京化工大学 | A kind of hydrotalcite supported palladium based alloy catalyst and preparation method thereof |
| CN111939983A (en) * | 2020-08-20 | 2020-11-17 | 淮北师范大学 | Magnetic material loaded nitrogen heterocyclic carbene copper catalyst and preparation method and application thereof |
-
2021
- 2021-04-14 CN CN202110398134.3A patent/CN113117754B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2555613A1 (en) * | 2014-06-26 | 2016-01-05 | Universidad De Alcalá | Nhl palladium heterogeneous complexes and their uses as recoverable catalysts (Machine-translation by Google Translate, not legally binding) |
| CN105771904A (en) * | 2016-03-09 | 2016-07-20 | 清华大学 | Magnetic adsorbent as well as preparation method thereof, and recycling of palladium in nitric acid medium |
| EP3339313A1 (en) * | 2016-12-22 | 2018-06-27 | Umicore Ag & Co. Kg | Metal organic compounds |
| CN108465472A (en) * | 2018-03-26 | 2018-08-31 | 北京化工大学 | A kind of hydrotalcite supported palladium based alloy catalyst and preparation method thereof |
| CN111939983A (en) * | 2020-08-20 | 2020-11-17 | 淮北师范大学 | Magnetic material loaded nitrogen heterocyclic carbene copper catalyst and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| Magnetic core–shell-structured nanoporous organosilica microspheres for the Suzuki–Miyaura coupling of aryl chlorides: improved catalytic activity and facile catalyst recovery;Hengquan Yang et al.;《Journal of Materials Chemistry》;20120224;第6639-6648页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113117754A (en) | 2021-07-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Tahmasbi et al. | Magnetic MCM-41 nanoparticles as a support for the immobilization of a palladium organometallic catalyst and its application in C–C coupling reactions | |
| Lili et al. | Catalysis by metal–organic frameworks: proline and gold functionalized MOFs for the aldol and three-component coupling reactions | |
| CN109020891B (en) | Synthesis of zeolite-like imidazole ester framework material Cu-ZIF and application of zeolite-like imidazole ester framework material Cu-ZIF as catalyst | |
| Pawar et al. | Supported NHC-benzimi@ Cu complex as a magnetically separable and reusable catalyst for the multicomponent and click synthesis of 1, 4-disubstituted 1, 2, 3-triazoles via huisgen 1, 3-dipolar cycloaddition | |
| CN112221540B (en) | Pd 2+ Supported metal organic framework composite catalyst and preparation method and application thereof | |
| CN112876516B (en) | N- (4-indolyl) N-heterocyclic carbene palladium complex and application thereof | |
| CN109912809B (en) | Non-noble metal-metal organic framework composite material, preparation method and application thereof | |
| CN113117754B (en) | Flower-shaped core-shell type magnetic mesoporous microsphere immobilized N-heterocyclic carbene cyclic palladium catalyst and preparation method and application thereof | |
| Abdel-Fatah et al. | Nanostructured metal oxides prepared from schiff base metal complexes: Study of the catalytic activity in selective oxidation and C–C coupling reactions | |
| Taghiyar et al. | New perspective to catalytic epoxidation of olefins by Keplerate containing Keggin polyoxometalates | |
| CN103980086A (en) | Preparation method of 1,3-diacetylene catalytic system | |
| Çakır et al. | Synthesis of water soluble Pd‐Piperidoimidazolin‐2‐ylidene complexes and their catalytic activities in neat water | |
| Patra et al. | Hydrothermal syntheses of d10-based Zn (II) and Cd (II) metal–organic frameworks for the catalysis of the Knoevenagel condensation | |
| CN111848974A (en) | Polyacid-based metal-organic framework material, synthesis method thereof and application thereof in coupling of photocatalytic oxidation benzylamine | |
| CN110935481B (en) | Catalyst for selective hydrogenolysis of aromatic ether bond, preparation and application thereof | |
| Chen et al. | Synergistic effect of amino-functionalized SBA-15 in Cu-catalyzed oxidative homocoupling of phenylacetylene | |
| Wang et al. | Microcrystalline Zinc Coordination Polymers as Single‐site Heterogeneous Catalysts for the Selective Synthesis of Mono‐oxazolines from Amino Alcohol and Dinitriles | |
| CN114591284B (en) | Zn-MOF-based catalyst in CO 2 Process for synthesizing cyclic carbonates | |
| Ma et al. | Cationic quaternary ammonium-stabilized Nb oxoclusters catalyze reductive amination of carbon dioxide with hydrosilane | |
| CN110302836B (en) | Preparation method and application of graphene oxide supported diimine coordination palladium | |
| CN115894955A (en) | Zirconium-based metal organic framework material, and synthesis method and application thereof | |
| CN114105901B (en) | Metal organic framework based on Cd (II), composite catalyst, preparation method and application thereof | |
| CN114950527A (en) | Catalyst for synthesis of azobenzene compounds | |
| CN114588929A (en) | Supported copper nanocluster catalyst and application thereof in AHA coupling reaction | |
| CN114558618B (en) | Preparation method of azide-alkyne cycloaddition multi-acid-based photocatalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |