CN113333021A - Porous polymer supported palladium catalyst with high catalytic activity and application thereof in catalyzing Suzuki-Miyaura reaction - Google Patents
Porous polymer supported palladium catalyst with high catalytic activity and application thereof in catalyzing Suzuki-Miyaura reaction Download PDFInfo
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- CN113333021A CN113333021A CN202110374811.8A CN202110374811A CN113333021A CN 113333021 A CN113333021 A CN 113333021A CN 202110374811 A CN202110374811 A CN 202110374811A CN 113333021 A CN113333021 A CN 113333021A
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- catechol
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 199
- 239000003054 catalyst Substances 0.000 title claims abstract description 127
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 103
- 229920000642 polymer Polymers 0.000 title claims abstract description 63
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 24
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 title claims abstract description 20
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims abstract description 92
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 76
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 58
- 239000000047 product Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 17
- -1 aromatic halide Chemical class 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 15
- 238000004949 mass spectrometry Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000003760 magnetic stirring Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000012634 fragment Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 claims description 2
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 claims description 2
- 150000001642 boronic acid derivatives Chemical class 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 150000004032 porphyrins Chemical class 0.000 claims description 2
- 238000005070 sampling Methods 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- 238000002360 preparation method Methods 0.000 description 24
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- 239000007789 gas Substances 0.000 description 13
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- UDHAWRUAECEBHC-UHFFFAOYSA-N 1-iodo-4-methylbenzene Chemical compound CC1=CC=C(I)C=C1 UDHAWRUAECEBHC-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 238000006880 cross-coupling reaction Methods 0.000 description 10
- 238000006069 Suzuki reaction reaction Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 235000012239 silicon dioxide Nutrition 0.000 description 9
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 description 8
- 239000010453 quartz Substances 0.000 description 8
- 101150003085 Pdcl gene Proteins 0.000 description 7
- 238000005859 coupling reaction Methods 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- RINOYHWVBUKAQE-UHFFFAOYSA-N 1-iodo-2-methylbenzene Chemical compound CC1=CC=CC=C1I RINOYHWVBUKAQE-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 239000002638 heterogeneous catalyst Substances 0.000 description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000010791 quenching Methods 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 4
- GQPLZGRPYWLBPW-UHFFFAOYSA-N calix[4]arene Chemical compound C1C(C=2)=CC=CC=2CC(C=2)=CC=CC=2CC(C=2)=CC=CC=2CC2=CC=CC1=C2 GQPLZGRPYWLBPW-UHFFFAOYSA-N 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- HBMNRHWHAHVIHW-UHFFFAOYSA-N 1,3,5-tris[(3,4-dimethoxyphenyl)methyl]benzene Chemical compound COc1ccc(Cc2cc(Cc3ccc(OC)c(OC)c3)cc(Cc3ccc(OC)c(OC)c3)c2)cc1OC HBMNRHWHAHVIHW-UHFFFAOYSA-N 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000007341 Heck reaction Methods 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical class C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 229930014626 natural product Natural products 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- BIWQNIMLAISTBV-UHFFFAOYSA-N (4-methylphenyl)boronic acid Chemical compound CC1=CC=C(B(O)O)C=C1 BIWQNIMLAISTBV-UHFFFAOYSA-N 0.000 description 1
- CAULOKPIRVGVRU-UHFFFAOYSA-N 1,2,3-tribenzylbenzene Chemical group C=1C=CC(CC=2C=CC=CC=2)=C(CC=2C=CC=CC=2)C=1CC1=CC=CC=C1 CAULOKPIRVGVRU-UHFFFAOYSA-N 0.000 description 1
- AGUNPFIFLDXKPR-UHFFFAOYSA-N 2-trityl-1h-imidazole Chemical compound C1=CNC(C(C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=N1 AGUNPFIFLDXKPR-UHFFFAOYSA-N 0.000 description 1
- ZCJZVMNBJKPQEV-UHFFFAOYSA-N 4-[3,5-bis(4-formylphenyl)phenyl]benzaldehyde Chemical compound C1=CC(C=O)=CC=C1C1=CC(C=2C=CC(C=O)=CC=2)=CC(C=2C=CC(C=O)=CC=2)=C1 ZCJZVMNBJKPQEV-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 241000928106 Alain Species 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000012696 Pd precursors Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910000929 Ru alloy Inorganic materials 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004305 biphenyl Chemical class 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 239000013310 covalent-organic framework Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- OYJSZRRJQJAOFK-UHFFFAOYSA-N palladium ruthenium Chemical compound [Ru].[Pd] OYJSZRRJQJAOFK-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 1
- 125000004151 quinonyl group Chemical group 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229940109850 royal jelly Drugs 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
-
- 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
- B01J31/165—Polymer immobilised coordination complexes, e.g. organometallic complexes
-
- 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
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a porous polymer supported palladium catalyst with high catalytic activity: the porous polymer derived from catechol is used as a catalyst framework and reacts with a palladium source to obtain the supported palladium catalyst. The invention also discloses that the catechol-derived porous polymer supported palladium catalyst can catalyze the Suzuki-Miyaura coupling reaction at room temperature without water and oxygen. The catalyst has high catalytic activity, high selectivity and high stability, and is simple to prepare and can be repeatedly used.
Description
Technical Field
The invention relates to a porous polymer supported palladium catalyst with high catalytic activity and application thereof in catalyzing Suzuki-Miyaura reaction.
Background
Noble metals are highly reactive to adsorption of reactants due to their incomplete d-electron orbitals, which facilitates the formation of intermediates, and thus have high catalytic activity in various chemical reactions including oxidation, hydrogenation, and coupling reactions (m.s. hegde, giridhara madras, k.c. title, Noble Metal Catalysts, acc.chem.res.,2009,42, 704-712). The most studied noble metal is palladium, and the homogeneously catalyzed coupling reaction thereof is an important component of organic synthesis (such as Suzuki-Miyaura reaction, Heck reaction, etc.), and is a popular direction in organic chemistry research at present, and is now widely used for synthesizing various natural products, drugs, functional materials, etc. (q. -h.xia, h. -q.ge, c. -p.ye, z. -m.liu, k. -x.su, advanced in homogenetic and heterologous Catalytic oxidation, chem.rev., 2005,105,1603).
The Suzuki-Miyaura reaction (Suzuki-Miyaura reaction, also called Suzuki reaction) is an organic coupling reaction, and aryl or alkenyl boric acid or boric acid ester and chlorine, bromine, iodo arene or olefin are subjected to cross coupling under the catalysis of a palladium catalyst and the like. The reaction has wide application in organic synthesis, stronger substrate adaptability and functional group tolerance, and is commonly used for synthesizing derivatives of polyene hydrocarbon, styrene and biphenyl, thereby being applied to the synthesis of a plurality of natural products and organic materials. Wherein the palladium catalyst is the core of the reaction. The development of highly active, recyclable palladium catalysts is currently the focus of research. However, the palladium homogeneous catalyst has basic defects, such as difficult separation and purification, product pollution and separation and purification cost increase; expensive itself, etc. These do not meet the green sustainable development call, which hinders further industrial development. In general, palladium is immobilized on a solid substrate with high specific surface area to prepare a corresponding heterogeneous catalyst, which can retain the activity of palladium and can be effectively separated from the mixture for reuse, thereby well solving the "pain point" in the field. Therefore, we can effectively solve these problems by a heterogeneous catalytic system.
At present, the preparation of supported palladium catalysts is mainly divided into two types: one is to directly attach palladium to the surface of the carrier (such as silicon dioxide, carbon nanotubes, metal oxides, etc.) by physical adsorption [3 ]. For example, northern chuan macro et al can realize a coupling reaction of p-methylbenzeneboronic acid and bromobenzene at 100 ℃ with high yield using palladium ruthenium alloy particles as a catalyst (northern chuan macro, grassland kangping, yonggangsheng jun, zoteng jun, madet saaka han kukograph, catalyst using PdRu solid solution type alloy particles, chinese patent CN 104661746A). Okumura Kazu et al disclose a catalyst for suzuki reaction, which is a composite obtained from palladium and USY type zeolite, has good catalytic activity and has an excellent TON (conversion number) value (EP2402083a 1). Japanese patent JP2010-069415a discloses a heterogeneous catalyst for suzuki reaction, Heck reaction and the like, which is a composite obtained from palladium and FAU type zeolite and has high yield, and excellent TON (number of conversions) and TOF (frequency of conversion) values. Eric Gaigneaux et Al SUPPORTED palladium sources on various OXIDE surfaces successfully prepared heterogeneous palladium catalysts, a series OF which were capable OF efficiently catalyzing Suzuki-Miyaura coupling REACTIONS at 95 ℃ (Eric Gaigneaux, Marc Jacquemin, Damien Hauwaert, Caroline Cellier, Alain Merschaurt, Raquel Mateos Blanco, METHOD OF CARRYING OUT CC-COUPFING REACTION USING OXIDE SUP PD-CATAEYSTS, US patent 2014/0163283 Al). Japanese patent JP2020-163296a discloses that palladium and TiO2 are used for suzuki coupling reaction, which is environmentally friendly and has good yield and the like. Chuaijianhua et al disclose a preparation method of a Pd monatomic catalyst for catalyzing Suzuki coupling reaction, which comprises the steps of preparing a Ti0.87O2 nanosheet containing a Ti vacancy by calcining at high temperature, adding a Pd precursor into a colloidal suspension of a single-layer Ti0.87O2 nanosheet, uniformly stirring to obtain a suspension, and then freeze-drying to obtain the monatomic catalyst Pd1-Ti0.87O2 (a preparation method of the Pd monatomic catalyst for catalyzing Suzuki coupling reaction, CN 111686720A). However, the production of such heterogeneous catalysts requires severe reaction conditions (e.g., high pressure and high temperature). Secondly, it may be detached from the support substrate during the catalytic process due to weak interaction between palladium (platinum) and the support, so that self-polymerization occurs to lose catalytic activity. The other method is to fix the noble metal on the carrier by chemical bonding. Compared with the former method, the method has mild preparation conditions, and generally adopts the method of introducing the surface functional group of the carrier into a heteroatom structural unit, mainly a nitrogen-containing and phosphorus-containing structural fragment. For example, dun et al prepared Pd @ COF-QA catalyst by using an organic framework containing a quaternary ammonium salt fragment as a carrier of the catalyst and then loading palladium metal, and the catalyst could effectively catalyze Suzuki-Miyaura coupling reaction at 50 ℃ (dun, royal jelly, liu yao, a three-phase catalyst Pd @ C0F-QA and its preparation method and application, chinese patent CN 109988079A). Liliang et al use a triazine group connected calix [4] arene as a carrier, and react with palladium acetate to prepare a CaP0P3@ Pd catalyst, and the catalyst can realize a Suzuki-Miyaura coupling reaction at 80 ℃ (Liliang, Zhangzhi faithful, Anduo, Lihanxue, Zhang Xinghua, porous polymer immobilized palladium catalyst CaP0P3@ Pd of triazine group connected calix [4] arene, a preparation method and application thereof, and Chinese patent CN 110270378A). Liu Jian et al disclose a covalent organic framework material supported Pd catalyst for Suzuki reaction, which has the advantages of high catalytic activity, good selectivity, wide substrate application range, easy recovery and reuse, mild reaction conditions, green and environment-friendly reaction solvent and the like, and the preparation process is simple, the raw materials are easy to obtain, and the production cost is low (Chinese patent CN 111097520A). Liugui Yan et al disclose a Pd-NHC complex modified by a group with high steric hindrance, which takes N-heterocyclic carbene modified by the group with high steric hindrance as a ligand and also selects trityl imidazole as an auxiliary ligand. The Pd-NHC complex has higher stability, and can catalyze the Suzuki-Miyaura coupling reaction of chlorinated aromatic hydrocarbon and aryl boric acid with steric hindrance (Chinese patent CN 108690086A). Patents publication nos. CN107880079A, CN103418438A, etc. relate to an azacarbene-based palladium catalyst having excellent reactivity for suzuki reaction. The patent with the publication number of CN105327713A discloses an adamantane supported NHC-Pd catalyst, which is prepared by using 1,3,5, 7-tetra (4- (1-imidazole) phenyl) adamantane as a raw material, quaternizing the raw material, and coordinating the quaternized raw material with palladium acetate [ Pd (OAc)2] to prepare a porous adamantane supported NHC-Pd catalyst with a three-dimensional configuration. The obtained catalyst has higher thermal stability and certain porosity, can catalyze the Suzuki-Miyaura coupling reaction under mild and aerobic conditions and obtain excellent catalytic effect, and can be reused through simple centrifugal filtration after the catalytic reaction is finished, thereby solving the problem of recycling of homogeneous catalysts. The method has simple and feasible reaction route, and can be used as an efficient catalyst for synthesizing medicines, pesticides, spices and functional materials. Patent publication No. CN107746452A discloses a palladium supported heterogeneous catalyst based on micro-mesoporous phenolic resin, which is prepared by polymerizing tris (4-aldehyde phenyl) phosphine and a phenolic hydroxyl compound to obtain a micro-mesoporous phenolic resin with a large specific surface area and rich in hydroxyl and triphenylphosphine, and then performing a coordination reaction of palladium metal and triphenylphosphine to obtain a porous phenolic resin based palladium metal supported heterogeneous catalyst. Because palladium and the corresponding heteroatom have strong coordination, the loss of an active center in the catalysis process can be effectively prevented, the service life of the catalyst is prolonged, and the catalysis cost is reduced. As commercially available noble metal (Pd) heterogeneous catalysts, there are Fibrecat (Johnson Matthey), Noblyst (Evonik), EnCats (Reaxa; today's S.Amit), PdTekits (polymer-bound) (Biotage) and Silicat (Siliccycle), among others. However, these catalyst functionalizations often involve cumbersome procedures and are structurally simple.
The catechol structure unit has rich electrochemical performance, easy reversible oxidation to semiquinone and quinone forms and strong interaction with metal track, so that it has been used widelyIn coordination chemistry of various metal ions, e.g. Pd, Pt, Ru[8]And the like. Therefore, a porous two-dimensional material containing ortho-diphenol structural fragments would be an ideal carrier material. Based on the above, it is very important to develop a catechol-derived porous polymer supported palladium catalyst, which can realize high conversion and high selectivity of aromatic halogenated hydrocarbon boric acid derivatives to generate cross-coupled products at room temperature.
Disclosure of Invention
In order to solve the problems, the invention provides a porous polymer supported palladium catalyst with high catalytic activity and a preparation method thereof, and also provides related application of a method for realizing high conversion and high selectivity generation of a cross-coupling product of an aromatic halogenated hydrocarbon boric acid derivative at room temperature. Specifically, the palladium and the porous polymer have strong interaction through the structural design of the catalyst, and the catalyst has a good catalytic effect (the porous polymer supported palladium catalyst has the advantages of high reaction activity, good selectivity and the like, and has an ideal TOF value); the catalyst has various structural modes, can be repeatedly used for many times, and simultaneously has no loss of catalytic activity and selectivity; the catalyst is prepared under mild reaction conditions without reaction conditions such as high temperature and high pressure.
The technical scheme adopted by the invention is as follows:
a porous polymer supported palladium catalyst derived from catechol and having the structure of compound I or II (II') or III:
or
In the compound, R1, R4, R5, R6 and R9 are selected from CH and various alkyl chains derived from the CH, N, O, S; n1, n2 and n3 are integers respectively, and n1+ n2+ n3> is 1; r7 is selected from CH and various alkyl chains derived from CH, benzene ring, 1,3, 5-triazine; r8 is selected from C, C ═ C, porphyrin; r2, R3 may be two H or 1 Pd, giving the following structural fragments with adjacent groups:
in one of the porous polymer supported palladium catalyst structures,
is at least 1.
The preparation method of the catechol-derived porous polymer supported palladium catalyst is characterized in that alkali is added into the catechol-derived porous polymer for reaction, and then a palladium source is added for reaction to finally obtain the catechol-derived porous polymer supported palladium catalyst.
The preparation method of the catechol-derived porous polymer supported palladium catalyst is characterized by comprising the following steps of:
(1) dispersing a catechol-derived porous polymer in a solvent, adding alkali, reacting, filtering and washing to obtain solid powder;
(2) and (2) dispersing the solid powder obtained in the step (1) in a solvent, adding a palladium source, reacting, and carrying out post-treatment to obtain the catechol-derived porous polymer supported palladium catalyst.
The preparation method of the catalyst is characterized in that the solvent in the step (1) is ethanol, the alkali in the step (1) is NaOH, and the mixing mass ratio of the dosage of the porous polymer derived from the compound catechol in the step (1) and the dosage of the alkali is m (the porous polymer derived from the catechol): m (base) ═ 1:0.0001 to 1:1, where m is mass; the reaction condition in the step (1) is ultrasonic reaction or magnetic stirring reaction, and ethanol and deionized water are used for washing.
The preparation method of the catalyst is characterized in that the palladium source in the step (2) is PdY or hydrate thereof, Y is-Cl, -AcO or Cl2(NH3)4In the amount ratio of m (compound II/V (V')/VIII): m (palladium source) is 1:0.0001 to 1:1, wherein m is mass; the reaction condition in the step (2) is ultrasonic reaction or magnetic stirring reaction, the post-treatment in the step (2) is filtration, and the solid residue is washed by an organic solvent and water.
The preparation method of the catechol-derived porous polymer comprises the following steps: a) preparation of the porous Polymer: tribenzylbenzene substituted at hexaalkoxy, dialdehydes (trialdehyde, tetraaldehyde) or derivatives thereof, acetic anhydride, and a catalyst (e.g., FeCl)3) Adding a solvent (such as dichloromethane) into the mixed system and heating for reaction; adding catalyst (e.g. FeCl)3) Further reaction; carrying out post-treatment (such as adding methanol for quenching, then filtering, and washing solid residues) on the mixed solution to obtain a porous polymer; b) preparation of catechol-derived porous Polymer: adding a solvent into a mixed system of the porous polymer prepared in the step a) and a catalyst (such as boron tribromide), and then stirring for reaction; and adding water to the solution for quenching, then filtering, and washing the solid residue to obtain the catechol-derived porous polymer.
The application of the catalyst in Suzuki-Miyaura is characterized in that: the Suzuki-Miyaura reaction can be realized at room temperature without the harsh conditions of water and oxygen at room temperature by using a porous polymer load palladium catalyst derived from catechol. The application is characterized by comprising the following steps: the aromatic halide and the boric acid derivative are mixed with the catalyst prepared above, the solvent is added, the reaction is carried out at room temperature, and the (optional) mixture is sampled and the product yield is determined.
The application is characterized by comprising the following steps:
(1) mixing aromatic halide and boric acid derivative with the catalyst, and adding solvent;
(2) magnetically stirring and reacting for 3-24h at 10-35 ℃;
and optionally, (3) sampling the mixture to determine the product yield.
The application is characterized in that: the solvent in step (1) is preferably ethanol: 2:1 of water; the mixing molar ratio in the step (1) is n (aromatic halide): n (boronic acid derivative): n (catalyst) ═ 1 (1-2) (0.0001-0.1), where n is the amount of material; the yield is preferably determined by a high performance gas mass spectrometer. The application is characterized in that: the catalyst can be repeatedly used for at least 5 times, and meanwhile, the catalytic activity and the selectivity are not obviously lost.
The invention has the following beneficial effects by adopting the technical scheme:
1. the invention provides a preparation method of a palladium catalyst loaded on a porous polymer which can be successfully prepared and derived from catechol; the catalyst is prepared under mild reaction conditions without reaction conditions such as high temperature and high pressure.
2. The invention also provides an application method of the catechol-derived porous polymer-supported palladium catalyst with a brand-new structure, and the palladium catalyst can effectively catalyze the coupling reaction of aromatic halide and boric acid derivatives; according to the invention, through the structural design of the catalyst, strong interaction exists between palladium and a porous polymer, and the catalyst has a good catalytic effect when being used in Suzuki-Miyaura reaction (the porous polymer supported palladium catalyst has the advantages of high reaction activity, good selectivity and the like, and has an ideal TOF value); in ten thousandth minute of useThe catalyst has the advantages that when palladium chloride and palladium acetate are used as palladium sources, the conversion rate can reach 91% in 6 hours, the selectivity is 100%, and the TOF value is 2167 hours-1(ii) a When the tetraaminopalladium chloride is used as a palladium source, the conversion rate can reach 85 percent in 6 hours, the selectivity is 100 percent, and the TOF value is 2215h-1. It can be seen that the catechol-derived porous polymer supported palladium catalyst synthesized by the method has the advantages of high reaction activity, good selectivity and the like, which are difficult to realize by other palladium catalysts.
3. The palladium catalyst loaded by the porous polymer has various structural modes, and the catalyst can be repeatedly used. Most of the catalysts used in the prior art cannot be recycled due to no recycling value, difficulty in separation or difficulty in ensuring the purity after separation, and the catalysts can overcome the defects of the catalysts, can be used for multiple times, and are circulated for at least 5 times without loss of catalytic activity and selectivity.
Drawings
FIG. 1: 10% Pd @ POG-OH and 10% Pd (NH)3)4High-efficiency gas-phase mass spectrogram of result of @ POG-OH catalyzed Suzuki-Miyaura coupling reaction
FIG. 2: data plot for catalytic cycle of Suzuki-Miyaura coupling reaction
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for the purpose of illustration only, and are not intended to limit the scope of the present invention.
Example 1
The preparation method of the catechol-derived porous polymer supported palladium catalyst comprises the following steps of 10% of Pd @ POG-OH (10% of palladium element accounts for the mass ratio of the catalyst): catechol-derived porous polymer, POG-OH (40mg) and potassium hydroxide (4.22mg), were weighed into 80mL of ethanol, i.e., m (POG-OH): sonicating for 1h at room temperature, filtering and washing the solid 3 times with deionized water, transferring to a beaker and adding PdCl, all according to the criteria of claim 52Or Pd (AcO)2(6.67 or 8.44mg), i.e., m (POG-OH): m (PdCl)2Or Pd (AcO)2) 1:0.16(0.21) meets the criteria of claim 6,80mL of ethanol is subjected to ultrasonic treatment for 1h at room temperature, and the mixture is filtered and washed with water and ethanol for 3 times to obtain the catechol-derived porous polymer supported palladium catalyst 10% Pd @ POG-OH (10% of palladium element accounts for the mass ratio of the catalyst) shown in the formula 1, wherein the yield is 100%. The actual metal content was determined by ICP to be 7%.
The preparation method of the catechol-derived porous polymer POG-OH comprises the following steps: 100mL of dichloromethane solvent was added to a mixed system of 1,3, 5-tris (3, 4-dimethoxybenzyl) benzene (0.4mmol), 9-dimethyl-2, 7-fluorenedial (0.6mmol), acetic anhydride (20mmol) and ferric trichloride (0.08mmol), and the mixture was reacted for 48 hours under magnetic stirring at 25 ℃. Ferric trichloride (72mmol) was added again to the system, and the reaction was magnetically stirred at 25 ℃ under an argon atmosphere for 12 hours. Adding methanol into the system for quenching, filtering under reduced pressure, and washing solid residues with water and methanol to obtain a product POG-OMe; 100mg of POG-OMe are weighed out and 200mL of CH are added under argon2Cl2The reaction system is placed at-20 ℃, boron tribromide (1mL) is added, the reaction system is transferred to an oil bath at 50 ℃, and the reaction is carried out for 48 hours by magnetic stirring. The reaction was quenched by adding deionized water and the solid residue was washed with water and methanol to give a porous polymer, POG-OH.
Example 2
10％Pd(NH3)4The preparation method of @ POG-OH (10% of palladium element in the mass ratio of the catalyst) comprises the following steps: catechol-derived porous polymer, POG-OH (40mg) and potassium hydroxide (4.22mg), were weighed into 80mL of ethanol, i.e., m (POG-OH): sonicating for 1h at room temperature, filtering and washing the solid 3 times with deionized water, transferring to a beaker and adding Pd (NH) in accordance with the criteria of claim 53)4Cl2(9.23mg), i.e., m (POG-OH): m (Pd (NH)3)4Cl2) The method comprises the steps of (1: 0.23) meeting the standard of claim 6, carrying out ultrasonic treatment for 1h at room temperature by 80mL of ethanol, filtering, washing with water and ethanol for 3 times, and obtaining the catechol-derived porous polymer supported palladium catalyst shown in the formula 2Agent (10% Pd (NH)3)4@ POG-OH), yield 100%. The actual metal content was determined by ICP to be 6.4%.
Example 3
5％Pd(NH3)4The preparation method of @ POG-OH (5% of palladium element in the mass ratio of the catalyst) comprises the following steps: catechol-derived porous polymer, POG-OH (40mg) and potassium hydroxide (2.11mg) were weighed into 80mL of ethanol, i.e., m (POG-OH): sonicating for 1h at room temperature, filtering and washing the solid 3 times with deionized water, transferring to a beaker and adding Pd (NH) in accordance with the criteria of claim 53)4Cl2(4.61mg), i.e., m (POG-OH): m (Pd (NH)3)4Cl2) (ii) 80mL of ethanol, sonicated at room temperature for 1h, filtered and washed 3 times with water and ethanol to give catechol-derived porous polymer-supported palladium catalyst (5% Pd (NH) in accordance with claim 6: (1: 0.12) as defined in claim 63)4@ POG-OH), yield 100%. The metal content was determined by ICP.
Example 4
Preparation of 10% Pd @ POG-3S-OH (10% of palladium element in the mass ratio of the catalyst): POG-3S-OH (40mg) and potassium hydroxide (4.22mg) were weighed into 80mL of ethanol, i.e., m (POG-3S-OH): sonicating for 1h at room temperature, filtering and washing the solid 3 times with deionized water, transferring to a beaker and adding PdCl, all according to the criteria of claim 52Or Pd (AcO)2(6.67 or 8.44mg), i.e., m (POG-3S-OH): m (PdCl)2Or Pd (AcO)2) The catechol-derived porous polymer supported palladium catalyst shown in the formula 3, namely 10% Pd @ POG-3S-OH (10% of palladium element accounts for the mass ratio of the catalyst), is obtained by performing ultrasonic treatment on 80mL of ethanol at room temperature for 1h, filtering and washing 3 times with water and ethanol, wherein the yield is 100%. The metal content was determined by ICP.
The preparation method of the catechol-derived porous polymer POG-3S-OH comprises the following steps: 100mL of dichloromethane solvent was added to a mixed system of 1,3, 5-tris (3, 4-dimethoxybenzyl) benzene (0.4mmol), 1,3, 5-tris (p-formylphenyl) benzene (0.6mmol), acetic anhydride (20mmol) and ferric trichloride (0.08mmol), and the reaction was magnetically stirred at 25 ℃ for 48 hours. Ferric trichloride (72mmol) was added again to the system, and the reaction was magnetically stirred at 25 ℃ under an argon atmosphere for 12 hours. Then, methanol was added to the system to quench, and the solid residue was filtered under reduced pressure and washed with water and methanol to obtain a product. 100mg of the above product was weighed out and 200mL CH was added under argon2Cl2The reaction system is placed at-20 ℃, boron tribromide (1mL) is added, the reaction system is transferred to an oil bath at 50 ℃, and the reaction is carried out for 48 hours by magnetic stirring. The reaction was quenched by adding deionized water and the solid residue was washed with water and methanol to give a porous polymer, POG-3S-OH.
Example 5
Preparation of 10% Pd @ POG-4S-OH (10% of palladium element in the mass ratio of the catalyst): POG-4S-OH (100mg) and potassium hydroxide (4.22mg) were weighed into 80mL of ethanol, i.e., m (POG-4S-OH): sonicating for 1h at room temperature, filtering and washing the solid 3 times with deionized water, transferring to a beaker and adding PdCl, all according to the criteria of claim 52Or Pd (AcO)2(6.67 or 8.44mg), i.e., m (POG-4S-OH): m (PdCl)2Or Pd (AcO)2) The catechol-derived porous polymer supported palladium catalyst shown in the formula 4, namely 10% Pd @ POG-4S-OH (10% of palladium element accounts for the mass ratio of the catalyst), is obtained by performing ultrasonic treatment on 80mL of ethanol at room temperature for 1h, filtering and washing with water and ethanol for 3 times, wherein the yield is 100%, and the standard of the catalyst is met by 1:0.16 (0.21). The metal content was determined by ICP.
The preparation method of the catechol-derived porous polymer POG-4S-OH comprises the following steps: 100mL of dichloromethane solvent was added to a mixed system of 1,3, 5-tris (3, 4-dimethoxybenzyl) benzene (0.4mmol), tetrakis (4-formylbenzene) methane (0.6mmol), acetic anhydride (20mmol) and ferric trichloride (0.08mmol), and the reaction was magnetically stirred at 25 ℃ for 48 hours. Ferric trichloride (72mmol) was added again to the system, and the reaction was magnetically stirred at 25 ℃ under an argon atmosphere for 12 hours. Then, methanol was added to the system to quench, and the solid residue was filtered under reduced pressure and washed with water and methanol to obtain a product. 100mg of the above product was weighed out and 200mL CH was added under argon2Cl2The reaction system is placed at-20 ℃, boron tribromide (1mL) is added, the reaction system is transferred to an oil bath at 50 ℃, and the reaction is carried out for 48 hours by magnetic stirring. The reaction was quenched by adding deionized water and the solid residue was washed with water and methanol to give a porous polymer, POG-4S-OH.
Suzuki-Miyaura reaction (Suzuki reaction): respectively taking 10% Pd @ POG-OH, 10% Pd @ POG-3S-OH, 10% Pd @ POG-4S-OH and 10% Pd (NH)3)4@POG-OH、5％Pd(NH3)4@ POG-OH as a catalyst and the reaction without the catalyst were also tested, and the comparative data are shown in Table 1:
application example 1
P-methyliodobenzene (0.1mmol), phenylboronic acid (0.15mmol), potassium carbonate (0.3mmol) and catechol-derived porous polymer-supported palladium catalyst (0.01 mol%, 10% Pd @ POG-OH) were weighed into a 10mL quartz tube, and 1mL of ethanol was added: the mixed solution of 2:1 water is magnetically stirred for 6 hours at room temperature, the conversion rate of the methyl iodobenzene can reach 91 percent through high-efficiency gas mass spectrometry detection, and the selectivity of the cross-coupling product is 100 percent (the gas mass spectrogram of the catalysis result is shown in figure 1). The catalyst is recovered by centrifugation and reused for 5 times, and the catalyst still maintains the original catalytic activity and selectivity (the recycling result is shown in figure 2 of the attached drawing). All the yield and selectivity are determined by high performance gas mass spectrometry, toluene is used as an internal standard substance, a peak appears at the position of t & ltSUB & gt 3.65min before the system reaction, a raw material peak basically disappears after the reaction, and a characteristic peak of a coupling product appears at the position of t & ltSUB & gt 5.20 min.
Application example 2
P-methyliodobenzene (0.1mmol), phenylboronic acid (0.15mmol), potassium carbonate (0.3mmol) and catechol-derived porous polymer-supported palladium catalyst (0.01 mol%, 10% Pd (NH))3)4@ POG-OH) was placed in a 10mL quartz tube, 1mL ethanol: the mixed solution of 2:1 water is magnetically stirred for 6 hours at room temperature, the conversion rate of the methyl iodobenzene can reach 85 percent through high-efficiency gas mass spectrometry detection, and the selectivity of the cross-coupling product is 100 percent (the gas mass spectrogram of the catalysis result is shown in figure 1). The catalyst is recovered by centrifugation and reused for 5 times, and the catalyst still maintains the original catalytic activity and selectivity (the recycling result is shown in figure 2 of the attached drawing). All the yield and selectivity are determined by high performance gas mass spectrometry, toluene is used as an internal standard substance, a peak appears at the position of t & ltSUB & gt 3.65min before the system reaction, a raw material peak basically disappears after the reaction, and a characteristic peak of a coupling product appears at the position of t & ltSUB & gt 5.20 min.
Application example 3
P-methyliodobenzene (0.1mmol), phenylboronic acid (0.15mmol), potassium carbonate (0.3mmol) and catechol-derived porous polymer-supported palladium catalyst (0.01 mol%, 5% Pd (NH)3)4@ POG-OH) was placed in a 10mL quartz tube, 1mL ethanol: the mixed solution of 2:1 water is magnetically stirred for 6 hours at room temperature, the conversion rate of the methyl iodobenzene can reach 79 percent through high-efficiency gas mass spectrometry detection, and the selectivity of the cross-coupling product is 100 percent.
Application example 4
P-methyliodobenzene (0.1mmol), phenylboronic acid (0.15mmol), potassium carbonate (0.3mmol) and catechol-derived porous polymer-supported palladium catalyst (0.01 mol%, 10% Pd @ POG-3S-OH) were weighed into a 10mL quartz tube, and 1mL of ethanol was added: the mixed solution of 2:1 water is magnetically stirred for 6 hours at room temperature, the conversion rate of the methyl iodobenzene can reach 90 percent through high-efficiency gas mass spectrometry detection, and the selectivity of the cross-coupling product is 100 percent.
Application example 5
P-methyliodobenzene (0.1mmol), phenylboronic acid (0.15mmol), potassium carbonate (0.3mmol) and catechol-derived porous polymer-supported palladium catalyst (0.01 mol%, 10% Pd @ POG-4S-OH) were weighed into a 10mL quartz tube, and 1mL of ethanol was added: the mixed solution of 2:1 water is magnetically stirred for 6 hours at room temperature, the conversion rate of the methyl iodobenzene can reach 88 percent through high-efficiency gas mass spectrometry detection, and the selectivity of the cross-coupling product is 100 percent.
Application comparative example 1
P-methyl iodobenzene (0.1mmol), phenylboronic acid (0.15mmol), potassium carbonate (0.3mmol) and catechol-derived porous polymer supported palladium catalyst (0.01 mol%, PdCl) were weighed2) Put into a 10mL quartz tube, 1mL ethanol: the mixed solution of 2:1 water is magnetically stirred for 6 hours at room temperature, the conversion rate of the methyl iodobenzene is 8 percent and the selectivity of the cross-coupling product is 100 percent through high-efficiency gas mass spectrometry detection.
Application comparative example 2(CN110394190A)
Firstly, synthesizing a porous polymer supported palladium catalyst CaCOP2@ Pd of triazine group connected calix [4] arene. Weighing P-methyl iodobenzene (0.1mmol), phenylboronic acid (0.15mmol), potassium carbonate (0.3mmol) and CaP0P3@ Pd (0.4 mol%) and placing the materials into a 10mL quartz tube, adding 1mL ethanol, stirring and reacting for 8h at room temperature, wherein the conversion rate of the P-methyl iodobenzene is 12% and the selectivity of a cross-coupling product is 100% through high-efficiency gas mass spectrometry.
Application comparative example 3(CN110270378A)
Firstly, synthesizing a porous polymer supported palladium catalyst CaP0P3@ Pd of triazine group connected calix [4] arene. Weighing P-methyl iodobenzene (0.1mmol), phenylboronic acid (0.15mmol), potassium carbonate (0.3mmol) and CaP0P3@ Pd (0.2 mol%) and placing the materials into a 10mL quartz tube, adding 1mL ethanol, stirring and reacting for 6h at 80 ℃, and detecting by high performance gas mass spectrometry to obtain the P-methyl iodobenzene conversion rate of 20% and the selectivity of a cross-coupling product of 100%.
Table 1:
it can be seen that, compared with the comparative example, the catechol-derived porous polymer supported palladium catalyst synthesized by the method has the advantages of high reaction activity, good selectivity and the like, and compared with other palladium catalysts, the method simultaneously realizes higher conversion rate and selectivity, and the reaction conversion frequency (TOF value) is far higher than that reported in the prior patent, so that the method can completely meet the requirements of the existing production.
In addition, it is mentioned that most of the catalysts used in the prior art cannot be recycled due to no recycling value, difficult separation or difficult guarantee of purity after separation, and the catalysts mentioned above can overcome the above-mentioned defects of the catalysts, can be used for many times, and can be recycled for at least 5 times without loss of catalytic activity and selectivity (see the attached figure 2 of the specification).
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (13)
1. A porous polymer supported palladium catalyst characterized by: the porous polymer is derived from catechol.
2. The porous polymer-supported palladium catalyst of claim 1 wherein: the catalyst has the structure of compound I or II (II') or III:
in the compound, R1, R4, R5, R6 and R9 are selected from CH and various alkyl chains derived from the CH, N, O, S; n1, n2 and n3 are integers respectively, and n1+ n2+ n3> is 1; r7 is selected from CH and various alkyl chains derived from CH, benzene ring, 1,3, 5-triazine; r8 is selected from C, C ═ C, porphyrin; r2, R3 may be two H or 1 Pd, giving the following structural fragments with adjacent groups:
in one of the porous polymer supported palladium catalyst structures,
is at least 1.
3. The method for preparing a porous polymer supported palladium catalyst according to claim 1 or 2, wherein the catechol-derived porous polymer is reacted by adding an alkali, and then a palladium source is added to the reaction product to obtain the catechol-derived porous polymer supported palladium catalyst.
4. The method for preparing a porous polymer supported palladium catalyst according to claim 3, characterized by comprising the steps of:
(1) dispersing a catechol-derived porous polymer in a solvent, adding alkali, reacting, filtering and washing to obtain solid powder;
(2) and (2) dispersing the solid powder obtained in the step (1) in a solvent, adding a palladium source, reacting, and carrying out post-treatment to obtain the catechol-derived porous polymer supported palladium catalyst.
5. The method for producing a catalyst according to claim 3 or 4, wherein the solvent in the step (1) is ethanol, the base in the step (1) is NaOH, and the amount of the catechol-derived porous polymer compound in the step (1) and the amount of the base are mixed in a mass ratio of m (catechol-derived porous polymer): m (base) ═ 1:0.0001 to 1:1, where m is mass; the reaction condition in the step (1) is ultrasonic reaction or magnetic stirring reaction, and ethanol and deionized water are used for washing.
6. The method for preparing the catalyst according to claim 3 or 4, wherein the palladium source in the step (2) is PdY or a hydrate thereof, Y is-Cl, -AcO or Cl2(NH3)4In the amount ratio of m (compound II/V (V')/VIII): m (palladium source) is 1:0.0001 to 1:1, wherein m is mass; the reaction condition in the step (2) is ultrasonic reaction or magnetic stirring reaction, the post-treatment in the step (2) is filtration, and the solid residue is washed by an organic solvent and water.
7. Use of a catalyst according to claim 1 or 2 or of a catalyst obtained by a method according to claims 2 to 6 in a Suzuki-Miyaura reaction.
8. Use of a catalyst according to claim 7 in a Suzuki-Miyaura reaction, wherein: the reaction is carried out at room temperature and does not require anhydrous and oxygen-free reaction conditions.
9. The use according to claim 7, 8, comprising: mixing an aromatic halide and a boric acid derivative with the catalyst of claims 1 and 2 or the catalyst obtained by the production method of claims 2 to 6, adding a solvent, and reacting at room temperature to obtain a mixture.
10. Use according to claims 7-9, characterized in that it comprises the following steps:
(1) mixing an aromatic halide and a boric acid derivative with the catalyst of claim 1 or 2 or the catalyst obtained by the production method of claims 2 to 6, and adding a solvent;
(2) the reaction was magnetically stirred at a certain temperature to give a mixture.
11. Use according to claims 7-10, characterized in that: the solvent in step (1) is preferably ethanol: 2:1 of water; the mixing molar ratio in the step (1) is n (aromatic halide): n (boronic acid derivative): n (catalyst) ═ 1 (1-2) (0.0001-0.1), where n is the amount of material; the reaction temperature of the step (2) is preferably 10-35 ℃, and the stirring reaction time is preferably 3-24 h.
12. The use according to claims 9, 10, which further comprises the step of sampling the resulting mixture to determine the product yield, preferably by high performance gas mass spectrometry.
13. Use according to claims 7-10, characterized in that: the catalyst can be repeatedly used for at least 5 times, and simultaneously, the catalytic activity and the selectivity are not lost.
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