CN115739189B - Preparation method of nanoparticle composite material for rapidly catalyzing suzuki reaction at room temperature - Google Patents
Preparation method of nanoparticle composite material for rapidly catalyzing suzuki reaction at room temperature Download PDFInfo
- Publication number
- CN115739189B CN115739189B CN202211403573.XA CN202211403573A CN115739189B CN 115739189 B CN115739189 B CN 115739189B CN 202211403573 A CN202211403573 A CN 202211403573A CN 115739189 B CN115739189 B CN 115739189B
- Authority
- CN
- China
- Prior art keywords
- pcn
- reaction
- room temperature
- composite material
- nanoparticle composite
- 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
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 48
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 238000006069 Suzuki reaction reaction Methods 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 68
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 239000003446 ligand Substances 0.000 claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 23
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 23
- 239000013096 zirconium-based metal-organic framework Substances 0.000 claims abstract description 17
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 239000011148 porous material Substances 0.000 claims abstract description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 51
- 239000000047 product Substances 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 28
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- NBXKUSNBCPPKRA-UHFFFAOYSA-N 1,4,7,10,13-pentaoxa-16-azacyclooctadecane Chemical compound C1COCCOCCOCCOCCOCCN1 NBXKUSNBCPPKRA-UHFFFAOYSA-N 0.000 claims description 7
- PFAYEBBXANMZEZ-UHFFFAOYSA-N (3,6-dibromopyridin-2-yl)methanol Chemical compound BrC=1C(=NC(=CC=1)Br)CO PFAYEBBXANMZEZ-UHFFFAOYSA-N 0.000 claims description 6
- ZLNFACCFYUFTLD-UHFFFAOYSA-N (4-ethoxycarbonylphenyl)boronic acid Chemical compound CCOC(=O)C1=CC=C(B(O)O)C=C1 ZLNFACCFYUFTLD-UHFFFAOYSA-N 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 6
- -1 6- (hydroxymethyl pyridine-2, 5-diyl) dibenzoate Chemical compound 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 claims description 4
- 101150003085 Pdcl gene Proteins 0.000 claims description 4
- MHIQZUBVBHZGLB-UHFFFAOYSA-N 2-[6-(2-carboxyphenyl)pyridin-3-yl]benzoic acid Chemical compound C1=CC=C(C(=C1)C2=CN=C(C=C2)C3=CC=CC=C3C(=O)O)C(=O)O MHIQZUBVBHZGLB-UHFFFAOYSA-N 0.000 claims description 3
- VUYFKAXNJXFNFA-UHFFFAOYSA-N 4-(4-carboxy-2-methylphenyl)-3-methylbenzoic acid Chemical compound CC1=CC(C(O)=O)=CC=C1C1=CC=C(C(O)=O)C=C1C VUYFKAXNJXFNFA-UHFFFAOYSA-N 0.000 claims description 3
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 3
- 239000011011 black crystal Substances 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000012263 liquid product Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 239000005297 pyrex Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000010898 silica gel chromatography Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 229910007926 ZrCl Inorganic materials 0.000 claims 1
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 abstract description 18
- 230000003197 catalytic effect Effects 0.000 abstract description 15
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 9
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 abstract description 8
- 238000006880 cross-coupling reaction Methods 0.000 abstract description 5
- 230000005669 field effect Effects 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 239000007809 chemical reaction catalyst Substances 0.000 abstract description 2
- 230000009257 reactivity Effects 0.000 abstract 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 12
- ZZLCFHIKESPLTH-UHFFFAOYSA-N 4-Methylbiphenyl Chemical group C1=CC(C)=CC=C1C1=CC=CC=C1 ZZLCFHIKESPLTH-UHFFFAOYSA-N 0.000 description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 description 6
- 238000012986 modification Methods 0.000 description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 2
- HSSYVKMJJLDTKZ-UHFFFAOYSA-N 3-phenylphthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(O)=O HSSYVKMJJLDTKZ-UHFFFAOYSA-N 0.000 description 2
- LFBALUPVVFCEPA-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 LFBALUPVVFCEPA-UHFFFAOYSA-N 0.000 description 2
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 description 2
- BPMBNLJJRKCCRT-UHFFFAOYSA-N 4-phenylbenzonitrile Chemical group C1=CC(C#N)=CC=C1C1=CC=CC=C1 BPMBNLJJRKCCRT-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-MZCSYVLQSA-N Deuterated methanol Chemical compound [2H]OC([2H])([2H])[2H] OKKJLVBELUTLKV-MZCSYVLQSA-N 0.000 description 2
- JVVXZOOGOGPDRZ-SLFFLAALSA-N [(1R,4aS,10aR)-1,4a-dimethyl-7-propan-2-yl-2,3,4,9,10,10a-hexahydrophenanthren-1-yl]methanamine Chemical compound NC[C@]1(C)CCC[C@]2(C)C3=CC=C(C(C)C)C=C3CC[C@H]21 JVVXZOOGOGPDRZ-SLFFLAALSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000003983 crown ethers Chemical class 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- ZBTMRBYMKUEVEU-UHFFFAOYSA-N 1-bromo-4-methylbenzene Chemical compound CC1=CC=C(Br)C=C1 ZBTMRBYMKUEVEU-UHFFFAOYSA-N 0.000 description 1
- DAWHTISAONTGQE-UHFFFAOYSA-N 3-(2-phenylphenyl)phthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C(=CC=CC=2)C=2C=CC=CC=2)=C1C(O)=O DAWHTISAONTGQE-UHFFFAOYSA-N 0.000 description 1
- HQSCPPCMBMFJJN-UHFFFAOYSA-N 4-bromobenzonitrile Chemical compound BrC1=CC=C(C#N)C=C1 HQSCPPCMBMFJJN-UHFFFAOYSA-N 0.000 description 1
- GJNGXPDXRVXSEH-UHFFFAOYSA-N 4-chlorobenzonitrile Chemical compound ClC1=CC=C(C#N)C=C1 GJNGXPDXRVXSEH-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 description 1
- JVZRCNQLWOELDU-UHFFFAOYSA-N gamma-Phenylpyridine Natural products C1=CC=CC=C1C1=CC=NC=C1 JVZRCNQLWOELDU-UHFFFAOYSA-N 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002090 nanochannel Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- 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
- Pyridine Compounds (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of a nanoparticle composite material for rapidly catalyzing suzuki reaction at room temperature, relates to the technical field of suzuki reaction catalysts, and is based on a clamp-aza crown ether ligand L 1 And zirconium-based metal-organic framework material PCN-700 Metal-organic framework supported palladium nanoparticle composite Pd@PCN-700-L 1 Is prepared by the following steps. The nanoparticle composite material can rapidly catalyze the Suzuki reaction at room temperature under the air condition, and has the advantages of high activity, simple reaction treatment, mild reaction condition, environment-friendly chemical compliance of a solvent and the like. The catalyst shows good cross-coupling catalytic activity on bromobenzene and phenylboronic acid under the finite field effect of a metal-organic framework material PCN-700 nanometer pore canal, and simultaneously has good cross-coupling catalytic activity on bromobenzene and phenylboronic acidThe chlorobenzene with poor reactivity also has high catalytic performance.
Description
Technical Field
The invention relates to the technical field of suzuki reaction catalysts, in particular to a preparation method of a nanoparticle composite material for rapidly catalyzing suzuki reaction at room temperature.
Background
The Suzuk i (Suzuki) coupling reaction is one of effective methods for constructing carbon-carbon bonds, and is widely applied to the synthesis fields of functional materials, natural products, medical intermediates and the like. However, the homogeneous catalyst cannot be recovered and the experimental post-treatment is complex, so the preparation and research of the catalyst for heterogeneously catalyzing the Suzuki reaction are focused on. The zirconium-based metal-organic framework material with stable physical and chemical properties has a pore structure with nano-scale, and is a good carrier with catalytic activity nano particles; meanwhile, the nano-domain effect of the pore canal can improve the catalytic activity of the pore canal.
By utilizing a zirconium-based metal-organic framework material PCN-700 in which there are free sites available for insertion of building blocks of two different lengths, biphenyl dicarboxylic acid and terphenyl dicarboxylic acid, the synthetic strategy can be modified later to functionalize PCN-700. With this strategy, it is possible to introduce a clamp ligand with crown ether in zirconium-based metal-organic framework material PCN-700 and further prepare the corresponding nano palladium particles in its nanochannels. To obtain the heterogeneous catalyst for rapidly catalyzing the suzuki reaction at room temperature.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a nanoparticle composite material for rapidly catalyzing Suzuki reaction at room temperature, which aims to solve the problems in the prior art.
In order to achieve the above purpose, the present invention provides the following technical solutions: preparation method of nanoparticle composite material for rapidly catalyzing suzuki reaction at room temperatureMethod based on clamp-aza crown ether ligands L 1 And zirconium-based metal-organic framework material PCN-700 Metal-organic framework supported palladium nanoparticle composite Pd@PCN-700-L 1 Is prepared by the following steps.
Wherein the clamp-aza crown ether ligand L 1 The preparation of the composition comprises the following steps:
s1, under the nitrogen environment, adding (3, 6-dibromopyridine-2-yl) methanol, 4-ethoxycarbonyl phenylboronic acid, tetrakis (triphenylphosphine) palladium, sodium carbonate, dioxane and water into the mixture for reaction to obtain a product of diethyl 4,4' - (6- (hydroxymethyl pyridine-2, 5-diyl) dibenzoate;
s2, diethyl 4,4' - (6-hydroxymethylpyridine-2, 5-diyl) dibenzoate and CBr 4 And 25mL of ultra-dry tetrahydrofuran were incorporated into a 50mL flask, and PPh was added with stirring 3 Reacting for 12 hours at normal temperature to obtain a product of diethyl 4,4' - (6- (bromomethyl) pyridine-2, 5-diyl) dibenzoate;
s3, adding diethyl 4,4'- (6- (bromomethyl) pyridine-2, 5-diyl) dibenzoate, aza-18-crown-6, triethylamine and toluene solution into the mixture for reaction, heating and refluxing for 24 hours, stopping the reaction, evaporating and concentrating to obtain dark red solid, purifying by silica gel column chromatography, and finally obtaining yellow liquid product, namely diethyl crown ether structural unit-containing clamp-like ligand 4,4' - (6- (1, 4,7,10, 13-pentaoxa-16-azacyclooctadecane-16-yl) methyl) pyridine-2, 5-dibenzoate;
s4, heating the suspension of the product obtained in the step S3 in 30mL of tetrahydrofuran to 65 ℃ for reacting for half an hour, adding 30mL of sodium hydroxide solution, continuing to react for 24 hours, evaporating and spin-drying the tetrahydrofuran, adding dilute hydrochloric acid, acidifying until a large amount of precipitate is formed, and filtering to obtain white solid carboxylated ligand L 1 ；
Wherein, the preparation of the zirconium-based metal-organic framework material PCN-700 comprises the following steps:
s5, 200mg of ZrC l 4 100mg of 2,2' -dimethyl-4, 4' -biphenyldicarboxylic acid, 1.0mL of trifluoroacetic acid and 20mL of N, N ' -dimethylformamide were filled into Pyrex vials;
s6, heating the mixture in the bottle in a baking oven at 120 ℃ for 72 hours;
s7, cooling to room temperature, and preparing a zirconium-based metal-organic framework material PCN-700;
wherein the metal-organic framework supported palladium nanoparticle composite material Pd@PCN-700-L 1 The preparation of the composition comprises the following steps:
s8, activating PCN-700 and L 1 Adding 4,4' -biphenyl dicarboxylic acid and 4mL of N, N ' -dimethylformamide into a 10mL glass bottle, carrying out ultrasonic treatment for 5 minutes, heating the mixture in an oven at 85 ℃ for 24 hours, washing the mixture by fresh N, N ' -dimethylformamide for multiple times, removing unreacted ligand in a pore canal, soaking the mixture in fresh DMF solution, and finally obtaining pale yellow crystal PCN-700-L 1 ；
S9, 40mg of PCN-700-L 1 PdCl 4mg 2 And 5mL acetonitrile solution are filled into a 20mL glass vial, the mixture is heated for 30 hours at 50 ℃, the reaction is finished, and crystals are obtained by centrifugation;
s10, slowly adding the prepared NaBH into a small bottle filled with crystals 4 Reducing methanol solution for 20 min, removing salt and residual acetonitrile solution in pore canal with anhydrous methanol at least 3 times per day for 3 days, vacuum drying in vacuum oven at 65deg.C for 24 hr, and removing methanol to obtain black crystal Pd@PCN-700-L 1 。
Further optimizing the technical scheme, in the step S1, (3, 6-dibromopyridin-2-yl) methanol is 5.34g of 20mmo l, 4-ethoxycarbonyl phenylboronic acid is 9.31g of 48mmo l, tetrakis (triphenylphosphine) palladium is 80mg of 0.069mmo l, sodium carbonate is 10.18g,96mmo l, dioxane is 300mL, and water is 50mL.
Further optimizing the technical scheme, in the step S1, the reaction time is 40 hours, the reaction temperature is 105 ℃, 6.86g of product is obtained, and the yield of the product is 84.6%.
Further optimizing the technical scheme, in the step S2, the diethyl 4,4' - (6-hydroxymethylpyridine-2, 5-diyl) dibenzoate is 2.03g,5mmol, CBr 4 2.49g of 7.5mmol of product were obtained, 1.67g of product was obtainedThe yield of (2) was 71.6%.
Further optimizing the technical scheme, in the step S3, the diethyl 4,4'- (6- (bromomethyl) pyridine-2, 5-diyl) dibenzoate is 1.50g,3.21mmo l, aza-18-crown-6 is 0.93g,3.53mmo l and triethylamine is 0.4g, and the obtained clamp-like ligand 4,4' - (6- (1, 4,7,10, 13-pentaoxa-16-azaoctadeca-16-yl) methyl) pyridine-2, 5-dibenzoate diethyl ester is 1.67g, and the clamp-like ligand yield is 76.6%.
Further optimizing the technical scheme, in the step S4, the product in 30mL of tetrahydrofuran is 1.1g of 1.69mmo L, the sodium hydroxide solution is 0.20g of 5.07mmo L, and the ligand L is carboxylated by a white solid 1 0.83g, yield 82.5%.
Further optimizing the technical scheme, in the step S8, PCN-700 is 20mg 0.0106mmo l,L 1 1.5mg 0.0025mmo l,4,4' -Biphthalic acid 4.0mg 0.0165mmo L, crystalline PCN-700-L 1 Is 2300.81.
Further optimizing the technical scheme, in the step S10, naBH 4 The methanol solution was 3mg of 0.08mmol, crystalline Pd@PCN-700-L 1 Pd in the catalyst was 6wt%.
Compared with the prior art, the invention provides a preparation method of a nanoparticle composite material for rapidly catalyzing Suzuki reaction at room temperature, which has the following beneficial effects:
1. the preparation method of the nanoparticle composite material for rapidly catalyzing SUZUKI reaction at room temperature has the advantages of simpler preparation method, milder reaction conditions, commercially available raw materials, low price and the like, and the clamp-aza crown ether ligand L with room temperature SUZUKI reaction is successfully introduced into the PCN-700 material by adopting a post-modification synthesis strategy 1 The functional construction unit L 1 The palladium nano particles on the surface of the metal-organic framework are well dispersed and have very uniform size, and the size of the palladium nano particles is between 20 and 25nm after the palladium nano particles are reduced by a reducing agent.
2. Preparation of nanoparticle composite material for rapidly catalyzing Suzuki reaction at room temperatureThe preparation method can rapidly catalyze the Suzuki reaction under the conditions of room temperature and air, has the advantages of high activity, simple reaction treatment, mild reaction conditions, environment-friendly chemistry of solvents and the like, and introduces the catalytic unit ligand L 1 By utilizing the finite field effect of PCN-700 nanometer pore canal of the metal-organic framework material, the catalyst not only has good cross-coupling catalytic activity on bromobenzene and phenylboronic acid, but also has high catalytic performance on chlorobenzene with poor reaction activity, namely, the catalyst can rapidly catalyze Suzuki reaction at 40 ℃ under the air condition to obtain the expected product.
Drawings
FIG. 1 shows a clamp-aza crown ether ligand L of a preparation method of a nanoparticle composite material for rapidly catalyzing Suzuki reaction at room temperature 1 A structural schematic;
FIG. 2 is a schematic illustration of a nanoparticle composite material for rapid catalysis of Suzuki reaction at room temperature in accordance with the present invention;
FIG. 3 shows a clamp-aza crown ether ligand L of a nanoparticle composite material for rapidly catalyzing Suzuki reaction at room temperature 1 Is prepared by the preparation method;
fig. 4 is a palladium nanoparticle scanning electron microscope image of a nanoparticle composite material for rapidly catalyzing suzuki reaction at room temperature.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Embodiment one:
preparation method of nanoparticle composite material for rapidly catalyzing suzuki reaction at room temperature and based on clamp-aza crown ether ligand L 1 And zirconium-based metal-organic framework material PCN-700 Metal-organic framework supported palladium nanoparticle composite Pd@PCN-700-L 1 Is prepared from. Based on the structural characteristics of the zirconium-based metal-organic framework material PCN-700, which is provided with a free site for post-modification insertion of biphenyl dicarboxylic acid or terphthalic acid, a clamp-aza crown ether ligand L with a terphenyl dicarboxylic acid-like structure shown in figure 1 is designed and prepared 1 . The ligand palladium complex has the capability of rapidly catalyzing SUZUKI reaction at room temperature. And as shown in FIG. 2, it is introduced into PCN-700 skeleton by post-modification means, in combination with PdCl 2 After the reaction, the Pd nano-particle loaded zirconium-based metal-organic framework material is obtained by sodium borohydride reduction.
Wherein, as shown in FIG. 3, the clamp-aza crown ether ligand L 1 The preparation of the composition comprises the following steps:
s1, under the nitrogen environment, adding (3, 6-dibromopyridine-2-yl) methanol, 4-ethoxycarbonyl phenylboronic acid, tetrakis (triphenylphosphine) palladium, sodium carbonate, dioxane and water into the mixture for reaction to obtain a product of 4,4' - (6- (hydroxymethyl pyridine-2, 5-diyl) diethyl dibenzoate.
Further, in the step S1, (3, 6-dibromopyridin-2-yl) methanol was 5.34g of 20mmo l, 4-ethoxycarbonylphenylboronic acid was 9.31g of 48mmo l, tetrakis (triphenylphosphine) palladium was 80mg of 0.069mmo l, sodium carbonate was 10.18g,96mmo l, dioxane 300mL, and water 50mL.
Further, in the step S1, the reaction time was 40 hours, the reaction temperature was 105℃and 6.86g of a product was obtained in a yield of 84.6%.
S2, diethyl 4,4' - (6-hydroxymethylpyridine-2, 5-diyl) dibenzoate and CBr 4 And 25mL of ultra-dry tetrahydrofuran were incorporated into a 50mL flask, and PPh was added with stirring 3 The reaction is carried out for 12 hours at normal temperature, and the product diethyl 4,4' - (6- (bromomethyl) pyridine-2, 5-diyl) dibenzoate is obtained.
Further, in the step S2, diethyl 4,4' - (6-hydroxymethylpyridine-2, 5-diyl) dibenzoate was found to be 2.03g,5mmol, CBr 4 2.49g of 7.5mmol of product are obtained in a yield of 71.6%.
S3, adding diethyl 4,4'- (6- (bromomethyl) pyridine-2, 5-diyl) dibenzoate, aza-18-crown-6, triethylamine and toluene solution into the mixture for reaction, heating and refluxing for 24 hours, stopping the reaction, evaporating and concentrating to obtain dark red solid, and purifying by silica gel column chromatography to finally obtain yellow liquid product, namely the clamp-like ligand 4,4' - (6- (1, 4,7,10, 13-pentaoxa-16-azacyclooctadecane-16-yl) methyl) pyridine-2, 5-diethyl dibenzoate containing crown ether structural units.
In this example, in the step S3, diethyl 4,4'- (6- (bromomethyl) pyridine-2, 5-diyl) dibenzoate was 1.50g,3.21mmo l, aza-18-crown-6 was 0.93g,3.53mmo l, and triethylamine was 0.4g, and the resulting clamp-like ligand 4,4' - (6- (1, 4,7,10, 13-pentaoxa-16-azaoctadeca-16-yl) methyl) pyridine-2, 5-dibenzoate diethyl was 1.67g, and the clamp-like ligand yield was 76.6%.
S4, heating the suspension of the product obtained in the step S3 in 30mL of tetrahydrofuran to 65 ℃ for reacting for half an hour, adding 30mL of sodium hydroxide solution, continuing to react for 24 hours, evaporating and spin-drying the tetrahydrofuran, adding dilute hydrochloric acid, acidifying until a large amount of precipitate is formed, and filtering to obtain white solid carboxylated ligand L 1 。
In this example, in step S4, 30mL of tetrahydrofuran was used as the product of 1.1g of 1.69mmo L, 0.20g of 5.07mmo L of sodium hydroxide solution, and carboxylated ligand L as a white solid 1 0.83g, yield 82.5%.
Wherein, the preparation of the zirconium-based metal-organic framework material PCN-700 comprises the following steps:
s5, 200mg of ZrC l 4 100mg of 2,2' -dimethyl-4, 4' -biphenyldicarboxylic acid, 1.0mL of trifluoroacetic acid and 20mL of N, N ' -dimethylformamide were filled into Pyrex vials.
S6, heating the mixture in the bottle in an oven at 120 ℃ for 72 hours.
S7, cooling to room temperature, and preparing the zirconium-based metal-organic framework material PCN-700.
Wherein the metal-organic framework supported palladium nanoparticle composite material Pd@PCN-700-L 1 The preparation of the composition comprises the following steps:
s8, activating PCN-700 and L 1 Adding 4,4' -biphenyl dicarboxylic acid and 4mL of N, N ' -dimethylformamide into a 10mL glass bottle, carrying out ultrasonic treatment for 5 minutes, heating the mixture in an oven at 85 ℃ for 24 hours, washing the mixture by fresh N, N ' -dimethylformamide for multiple times, removing unreacted ligand in a pore canal, soaking the mixture in fresh DMF solution, and finally obtaining pale yellow crystal PCN-700-L 1 。
In the present embodiment, in the step S8, PCN-700 is 20mg 0.0106mmo l,L 1 1.5mg 0.0025mmo l,4,4' -Biphthalic acid 4.0mg 0.0165mmo L, crystalline PCN-700-L 1 Is 2300.81.
S9, 40mg of PCN-700-L 1 PdCl 4mg 2 And 5mL of acetonitrile solution were put into a 20mL glass vial, and the mixture was heated at 50℃for 30 hours, and after completion of the reaction, crystals were obtained by centrifugation.
S10, slowly adding the prepared NaBH into a small bottle filled with crystals 4 Reducing methanol solution for 20 min, removing salt and residual acetonitrile solution in pore canal with anhydrous methanol at least 3 times per day for 3 days, vacuum drying in vacuum oven at 65deg.C for 24 hr, and removing methanol to obtain black crystal Pd@PCN-700-L 1 。
Further, in the step S10, naBH 4 The methanol solution was 3mg of 0.08mmol, crystalline Pd@PCN-700-L 1 Pd in the catalyst was 6wt%.
According to the characteristics that zirconium-based metal-organic framework PCN-700 has two positions with different lengths (biphenyl and terphthalate), the invention designs a dicarboxylic acid ligand L with a terphenyl-like length 1 The main structure of the carboxylated phenyl-pyridine incorporates aza 18-crown-6, the functional building block L 1 The metal ion containing multiple electron donor N, O atoms can have good enrichment effect on metal cations and certain fixing and limiting effects on palladium ions. Meanwhile, the zirconium-based metal-organic framework PCN-700 finite field effect is utilized to cooperate with the ligand L 1 The catalytic unit and the palladium nano particles efficiently catalyze the Suzuki reaction.
Embodiment two:
based on the preparation method of the nanoparticle composite material for rapidly catalyzing suzuki reaction at room temperature in the first embodiment, application analysis is performed in the following application scene.
(1) Under air conditions, 3mg (0.001 mmol) of Pd@PCN-700-L 1 Adding 1mmol of p-bromobenzonitrile, 1.2 mmol of phenylboronic acid and 2.4 mmol of potassium carbonate into 3ml of deuterated methanol solution together for reaction for 15 minutes at room temperature, directly filtering after the experimental time is ended, and adding a nuclear magnetic internal standard CH into the obtained clear deuterated reaction solution 2 Br 2 The product yield was found to be 99% by analytical calculation of the peak area ratio of the product 4-cyanobiphenyl to the internal standard.
(2) Under air conditions, 3mg (0.001 mmol) of the composite Pd@PCN-700-L prepared in example 2 was reacted with 1 Adding 1mmol bromobenzene, 1.2 mmol phenylboric acid and 2.4 mmol potassium carbonate into 3ml methanol solution together, reacting for 15 minutes at room temperature, directly filtering after the experimental time, adding nuclear magnetic internal standard CH into the obtained clear deuterated reaction solution 2 Br 2 The product yield was found to be 98% by analytical calculation of the product biphenyl to internal standard peak area ratio.
(3) Under air conditions, 3mg (0.001 mmol) of the composite Pd@PCN-700-L prepared in example 2 was reacted with 1 Adding 1mmol of p-bromotoluene, 1.2 mmol of phenylboronic acid and 2.4 mmol of potassium carbonate into 3ml of methanol solution together for reaction for 15 minutes at room temperature, directly filtering after the experimental time is ended, and adding a nuclear magnetic internal standard CH into the obtained clear deuterated reaction solution 2 Br 2 The product yield was found to be 99% by analytical calculation of the peak area ratio of the product 4-methylbiphenyl to the internal standard.
(4) Under air conditions, 3mg (0.001 mmol) of the composite Pd@PCN-700-L prepared in example 2 was reacted with 1 Adding 1mmol of p-chlorobenzonitrile, 1.2 mmol of phenylboric acid and 2.4 mmol of potassium carbonate into 3ml of methanol solution together for reaction for 1 hour at 40 ℃, directly filtering after the experimental time is ended, and adding a nuclear magnetic internal standard CH into the obtained clear deuterated reaction solution 2 Br 2 The product yield was found to be 99% by analytical calculation of the peak area ratio of the product 4-cyanobiphenyl to the internal standard.
(5) Under air conditions, 3mg (0.001 mmol) of the composition of example 2 was preparedPrepared composite Pd@PCN-700-L 1 Adding 1mmol of p-chlorotoluene, 1.2 mmol of phenylboronic acid and 2.4 mmol of potassium carbonate into 3ml of methanol solution together for reaction for 1 hour at 40 ℃, directly filtering after the experimental time is ended, and adding a nuclear magnetic internal standard CH into the obtained clear deuterated reaction solution 2 Br 2 The product yield was found to be 99% by analytical calculation of the peak area ratio of the product 4-methylbiphenyl to the internal standard.
The metal-organic framework supported palladium nanoparticle composite material prepared by the method is simple in preparation method, mild in reaction condition and low in cost, and raw materials can be purchased commercially. The application of Suzuk i catalytic activity can be used for mild and rapid reaction under the air condition to obtain the expected product, and the gram-scale reactant is catalyzed by 0.1 mol% of low catalyst, so that the expected product is obtained in high yield. The prepared metal-organic framework supported palladium nanoparticle composite material has good application value and good application potential.
Embodiment III:
based on the application scenario listed in the second embodiment, the comparative example in this embodiment is compared, where the comparative example is:
under air conditions, 3mg (0.001 mmol) of the composite Pd@PCN-700-L prepared in example 2 was reacted with 1 Adding 1mmol of p-chlorotoluene, 1.2 mmol of phenylboronic acid and 2.4 mmol of potassium carbonate into 3ml of methanol solution together for reaction for 1 hour at 40 ℃, directly filtering after the experimental time is ended, and adding a nuclear magnetic internal standard CH into the obtained clear deuterated reaction solution 2 Br 2 The product yield was found to be 99% by analytical calculation of the peak area ratio of the product 4-methylbiphenyl to the internal standard.
The functional construction unit L 1 The catalyst comprises a plurality of electron supply N, O atoms, pd can be enriched in the pore canal after being coordinated with palladium, the catalyst provides possibility for further reduction, palladium nano particles on the surface of the metal-organic framework are well dispersed and quite uniform in size after being reduced by a reducing agent, the size of the palladium nano particles is between 20 and 25nm, and a Scanning Electron Microscope (SEM) is shown in figure 4. The method can rapidly catalyze the Suzuki reaction at room temperature under the condition of air, and has high activity, simple reaction treatment,The reaction condition is mild, and the solvent accords with green chemistry. Introduction of catalytic Unit ligand L 1 By utilizing the finite field effect of PCN-700 nanometer pore canal of the metal-organic framework material, the catalyst not only has good cross-coupling catalytic activity on bromobenzene and phenylboronic acid, but also has high catalytic performance on chlorobenzene with poor reaction activity, namely, the catalyst can rapidly catalyze Suzuki reaction at 40 ℃ under the air condition to obtain the expected product.
The beneficial effects of the invention are as follows:
1. the preparation method of the nanoparticle composite material for rapidly catalyzing SUZUKI reaction at room temperature has the advantages of simpler preparation method, milder reaction conditions, commercially available raw materials, low price and the like, and the clamp-aza crown ether ligand L with room temperature SUZUKI reaction is successfully introduced into the PCN-700 material by adopting a post-modification synthesis strategy 1 The functional construction unit L 1 The palladium nano particles on the surface of the metal-organic framework are well dispersed and have very uniform size, and the size of the palladium nano particles is between 20 and 25nm after the palladium nano particles are reduced by a reducing agent.
2. The nanoparticle composite material can rapidly catalyze the Suzuki reaction at room temperature under the air condition, and has the advantages of high activity, simple reaction treatment, mild reaction condition, environment-friendly chemical compliance of a solvent and the like. Under the finite field effect of a PCN-700 nanometer pore canal of a metal-organic framework material, the catalyst shows good cross-coupling catalytic activity on bromobenzene and phenylboronic acid, and simultaneously has high catalytic performance on chlorobenzene with poor reaction activity, namely, the catalyst rapidly catalyzes Suzuki reaction at 40 ℃ under the air condition to obtain an expected product.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. A preparation method of a nanoparticle composite material for rapidly catalyzing suzuki reaction at room temperature is characterized by comprising the step of preparing a nanoparticle composite material based on a clamp-aza crown ether ligand L 1 And zirconium-based metal-organic framework material PCN-700 Metal-organic framework supported palladium nanoparticle composite Pd@PCN-700-L 1 Is prepared by the steps of (1);
wherein the clamp-aza crown ether ligand L 1 The preparation of the composition comprises the following steps:
s1, under the nitrogen environment, adding (3, 6-dibromopyridine-2-yl) methanol, 4-ethoxycarbonyl phenylboronic acid, tetrakis (triphenylphosphine) palladium, sodium carbonate, dioxane and water into the mixture for reaction to obtain a product of diethyl 4,4' - (6- (hydroxymethyl pyridine-2, 5-diyl) dibenzoate;
s2, diethyl 4,4' - (6-hydroxymethylpyridine-2, 5-diyl) dibenzoate and CBr 4 And 25mL of ultra-dry tetrahydrofuran were incorporated into a 50mL flask, and PPh was added with stirring 3 Reacting for 12 hours at normal temperature to obtain a product of diethyl 4,4' - (6- (bromomethyl) pyridine-2, 5-diyl) dibenzoate;
s3, adding diethyl 4,4'- (6- (bromomethyl) pyridine-2, 5-diyl) dibenzoate, aza-18-crown-6, triethylamine and toluene solution into the mixture for reaction, heating and refluxing for 24 hours, stopping the reaction, evaporating and concentrating to obtain dark red solid, purifying by silica gel column chromatography, and finally obtaining yellow liquid product, namely diethyl crown ether structural unit-containing clamp-like ligand 4,4' - (6- (1, 4,7,10, 13-pentaoxa-16-azacyclooctadecane-16-yl) methyl) pyridine-2, 5-dibenzoate;
s4, heating the suspension of the product obtained in the step S3 in 30mL of tetrahydrofuran to 65 ℃ for reacting for half an hour, adding 30mL of sodium hydroxide solution, continuing to react for 24 hours, evaporating and spin-drying the tetrahydrofuran, adding dilute hydrochloric acid, acidifying until a large amount of precipitate is formed, and filtering to obtain white solid carboxylated ligand L 1 ；
Wherein, the preparation of the zirconium-based metal-organic framework material PCN-700 comprises the following steps:
s5, 200mg of ZrCl 4 100mg of 2,2' -dimethyl-4, 4' -biphenyldicarboxylic acid, 1.0mL of trifluoroacetic acid and 20mL of N, N ' -dimethylformamide were filled into Pyrex vials;
s6, heating the mixture in the bottle in a baking oven at 120 ℃ for 72 hours;
s7, cooling to room temperature, and preparing a zirconium-based metal-organic framework material PCN-700;
wherein the metal-organic framework supported palladium nanoparticle composite material Pd@PCN-700-L 1 The preparation of the composition comprises the following steps:
s8, activating PCN-700 and L 1 Adding 4,4' -biphenyl dicarboxylic acid and 4mL of N, N ' -dimethylformamide into a 10mL glass bottle, carrying out ultrasonic treatment for 5 minutes, heating the mixture in an oven at 85 ℃ for 24 hours, washing the mixture by fresh N, N ' -dimethylformamide for multiple times, removing unreacted ligand in a pore canal, soaking the mixture in fresh DMF solution, and finally obtaining pale yellow crystal PCN-700-L 1 ；
S9, 40mg of PCN-700-L 1 PdCl 4mg 2 And 5mL acetonitrile solution are filled into a 20mL glass vial, the mixture is heated for 30 hours at 50 ℃, the reaction is finished, and crystals are obtained by centrifugation;
s10, slowly adding the prepared NaBH into a small bottle filled with crystals 4 Reducing with methanol solution for 20 min, removing salt and residual acetonitrile solution in pore canal with anhydrous methanol at least 3 times per dayDisplacing for 3 days, vacuum drying at 65deg.C for 24 hr, and removing methanol to obtain black crystal Pd@PCN-700-L 1 。
2. The method for preparing the nanoparticle composite material for rapidly catalyzing Suzuki reaction at room temperature according to claim 1, wherein in the step S1, (3, 6-dibromopyridin-2-yl) methanol is 5.34g 20mmol, 4-ethoxycarbonylphenylboronic acid is 9.31g 48mmol, tetrakis (triphenylphosphine) palladium is 80mg 0.069mmol, sodium carbonate is 10.18g,96mmol, dioxane is 300mL, and water is 50mL.
3. The method for preparing a nanoparticle composite material for rapidly catalyzing suzuki reaction at room temperature according to claim 1, wherein in the step S1, the reaction time is 40 hours, the reaction temperature is 105 ℃, and 6.86g of product is obtained, and the yield of the product is 84.6%.
4. The method for preparing a nanoparticle composite material for rapidly catalyzing Suzuki reaction at room temperature according to claim 1, wherein in the step S2, the diethyl 4,4' - (6-hydroxymethylpyridine-2, 5-diyl) dibenzoate is 2.03g,5mmol, CBr 4 2.49g of 7.5mmol gave 1.67g of product in 71.6% yield.
5. The method for preparing a nanoparticle composite material for rapid catalysis of Suzuki reaction at room temperature according to claim 1, wherein in the step S3, diethyl 4,4'- (6- (bromomethyl) pyridine-2, 5-diyl) dibenzoate is 1.50g,3.21mmol, aza-18-crown-6 is 0.93g,3.53mmol, triethylamine is 0.4g, and the obtained clamp-like ligand 4,4' - (6- (1, 4,7,10, 13-pentaoxa-16-azacyclooctadec-16-yl) methyl) pyridine-2, 5-dibenzoate is 1.67g, and the clamp-like ligand yield is 76.6%.
6. The method for preparing the nano particle composite material for rapidly catalyzing Suzuki reaction at room temperature according to claim 1,characterized in that in the step S4, the product in 30mL of tetrahydrofuran is 1.1g of 1.69mmol, the sodium hydroxide solution is 0.20g of 5.07mmol, and the ligand L is carboxylated by a white solid 1 0.83g, yield 82.5%.
7. The method for preparing a nanoparticle composite material for rapidly catalyzing Suzuki reaction at room temperature according to claim 1, wherein in the step S8, PCN-700 is 20mg 0.0106mmol,L 1 Crystalline PCN-700-L of 1.5mg 0.0025mmol,4,4' -biphenyldicarboxylic acid 4.0mg 0.0165mmol 1 Is 2300.81.
8. The method for preparing a nanoparticle composite material for rapidly catalyzing Suzuki reaction at room temperature according to claim 1, wherein in the step S10, naBH is adopted 4 The methanol solution was 3mg of 0.08mmol, crystalline Pd@PCN-700-L 1 Pd in the catalyst was 6wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211403573.XA CN115739189B (en) | 2022-11-10 | 2022-11-10 | Preparation method of nanoparticle composite material for rapidly catalyzing suzuki reaction at room temperature |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211403573.XA CN115739189B (en) | 2022-11-10 | 2022-11-10 | Preparation method of nanoparticle composite material for rapidly catalyzing suzuki reaction at room temperature |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115739189A CN115739189A (en) | 2023-03-07 |
| CN115739189B true CN115739189B (en) | 2024-02-13 |
Family
ID=85368122
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211403573.XA Active CN115739189B (en) | 2022-11-10 | 2022-11-10 | Preparation method of nanoparticle composite material for rapidly catalyzing suzuki reaction at room temperature |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115739189B (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102329199A (en) * | 2011-07-19 | 2012-01-25 | 黑龙江大学 | Method for synthesizing biphenyl compounds under composite catalytic actions of Pd/C and crown ether |
| CN105233872A (en) * | 2015-10-22 | 2016-01-13 | 辽宁大学 | Pd @MIL-101 composite and preparation method and application thereof |
| CN110229206A (en) * | 2019-05-22 | 2019-09-13 | 南京师范大学 | Application of the zirconium-based metallic organic backbone as alkaline phosphatase analogue enztme |
| CN112221540A (en) * | 2020-09-01 | 2021-01-15 | 沈阳化工大学 | Pd2+Loaded metal organic framework composite catalyst, preparation method and application |
| CN113262822A (en) * | 2021-05-28 | 2021-08-17 | 刘建红 | N-heterocyclic carbene metal palladium complex catalyst, and synthesis method and application thereof |
| CN113666826A (en) * | 2021-07-30 | 2021-11-19 | 五邑大学 | Method for methoxylation of aryl or heteroaryl |
| CN113694968A (en) * | 2021-09-27 | 2021-11-26 | 常州大学 | Palladium-loaded magnetic UiO-66 ternary composite catalytic material and preparation method and application thereof |
| WO2022018697A1 (en) * | 2020-07-24 | 2022-01-27 | Monash University | Crown ether metal organic framework compositions and methods |
| WO2022016232A1 (en) * | 2020-07-24 | 2022-01-27 | Monash University | Macrocycle-metal organic frameworks |
| CN114685461A (en) * | 2020-12-25 | 2022-07-01 | 中国科学院化学研究所 | Crown ether-containing chiral o-diamine compound, transition metal complex and chiral biaryl compound, and preparation method and application thereof |
| CN115232320A (en) * | 2022-04-27 | 2022-10-25 | 北京工业大学 | Green method for regulating and controlling size and morphology of MOFs crystal by adopting modifier system |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015149072A1 (en) * | 2014-03-28 | 2015-10-01 | The University Of Chicago | Metal-organic frameworks containing nitrogen-donor ligands for efficient catalytic organic transformations |
| US10280147B2 (en) * | 2016-03-28 | 2019-05-07 | King Fahd University Of Petroleum And Minerals | Solid-supported palladium (II) complex as a heterogeneous catalyst for cross coupling reactions and methods thereof |
| KR102456622B1 (en) * | 2020-06-09 | 2022-10-19 | 한국화학연구원 | Modified organometallic framework and catalyst for hydrogenation reactions comprising the same |
-
2022
- 2022-11-10 CN CN202211403573.XA patent/CN115739189B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102329199A (en) * | 2011-07-19 | 2012-01-25 | 黑龙江大学 | Method for synthesizing biphenyl compounds under composite catalytic actions of Pd/C and crown ether |
| CN105233872A (en) * | 2015-10-22 | 2016-01-13 | 辽宁大学 | Pd @MIL-101 composite and preparation method and application thereof |
| CN110229206A (en) * | 2019-05-22 | 2019-09-13 | 南京师范大学 | Application of the zirconium-based metallic organic backbone as alkaline phosphatase analogue enztme |
| WO2022018697A1 (en) * | 2020-07-24 | 2022-01-27 | Monash University | Crown ether metal organic framework compositions and methods |
| WO2022016232A1 (en) * | 2020-07-24 | 2022-01-27 | Monash University | Macrocycle-metal organic frameworks |
| CN112221540A (en) * | 2020-09-01 | 2021-01-15 | 沈阳化工大学 | Pd2+Loaded metal organic framework composite catalyst, preparation method and application |
| CN114685461A (en) * | 2020-12-25 | 2022-07-01 | 中国科学院化学研究所 | Crown ether-containing chiral o-diamine compound, transition metal complex and chiral biaryl compound, and preparation method and application thereof |
| CN113262822A (en) * | 2021-05-28 | 2021-08-17 | 刘建红 | N-heterocyclic carbene metal palladium complex catalyst, and synthesis method and application thereof |
| CN113666826A (en) * | 2021-07-30 | 2021-11-19 | 五邑大学 | Method for methoxylation of aryl or heteroaryl |
| CN113694968A (en) * | 2021-09-27 | 2021-11-26 | 常州大学 | Palladium-loaded magnetic UiO-66 ternary composite catalytic material and preparation method and application thereof |
| CN115232320A (en) * | 2022-04-27 | 2022-10-25 | 北京工业大学 | Green method for regulating and controlling size and morphology of MOFs crystal by adopting modifier system |
Non-Patent Citations (3)
| Title |
|---|
| "An efficient and new protocol for the Heck reaction using palladium nanoparticle‐engineered dibenzo‐18‐crown‐6‐ ether/MCM‐41 nanocomposite in water";Maedeh Azaroon et al.;《Appl Organometal Chem.》;第32卷;1-11 * |
| "Palladium(II)@Zirconium-Based Mixed-Linker Metal– Organic Frameworks as Highly Efficient and Recyclable Catalysts for Suzuki and Heck Cross-Coupling Reactions";Rong Sun et al.;《ChemCatChem》;第8卷;3261-3271 * |
| MCM-41负载对羟基苯乙酮肟环钯催化剂的制备及催化Suzuki反应的研究;张井峰;白雪峰;;化学与黏合(第05期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115739189A (en) | 2023-03-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111054443A (en) | Zirconium-based MOF catalyst loaded with double active sites and preparation method and application thereof | |
| CN112221540A (en) | Pd2+Loaded metal organic framework composite catalyst, preparation method and application | |
| CN115739189B (en) | Preparation method of nanoparticle composite material for rapidly catalyzing suzuki reaction at room temperature | |
| CN104876971A (en) | Co (II) based metal organic framework as well as preparation method and application thereof | |
| CN102229534B (en) | Method for synthesizing alkyl carbonic ester | |
| CN112076776B (en) | Protonated carbon nitrides for selective photocatalytic oxidation of alcohols to esters and uses thereof | |
| CN102500418B (en) | Preparation method of magnetic bidentate imide palladium ligand catalyst | |
| CN100500291C (en) | Composite catalyst containing transient metal loaded by carrier | |
| CN116041253A (en) | Method for synthesizing diphenyl-2-pyridylmethane derivative | |
| CN116041204A (en) | Asymmetric synthesis method of cyclobutane derivative | |
| CN114797988B (en) | Synthesis of composite catalyst and method for preparing beta-isophorone | |
| CN114685298B (en) | Method for synthesizing baclofen based on photocatalytic migration strategy | |
| CN113351253B (en) | Preparation method of MOF@COF core-shell composite material with acid-base synergistic catalysis function | |
| CN111718262B (en) | Simple preparation method of 9-hydroxyfluorene-9-carboxylic ester compound | |
| CN111039767B (en) | Method for preparing deuterated aldehyde by using triazole carbene as catalyst | |
| CN109225333B (en) | Preparation method and application of trinuclear nickel-vanadium oxygen cluster catalyst | |
| CN107556230A (en) | Method for preparing 1, 4-dihydropyridine compound by using micro-reaction device | |
| CN110124738B (en) | Fe-Zn bimetal crystalline catalyst and preparation method and application thereof | |
| CN109369544B (en) | Method for preparing 5-methylpyrazine-2-carboxylic acid by catalytic oxidation | |
| JP6011769B2 (en) | Polystyrene-supported pyridine bisoxazoline derivative-calcium catalyst | |
| CN114632551B (en) | Difunctional chiral catalyst and preparation method and application thereof | |
| CN108610253A (en) | One-step synthesis method non-steroidal anti-inflammatory drugs difunisal | |
| CN113333030B (en) | N-heterocyclic carbene-based- [ Fe-Fe ] hydrogenase model compound and preparation method and application thereof | |
| CN114797984B (en) | Heterogeneous chiral bifunctional catalyst and preparation method and application thereof | |
| CN117777416A (en) | CuTEP-COF polymer and preparation method and application thereof |
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 |