CN116764680A - Preparation method and application of heterogeneous coupling catalyst - Google Patents
Preparation method and application of heterogeneous coupling catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 238000005859 coupling reaction Methods 0.000 title claims description 18
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 230000008878 coupling Effects 0.000 title description 6
- 238000010168 coupling process Methods 0.000 title description 6
- 239000002638 heterogeneous catalyst Substances 0.000 claims abstract description 51
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 27
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003446 ligand Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000002841 Lewis acid Substances 0.000 claims abstract description 9
- -1 aromatic ring compound Chemical class 0.000 claims abstract description 9
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 9
- 150000002940 palladium Chemical class 0.000 claims abstract description 9
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 9
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 5
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000000047 product Substances 0.000 claims description 19
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 229910052763 palladium Inorganic materials 0.000 claims description 10
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 9
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 8
- 239000004305 biphenyl Substances 0.000 claims description 8
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 claims description 8
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- AAXGWYDSLJUQLN-UHFFFAOYSA-N diphenyl(propyl)phosphane Chemical compound C=1C=CC=CC=1P(CCC)C1=CC=CC=C1 AAXGWYDSLJUQLN-UHFFFAOYSA-N 0.000 claims description 6
- WUOIAOOSKMHJOV-UHFFFAOYSA-N ethyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(CC)C1=CC=CC=C1 WUOIAOOSKMHJOV-UHFFFAOYSA-N 0.000 claims description 6
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 6
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 5
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical group OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 claims description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 5
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical group Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 5
- 238000004537 pulping Methods 0.000 claims description 5
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 claims description 4
- 229910015900 BF3 Inorganic materials 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 4
- WXMZPPIDLJRXNK-UHFFFAOYSA-N butyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(CCCC)C1=CC=CC=C1 WXMZPPIDLJRXNK-UHFFFAOYSA-N 0.000 claims description 4
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 claims description 4
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 3
- WTAPZWXVSZMMDG-UHFFFAOYSA-N 1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].C=1C=CC=CC=1C=CC(=O)C=CC1=CC=CC=C1 WTAPZWXVSZMMDG-UHFFFAOYSA-N 0.000 claims description 2
- 239000012043 crude product Substances 0.000 claims description 2
- 239000012452 mother liquor Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- WMKGGPCROCCUDY-PHEQNACWSA-N dibenzylideneacetone Chemical compound C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 WMKGGPCROCCUDY-PHEQNACWSA-N 0.000 claims 1
- 238000004064 recycling Methods 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 239000000758 substrate Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 4
- 230000014759 maintenance of location Effects 0.000 abstract description 4
- 125000004122 cyclic group Chemical group 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 28
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 12
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 230000035484 reaction time Effects 0.000 description 11
- MJGAKVFFADUFMG-UHFFFAOYSA-N 6-bromopyrazolo[1,5-a]pyridine Chemical compound C1=C(Br)C=CC2=CC=NN21 MJGAKVFFADUFMG-UHFFFAOYSA-N 0.000 description 8
- 239000012295 chemical reaction liquid Substances 0.000 description 8
- 235000011056 potassium acetate Nutrition 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- QJPJQTDYNZXKQF-UHFFFAOYSA-N 4-bromoanisole Chemical compound COC1=CC=C(Br)C=C1 QJPJQTDYNZXKQF-UHFFFAOYSA-N 0.000 description 4
- KFGVRWGDTLZAAO-UHFFFAOYSA-N cyclopenta-1,3-diene dicyclohexyl(cyclopenta-1,3-dien-1-yl)phosphane iron(2+) Chemical compound [Fe++].c1cc[cH-]c1.C1CCC(CC1)P(C1CCCCC1)c1ccc[cH-]1 KFGVRWGDTLZAAO-UHFFFAOYSA-N 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- WYECURVXVYPVAT-UHFFFAOYSA-N 1-(4-bromophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Br)C=C1 WYECURVXVYPVAT-UHFFFAOYSA-N 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 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 2
- PIMNFNXBTGPCIL-UHFFFAOYSA-N 1-(2-bromophenyl)ethanone Chemical compound CC(=O)C1=CC=CC=C1Br PIMNFNXBTGPCIL-UHFFFAOYSA-N 0.000 description 1
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical compound CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application discloses a preparation method and application of a heterogeneous catalyst, wherein an aromatic ring compound and a bidentate phosphine ligand are dispersed in a dihalide or dihalide equivalent solution, and a catalyst carrier is obtained through Fridel-Craft alkylation reaction under the catalysis of Lewis acid, and is prepared after palladium salt loading. The heterogeneous catalyst has the following characteristics: 1. the load is firm, the high-efficiency catalytic efficiency is realized, and the activity is not obviously reduced after multiple times of cyclic use; 2. the substrate has wide application range, and higher Pd retention rate and recycling potential are shown on the multi-heteroatom substrate; 3. the preparation and post-treatment processes of the catalyst are simple and safe, and can realize kilogram-level production and industrial application.
Description
Technical Field
The application belongs to the technical field of chemistry and new materials, and particularly relates to a preparation method and application of a heterogeneous catalyst.
Background
Palladium catalysts have been rapidly developed over the last decades and have been successfully used in coupling reactions for the formation of various types of C-C and C-heteroatom bonds, which are of great chemical significance for organic synthesis. Compared with other metal catalyzed coupling reactions, the palladium catalyzed coupling reaction has the advantages of mild reaction conditions, tolerance to various active functional groups, high yield, insensitivity to moisture and the like, and is widely applied to the fields of pharmacy, electronic industry, advanced materials and the like. However, after the reaction is completed, the homogeneous palladium catalyst is difficult to separate from the reaction system, so that the post-treatment and purification are difficult, the product often contains more palladium, the quality of the product is affected, and particularly, in daily chemical products, pharmacy and electronic industry, the content requirement on residual metal in the product is strict; in addition, expensive palladium is difficult to recycle, resulting in excessive costs. Thus, the use of homogeneous palladium catalysts in industry is greatly limited.
An effective way to solve the above problems is to use heterogeneous catalysts instead of conventional homogeneous catalysts. Tan Bien it is reported that the organic porous polymer is prepared by using the Scholl coupling reaction (CN 102887991B) and the coupling catalyst prepared by taking the organic porous polymer as a carrier has better catalytic performance, however, the Scholl coupling reaction needs to be completed under the oxidizing condition, is not suitable for the crosslinking of phosphorus-containing ligands (easy to be oxidized and deactivated), and is difficult to realize in scale-up. The Tao Li uses benzene, triphenylphosphine and dimethanol as raw materials to prepare a phosphorus-containing polymer through Fridel-Craft reaction, palladium chloride is loaded on the phosphorus-containing polymer as a carrier, and the obtained catalyst has good activity and palladium retention rate in Suzuki reaction of simple substrates, and can be used mechanically (adv. Mater.2012,24, 3390-3395). However, the catalyst preparation process of Tao Li has high safety risk, cannot be produced in a large scale, and cannot realize industrial application. In the coupling reaction practice of the substrate containing hetero atoms, the catalyst has the defects of weak load, high palladium loss rate and difficult application.
Disclosure of Invention
The application provides a preparation method and application of a heterogeneous coupling catalyst, which has the advantages of firm catalyst load, high catalytic efficiency, wide substrate application range and no obvious reduction of activity after repeated cyclic use.
In one aspect, the application provides a heterogeneous catalyst characterized in that the heterogeneous catalyst is prepared by dispersing an aromatic ring compound and a bidentate phosphine ligand in a dihalide or dihalide equivalent solution, and carrying out Fridel-Craft alkylation reaction under the catalysis of Lewis acid to obtain a catalyst carrier, wherein the catalyst carrier is loaded by palladium salt.
Preferably, the bidentate phosphine ligand is selected from 1,1 '-binaphthyl-2, 2' -bis-diphenylphosphine (BINAP), diphenylphosphino ferrocene (DPPF), 1 '-diphenyl ether-2, 2' -bis-diphenylphosphine (DPEPhos), diphenylphosphinoethane (DPPE), diphenylphosphinopropane (DPPP) or diphenylphosphinobutane (DPPD).
Preferably, the aromatic ring compound is selected from benzene, toluene, biphenyl or naphthalene.
Preferably, the dihalide is selected from dichloromethane, dibromomethane, diiodomethane, 1, 2-dichloroethane, 1, 2-dibromoethane, p-dibenzyl chloride or p-dibenzyl bromide; the dihalide equivalent is selected from dimethanol formal.
Preferably, the lewis acid is selected from aluminum trichloride, anhydrous ferric trichloride, titanium tetrachloride, boron trifluoride, boron trichloride, or boron tribromide.
Preferably, the palladium salt is selected from palladium chloride, palladium nitrate, palladium acetate or palladium bis dibenzylidene acetonate.
In another aspect, the present application provides a method for preparing a heterogeneous catalyst, comprising the steps of:
(1) Dispersing an aromatic ring compound and a bidentate phosphine ligand in a dihalide or dihalide equivalent solution, and carrying out Fridel-Craft alkylation reaction under the catalysis of Lewis acid to obtain a catalyst carrier crude product, wherein the specific temperature control process comprises the following steps of: heating to 35-45 ℃, and reacting for 2-12 hours at constant temperature; heating to 55-65 ℃, and reacting for 2-12 hours at constant temperature;
(2) Pulping, centrifuging or filtering the crude catalyst carrier product, and drying to obtain a catalyst carrier;
(3) Dissolving palladium salt in a solvent to form a salt solution, and adding the catalyst carrier obtained in the step (2) into the salt solution;
(4) Heating the system obtained in the step (3) to 50-100 ℃, and carrying out heat preservation reaction;
(5) And (3) carrying out suction filtration on the mother liquor obtained in the step (4), washing and drying to obtain the heterogeneous catalyst.
Preferably, the bidentate phosphine ligand is 1,1 '-binaphthyl-2, 2' -bis-diphenylphosphine (BINAP), diphenylphosphino ferrocene (DPPF), 1 '-diphenyl ether-2, 2' -bis-diphenylphosphine (DPEPhos), diphenylphosphinoethane (DPPE), diphenylphosphinopropane (DPPP) or diphenylphosphinobutane (DPPD).
Preferably, the aromatic ring compound is selected from benzene, toluene, biphenyl or naphthalene.
Preferably, the dihalide is selected from dichloromethane, dibromomethane, diiodomethane, 1, 2-dichloroethane, 1, 2-dibromoethane, p-dibenzyl chloride or p-dibenzyl bromide; the dihalide equivalent is selected from dimethanol formal.
Preferably, the lewis acid is selected from aluminum trichloride, anhydrous ferric trichloride, titanium tetrachloride, boron trifluoride, boron trichloride, or boron tribromide; the palladium salt is selected from palladium chloride, palladium nitrate, palladium acetate or bis dibenzylidene acetone palladium.
In another aspect, the present application provides the use of the aforementioned heterogeneous catalyst for a Suzuki coupling reaction or a Miyaura coupling reaction.
The heterogeneous catalyst of the application has the following beneficial effects: 1. the load is firm, the high-efficiency catalytic efficiency is realized, and the activity is not obviously reduced after multiple times of cyclic use; 2. the substrate has wide application range, and higher Pd retention rate and recycling potential are shown on the multi-heteroatom substrate; 3. the preparation and post-treatment processes of the catalyst are simple and safe, and can realize kilogram-level production and industrial application.
Detailed Description
Example 1 preparation of heterogeneous catalysts
Toluene (0.74 kg) and BINAP (1.3 kg) were dissolved in 1, 2-dichloroethane (7.4L), aluminum trichloride (4.0 kg) was added in portions at 17 to 25℃and then incubated at 40℃and 60℃in sequence for 2 hours; adding dilute hydrochloric acid (24.0L) to quench reaction after heat preservation is finished, heating to 70 ℃, and pulping for 12 hours; suction filtering, collecting filter cake, pulping with methanol (30.0L) and acetone (20.0L) at 70deg.C for 3 hr, collecting filter cake, and drying to obtain catalyst carrier.
Palladium acetate (43.0 g) was dissolved in acetone (4.2L) and stirred at room temperature for 1 hour until the solution was completely clear; adding a catalyst carrier (700.0 g) into a palladium acetate solution, heating to 70 ℃ and preserving heat for reaction; suction filtering, collecting filter cake, pulping with acetone (4.2L), suction filtering, and drying filter cake to obtain heterogeneous catalyst.
Experimental example 1 Suzuki coupling reaction of bromobenzene and phenylboronic acid
The heterogeneous catalyst provided in example 1 was used for a Suzuki coupling reaction of bromobenzene and phenylboronic acid, wherein bromobenzene was 1.57g (10.0 mmol), phenylboronic acid was 1.82g (15.0 mmol), potassium carbonate was 4.1g (30.0 mmol), heterogeneous catalyst was 0.6g, etOH was 30mL, water was 20mL, and the reaction temperature was 70℃and the reaction time was 1 hour. The content of the product in the reaction liquid is 99.1 percent. Filtering the heterogeneous catalyst, washing the catalyst with water and acetone in sequence, drying, and recycling. The catalytic performance of the heterogeneous catalyst does not change obviously after the heterogeneous catalyst is recycled for 6 times.
Experimental example 2 Suzuki coupling reaction of Parmethoxybromobenzene and phenylboronic acid
The heterogeneous catalyst provided in example 1 was used for a Suzuki coupling reaction of p-methoxybromobenzene with phenylboronic acid, wherein the p-methoxybromobenzene was 1.87g (10.0 mmol), phenylboronic acid was 1.82g (15.0 mmol), potassium carbonate was 4.1g (30.0 mmol), the heterogeneous catalyst was 0.6g, etOH was 30mL, water was 20mL, the reaction temperature was 70℃and the reaction time was 0.5 hours. The content of the product in the reaction solution was 92.8%. Filtering the heterogeneous catalyst, washing the catalyst with water and acetone in sequence, drying, and recycling. The catalytic performance of the heterogeneous catalyst does not change obviously after the heterogeneous catalyst is recycled for 6 times.
Experimental example 3 Suzuki coupling reaction of Acetylbromobenzene and phenylboronic acid
The heterogeneous catalyst provided in example 1 was used for a Suzuki coupling reaction of p-acetyl bromobenzene with phenylboronic acid, wherein the p-acetyl bromobenzene was 2.00g (10.0 mmol), phenylboronic acid was 1.82g (15.0 mmol), potassium carbonate was 4.1g (30.0 mmol), the heterogeneous catalyst was 0.6g, etOH was 30mL, water was 20mL, and the reaction temperature was 70℃and the reaction time was 1 hour. The content of the product in the reaction liquid is 87.1 percent. Filtering the heterogeneous catalyst, washing the catalyst with water and acetone in sequence, drying, and recycling. The catalytic performance of the heterogeneous catalyst does not change obviously after the heterogeneous catalyst is recycled for 6 times.
Experimental example 4 Miyaura coupling reaction of bromobenzene and pinacol biborate
The heterogeneous catalyst provided in the above example was used for Miyaura coupling reaction of bromobenzene and pinacol biborate, wherein bromobenzene was 3.14g (20.0 mmol), pinacol biborate was 5.33g (21.0 mmol), potassium acetate was 5.88g (60.0 mmol), heterogeneous catalyst was 0.8g, dioxane was 25mL, reaction temperature was 100℃and reaction time was 1 hour. The reaction liquid contains 88.7% of the product. Filtering the heterogeneous catalyst, washing the catalyst with water and acetone in sequence, drying, and recycling. The catalytic performance of the heterogeneous catalyst does not change obviously after the heterogeneous catalyst is recycled for 6 times.
Experimental example 5 Miyaura coupling reaction of Parmethoxybromobenzene and pinacol bisborate
The heterogeneous catalyst provided in the above example was used for Miyaura coupling of p-methoxybromobenzene with pinacol biborate, wherein p-methoxybromobenzene was 3.74g (20.0 mmol), pinacol biborate was 5.33g (21.0 mmol), potassium acetate was 5.88g (60.0 mmol), heterogeneous catalyst 0.8g, dioxane was 25mL, and the reaction temperature was 100℃and the reaction time was 2 hours. The content of the product in the reaction solution was 82.0%. Filtering the heterogeneous catalyst, washing the catalyst with water and acetone in sequence, drying, and recycling. The catalytic performance of the heterogeneous catalyst does not change obviously after the heterogeneous catalyst is recycled for 6 times.
Comparative example 1
Tao Li report (adv. Mater.2012,24, 3390-3395) catalyst (LT cat.) was used for Miyaura coupling reaction of 6-bromopyrazolo [1,5-a ] pyridine and pinacol bisborate, wherein 6-bromopyrazolo [1,5-a ] pyridine was 78g (3.97 mmol), pinacol bisborate was 131g (5.16 mmol), potassium acetate 117g (11.92 mmol), catalyst 15.6g, dioxane 300mL. The reaction temperature was 85℃and the reaction time was 2.5 hours. The content of the product in the reaction solution was 91.1%.
Filtering the heterogeneous catalyst, washing the catalyst with dioxane, water and methanol, drying, and recycling. Wherein 78g (3.97 mmol) of 6-bromopyrazolo [1,5-a ] pyridine, 131g (5.16 mmol) of pinacol biborate, 117g (11.92 mmol) of potassium acetate, 15.6g of catalyst and 300mL of dioxane were recovered. The reaction temperature was 85℃and the reaction time was 6 hours. The content of the product in the reaction solution was 82.3%. Compared with the fresh catalyst, the product content in the reaction liquid of the recovered catalyst reaction is obviously reduced, and the conversion speed is obviously slowed down. Further, ICP-MS test showed that the Pd content in the fresh state of the catalyst was 4.3wt% and the Pd content in the recovered state thereof was 2.0wt%.
The heterogeneous catalyst of the application was used in Miyaura coupling of 6-bromopyrazolo [1,5-a ] pyridine and pinacol bisborate, wherein the 6-bromopyrazolo [1,5-a ] pyridine was 78g (3.97 mmol), pinacol bisborate was 131g (5.16 mmol), potassium acetate 117g (11.92 mmol), catalyst 15.6g, dioxane 300mL. The reaction temperature was 85℃and the reaction time was 3 hours. The content of the product in the reaction solution was 91.6%.
First time of application: filtering the heterogeneous catalyst, washing the catalyst with dioxane, water and methanol, drying, and recycling. Wherein 78g (3.97 mmol) of 6-bromopyrazolo [1,5-a ] pyridine, 131g (5.16 mmol) of pinacol biborate, 117g (11.92 mmol) of potassium acetate, 15.6g of catalyst and 300mL of dioxane were recovered. The reaction temperature was 85℃and the reaction time was 3 hours. The content of the product in the reaction liquid is 90.8 percent.
And (3) secondary application: filtering the heterogeneous catalyst, washing the catalyst with dioxane, water and methanol in sequence, drying, and recycling. Wherein 78g (3.97 mmol) of 6-bromopyrazolo [1,5-a ] pyridine, 131g (5.16 mmol) of pinacol biborate, 117g (11.92 mmol) of potassium acetate, 15.6g of catalyst and 300mL of dioxane were recovered. The reaction temperature was 85℃and the reaction time was 3 hours. The content of the product in the reaction liquid is 90.4 percent.
And (3) third time of application: filtering the heterogeneous catalyst, washing the catalyst with dioxane, water and methanol in sequence, drying, and recycling. Wherein 78g (3.97 mmol) of 6-bromopyrazolo [1,5-a ] pyridine, 131g (5.16 mmol) of pinacol biborate, 117g (11.92 mmol) of potassium acetate, 15.6g of catalyst and 300mL of dioxane were recovered. The reaction temperature was 85℃and the reaction time was 3 hours. The content of the product in the reaction liquid is 82.3%, and the content of the product in the reaction liquid is reduced after the reaction of the recovered catalyst.
Further, ICP-MS test shows that the Pd content in the fresh catalyst is 3.0wt%, and the Pd content of the recovered catalyst is 1.7wt% after three times of application. Compared with LT Cat, the novel catalyst in the application shows higher Pd retention rate on a multi-heteroatom substrate, has higher application times, and can realize large-scale preparation.
Claims (12)
1. A heterogeneous catalyst is characterized in that an aromatic ring compound and a bidentate phosphine ligand are dispersed in a dihalide or dihalide equivalent solution, and under the catalysis of Lewis acid, a catalyst carrier is obtained through Fridel-Craft alkylation reaction, and the catalyst carrier is prepared after palladium salt loading.
2. The heterogeneous catalyst of claim 1, wherein the bidentate phosphine ligand is selected from 1,1 '-binaphthyl-2, 2' -bisdiphenylphosphine, diphenylphosphinferrocene, 1 '-diphenyl ether-2, 2' -bisdiphenylphosphine, diphenylphosphinoethane, diphenylphosphinopropane, or diphenylphosphinobutane.
3. Heterogeneous catalyst according to claim 1 or 2, characterized in that the aromatic ring compound is selected from benzene, toluene, biphenyl or naphthalene.
4. Heterogeneous catalyst according to claim 1 or 2, characterized in that the dihalide is selected from dichloromethane, dibromomethane, diiodomethane, 1, 2-dichloroethane, 1, 2-dibromoethane, p-dibenzyl chloride or p-dibenzyl bromide; the dihalide equivalent is selected from dimethanol formal.
5. Heterogeneous catalyst according to claim 1 or 2, characterized in that the lewis acid is selected from aluminium trichloride, anhydrous ferric trichloride, titanium tetrachloride, boron trifluoride, boron trichloride or boron tribromide.
6. Heterogeneous catalyst according to claim 1 or 2, characterized in that the palladium salt is selected from palladium chloride, palladium nitrate, palladium acetate or palladium bis dibenzylideneacetone.
7. A method for preparing a heterogeneous catalyst, comprising the steps of:
(1) Dispersing an aromatic ring compound and a bidentate phosphine ligand in a dihalide or dihalide equivalent solution, and carrying out Fridel-Craft alkylation reaction under the catalysis of Lewis acid to obtain a catalyst carrier crude product, wherein the specific temperature control process comprises the following steps of: heating to 35-45 ℃, and reacting for 2-12 hours at constant temperature; heating to 55-65 ℃, and reacting for 2-12 hours at constant temperature;
(2) Pulping, centrifuging or filtering the crude catalyst carrier product, and drying to obtain a catalyst carrier;
(3) Dissolving palladium salt in a solvent to form a salt solution, and adding the catalyst carrier obtained in the step (2) into the salt solution;
(4) Heating the system obtained in the step (3) to 50-100 ℃, and carrying out heat preservation reaction;
(5) And (3) carrying out suction filtration on the mother liquor obtained in the step (4), washing and drying to obtain the heterogeneous catalyst.
8. The method of claim 7, wherein the bidentate phosphine ligand is selected from 1,1 '-binaphthyl-2, 2' -bisdiphenylphosphine, diphenylphosphinferrocene, 1 '-diphenyl ether-2, 2' -bisdiphenylphosphine, diphenylphosphinoethane, diphenylphosphinopropane, and diphenylphosphinobutane.
9. The method of claim 7, wherein the aromatic ring compound is selected from benzene, toluene, biphenyl, and naphthalene.
10. The process according to claim 7, wherein the dihalide is selected from the group consisting of dichloromethane, dibromomethane, diiodomethane, 1, 2-dichloroethane, 1, 2-dibromoethane, p-dibenzyl chloride and p-dibenzyl bromide; the dihalide equivalent is selected from dimethanol formal.
11. The method of claim 7, wherein the lewis acid is selected from the group consisting of aluminum trichloride, anhydrous ferric trichloride, titanium tetrachloride, boron trifluoride, boron trichloride, and boron tribromide; the palladium salt is selected from palladium chloride, palladium nitrate, palladium acetate or bis dibenzylidene acetone palladium.
12. Use of the heterogeneous catalyst of claim 1 for a Suzuki coupling reaction or a Miyaura coupling reaction.
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