CN115477614A - Benzimidazole column [5] arene N-heterocyclic carbene ligand and preparation method and application thereof - Google Patents
Benzimidazole column [5] arene N-heterocyclic carbene ligand and preparation method and application thereof Download PDFInfo
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 46
- 239000003446 ligand Substances 0.000 title claims abstract description 43
- ADLVDYMTBOSDFE-UHFFFAOYSA-N 5-chloro-6-nitroisoindole-1,3-dione Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC2=C1C(=O)NC2=O ADLVDYMTBOSDFE-UHFFFAOYSA-N 0.000 title claims abstract description 37
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Natural products CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 8
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 8
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 claims abstract description 7
- FGYADSCZTQOAFK-UHFFFAOYSA-N 1-methylbenzimidazole Chemical compound C1=CC=C2N(C)C=NC2=C1 FGYADSCZTQOAFK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 8
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims description 8
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 5
- 238000004440 column chromatography Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000007872 degassing Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000004570 mortar (masonry) Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 238000010791 quenching Methods 0.000 claims description 3
- 230000000171 quenching effect Effects 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 238000007296 Stetter synthesis reaction Methods 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001556 benzimidazoles Chemical class 0.000 description 1
- 238000007193 benzoin condensation reaction Methods 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical compound COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- MSBXTPRURXJCPF-DQWIULQBSA-N cucurbit[6]uril Chemical compound N1([C@@H]2[C@@H]3N(C1=O)CN1[C@@H]4[C@@H]5N(C1=O)CN1[C@@H]6[C@@H]7N(C1=O)CN1[C@@H]8[C@@H]9N(C1=O)CN([C@H]1N(C%10=O)CN9C(=O)N8CN7C(=O)N6CN5C(=O)N4CN3C(=O)N2C2)C3=O)CN4C(=O)N5[C@@H]6[C@H]4N2C(=O)N6CN%10[C@H]1N3C5 MSBXTPRURXJCPF-DQWIULQBSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 150000002461 imidazolidines Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/06—Benzimidazoles; Hydrogenated benzimidazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2265—Carbenes or carbynes, i.e.(image)
- B01J31/2269—Heterocyclic carbenes
- B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
- B01J2231/4211—Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group
- B01J2231/4227—Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group with Y= Cl
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/80—Constitutive chemical elements of heterogeneous catalysts of Group VIII of the Periodic Table
- B01J2523/82—Metals of the platinum group
- B01J2523/824—Palladium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/22—Organic complexes
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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)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a benzimidazole column [5] arene N-heterocyclic carbene ligand, a preparation method and application thereof, belonging to the field of organic synthesis. The preparation method of the benzimidazole column [5] arene N-heterocyclic carbene ligand comprises the following steps: (1) Preparing column [5] arene S-I by using 1,1-dibromo para-phenyl diethyl ether and paraformaldehyde; (2) The benzimidazole column [5] arene N-heterocyclic carbene ligand I is prepared by reacting column [5] arene S-I with 1-methylbenzimidazole. The ligand preparation method provided by the invention has the advantages of high yield, strong operability, novel synthetic route, convenience in post-treatment and the like. The benzimidazole column [5] arene N-heterocyclic carbene ligand related by the invention can be successfully applied to Suzuki-Miyaura coupling reaction, and has the advantages of low dosage, simple and convenient operation, high yield and the like.
Description
Technical Field
The invention discloses a benzimidazole column [5] arene N-heterocyclic carbene ligand, and a preparation method and application thereof, belonging to the technical field of organic synthesis.
Background
The pillared aromatic hydrocarbon has unique structural advantages and excellent identification performance, and becomes a fifth-generation supermolecule main body after crown ether, cyclodextrin, calixarene and cucurbituril. The column [5] arene has 10 derived sites, can introduce diversified functional groups according to needs, and is widely applied to various aspects such as organic synthesis, biomedicine, functional materials, separation analysis and the like. Among them, the column [5] arene modified by the organic ligand shows good auxiliary catalytic activity in certain reactions, and has gradually become a research hotspot of chemists.
In recent years, N-heterocyclic carbenes have attracted a great deal of attention from organic synthesizers due to their excellent physical and chemical properties and good selectivity. The N-heterocyclic carbene itself can be used as a catalyst to catalyze organic reactions, such as benzoin reaction or Stetter reaction; can also act as ligands, participate in and promote certain transition metal catalyzed reactions, such as Heck coupling or Suzuki coupling. In common N-heterocyclic carbene types, imidazolidines and imidazoles (including benzimidazoles) are more applied as ligands, but the types of the N-heterocyclic carbene ligands are less at present, and the N-heterocyclic carbene ligands often need larger dosage, so that the application reaction range is greatly limited. In view of the important role of benzimidazole ligands in organic synthesis, a novel benzimidazole column [5] arene N-heterocyclic carbene ligand is synthesized through a high-efficiency, convenient and mild-condition route, and the research on the expression of the benzimidazole column [5] arene N-heterocyclic carbene ligand in the reaction has important application value.
Disclosure of Invention
The invention aims to overcome the problems of less types, more dosage and the like of the existing N-heterocyclic carbene ligands, design and synthesize a novel benzimidazole N-heterocyclic carbene ligand and research the application of the benzimidazole N-heterocyclic carbene ligand in transition metal catalytic reaction.
In order to achieve the purpose, the invention provides a method for synthesizing a benzimidazole column [5] arene N-heterocyclic carbene ligand with high efficiency, convenience and mild conditions, and researches the Suzuki-Miyaura coupling reaction of phenylboronic acid and bromobenzene which participates as the ligand. The benzimidazole column [5] arene N-heterocyclic carbene ligand has a structure shown in a formula I:
the preparation method is shown as formula II:
the present invention is described in steps, that is, the steps in the above formula are specifically described in sequence step by step.
The first step is the preparation of column [5] arene S-I:
putting paraformaldehyde into a mortar, fully grinding the paraformaldehyde, adding the paraformaldehyde into a three-neck flask, then adding 1,1-dibromo p-phenyl diethyl ether and magnetons into the three-neck flask, degassing the mixture in the three-neck flask three times by using pumped air, then adding 1,2-dichloroethane under a nitrogen environment, violently stirring the mixture for 30 minutes, adding boron trifluoride diethyl etherate into a reaction system, reacting at room temperature for 1 hour, adding methanol for quenching, carrying out suction filtration on the system, carrying out reduced pressure evaporation on filtrate, purifying the reaction mixture by fast column chromatography, and eluting by dichloromethane with petroleum ether =1:1 to obtain the corresponding column aromatic hydrocarbon S-I. The reaction formula of the step is as follows:
the second step is preparation of benzimidazole column [5] arene N-heterocyclic carbene ligand I:
adding column [5] arene S-I, 1-methylbenzimidazole and magnetons into a round-bottom flask, then adding acetonitrile, reacting for 72 hours at 50 ℃, decompressing and evaporating a solvent after the reaction is stopped, ultrasonically dissolving the obtained solid for 30 minutes by using methyl tert-butyl ether, removing a supernatant after standing, repeating the operation for multiple times, and finally filtering and drying to obtain the solid, namely the benzimidazole column [5] arene N-heterocyclic carbene ligand I. The reaction formula of the step is as follows:
in the first step, the molar ratio of 1,1-dibromo-p-phenyl-diethyl ether, paraformaldehyde and boron trifluoride-diethyl ether is 1.
The molar ratio of the cyclo [5] arene S-I and 1-methylbenzimidazole in the second step is 1.
The application of the benzimidazole column [5] arene N-heterocyclic carbene ligand I is as follows: ligands that are Pd (II) catalysts participate in and promote Suzuki-Miyaura coupling reactions of phenylboronic acid with bromobenzene.
Compared with the traditional method, the method has the beneficial effects that:
(1) The invention designs and synthesizes a novel benzimidazole column [5] arene N-heterocyclic carbene ligand, and the related ligand preparation method has the advantages of high yield, strong operability, novel synthetic route, convenient post-treatment and the like;
(2) The benzimidazole column [5] arene N-heterocyclic carbene ligand related by the invention can be successfully applied to Suzuki-Miyaura coupling reaction, and has the advantages of low dosage, high reaction efficiency, simple and convenient operation and the like.
Drawings
FIG. 1 is a diagram of Compound (I) prepared in example 1 1 An H NMR spectrum;
Detailed Description
The method of the present invention is described herein by way of specific examples, but the present invention is not limited thereto, and any modifications, equivalents, improvements, etc. made within the technical spirit of the present invention should be included within the scope of the present invention.
Example 1:
the invention provides a method for preparing benzimidazole column [5] arene N-heterocyclic carbene ligand, which comprises the following steps:
the first step is a column [5]]Preparation of aromatic hydrocarbon S-I: putting 0.7g paraformaldehyde into a mortar, fully grinding, adding into a three-neck flask, then adding 3.6g 1, 1-dibromo p-phenyl diethyl ether and magnetons into the three-neck flask, degassing the mixture in the three-neck flask three times by using a ventilation gas, adding 83mL 1, 2-dichloroethane under a nitrogen environment, violently stirring for 30 minutes, adding 2.8mL boron trifluoride diethyl ether into the reaction system, reacting at room temperature for 1 hour, adding methanol for quenching, carrying out suction filtration on the system, carrying out reduced pressure evaporation on the filtrate, purifying the reaction mixture by using rapid column chromatography, eluting with dichloromethane: petroleum ether =1:1 to obtain the corresponding column aromatic compoundA hydrocarbon S-I. The yield of compound S-I was 62%. The compound is a known compound which is capable of inhibiting the growth of the tumor, 1 H NMR、 13 c NMR was consistent with the standard spectrum.
The second step is preparation of benzimidazole column [5] arene N-heterocyclic carbene ligand I: adding 0.1g of column [5] arene S-I,0.2g of 1-methylbenzimidazole and magnetons into a 50mL round-bottom flask, then adding 1.6mL of acetonitrile, reacting at 50 ℃ for 72h, after the reaction is stopped, evaporating the solvent under reduced pressure, ultrasonically dissolving the obtained solid for 0.5h by using methyl tert-butyl ether, standing, removing the supernatant, repeating the operation for multiple times, and finally filtering and drying to obtain the solid, namely the benzimidazole column [5] arene N-heterocyclic carbene ligand I. The yield of compound I was 83%.
Nuclear magnetic data for I are as follows:
1 H NMR(500MHz,DMSO-d6)δ10.19(s,2H),7.71-7.59(m,8H),6.69(s,2H),4.57-4.54(m,8H),4.15(s,6H),4.10-4.03(m,2H)ppm.
example 2
The invention also researches the expression of the benzimidazole column [5] arene N-heterocyclic carbene ligand I in the Suzuki-Miyaura coupling reaction of phenylboronic acid and bromobenzene, and the reaction equation is as follows:
mixing compound 1 (5 mmol), 2 (5.5 mmol), palladium chloride (0.25 mmol) and benzimidazole column [ 5%]Sequentially adding arene N-heterocyclic carbene ligand I (0.05 mmol) and cesium carbonate (15 mmol) into a reactor under the inert gas atmosphere, adding 50mL of isopropanol, and reacting at 50 ℃ for 36h. After the reaction is finished, pure 3 is obtained by column chromatography separation. The yield of compound 3 was 85%. Compound 3 is a known compound, which 1 HNMR、 13 C NMR was consistent with the standard spectrum.
In the above examples, g represents "g"; mmol stands for "mmol"; mL represents "mL"; h represents "hour"; DEG C stands for "centigrade"; DCE stands for "1,2-dichloroethane"; NHC stands for benzimidazole column [5] arene N-heterocyclic carbene ligand; i-PrOH stands for "isopropanol".
It can be seen from the above examples that the method for synthesizing benzimidazole column [5] arene N-heterocyclic carbene ligands according to the invention can efficiently and conveniently obtain target products under mild conditions. The benzimidazole column [5] arene N-heterocyclic carbene ligand can be successfully applied to Suzuki-Miyaura coupling reaction, and has the advantages of low dosage, simplicity and convenience in operation, high yield and the like.
Claims (4)
1. A benzimidazole [5] arene N-heterocyclic carbene ligand, a preparation method and applications thereof, wherein the benzimidazole [5] arene N-heterocyclic carbene ligand has a structure shown in a formula I:
the preparation method is carried out according to the steps shown in the formula II:
the first step is the preparation of column [5] arene S-I:
putting paraformaldehyde into a mortar, fully grinding, adding into a three-mouth flask, then adding 1,1-dibromo p-phenyl diethyl ether and magnetons into the three-mouth flask, degassing the mixture in the three-mouth flask for three times by using a pumping gas, adding 1,2-dichloroethane in a nitrogen environment, violently stirring for 30 minutes, adding boron trifluoride diethyl ether into a reaction system, reacting for 1 hour at room temperature, adding methanol for quenching, carrying out suction filtration on the system, evaporating the filtrate under reduced pressure, purifying the reaction mixture by fast column chromatography, eluting with dichloromethane, petroleum ether =1:1, and obtaining corresponding column aromatic hydrocarbon S-I;
the second step is preparation of benzimidazole column [5] arene N-heterocyclic carbene ligand I:
adding column [5] arene S-I, 1-methylbenzimidazole and magnetons into a round-bottom flask, then adding acetonitrile, reacting for 72 hours at 50 ℃, after the reaction is stopped, evaporating the solvent under reduced pressure, ultrasonically dissolving the obtained solid for 30 minutes by using methyl tert-butyl ether, removing a supernatant after standing, repeating the operations for multiple times, and finally filtering and drying to obtain the solid, namely the benzimidazole column [5] arene N-heterocyclic carbene ligand I.
2. The process for the preparation of column [5] arene S-I according to claim 1, wherein the molar ratio of 1,1-dibromopara-phenyl diethyl ether, paraformaldehyde and boron trifluoride diethyl etherate is 1.
3. The preparation method of the benzimidazole column [5] arene N-heterocyclic carbene ligand I according to claim 1, wherein the molar ratio of the column [5] arene S-I to the 1-methylbenzimidazole is 1.
4. The application of the benzimidazole column [5] arene N-heterocyclic carbene ligand I in claim 1 is as follows: participate as a transition metal ligand and promote the Suzuki-Miyaura coupling reaction of phenylboronic acid with bromobenzene.
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| CN116217491A (en) * | 2023-03-21 | 2023-06-06 | 青岛科技大学 | Benzimidazole single-functionalized column [5] arene N-heterocyclic carbene catalyst and preparation method and application thereof |
| CN116217491B (en) * | 2023-03-21 | 2024-05-14 | 青岛科技大学 | Benzimidazole single-functionalized column [5] arene N-heterocyclic carbene catalyst and preparation method and application thereof |
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