CN116217491B - Benzimidazole single-functionalized column [5] arene N-heterocyclic carbene catalyst and preparation method and application thereof - Google Patents
Benzimidazole single-functionalized column [5] arene N-heterocyclic carbene catalyst and preparation method and application thereof Download PDFInfo
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 48
- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- 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 33
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Natural products CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 20
- OHBQPCCCRFSCAX-UHFFFAOYSA-N 1,4-Dimethoxybenzene Chemical compound COC1=CC=C(OC)C=C1 OHBQPCCCRFSCAX-UHFFFAOYSA-N 0.000 claims abstract description 12
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 12
- FGYADSCZTQOAFK-UHFFFAOYSA-N 1-methylbenzimidazole Chemical compound C1=CC=C2N(C)C=NC2=C1 FGYADSCZTQOAFK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000007193 benzoin condensation reaction Methods 0.000 claims abstract description 8
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 7
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 7
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 23
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims description 9
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 8
- 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
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 4
- 238000005086 pumping Methods 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000012530 fluid Substances 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
- 238000001556 precipitation Methods 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
- 238000010992 reflux Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 238000007872 degassing Methods 0.000 claims description 2
- 238000003818 flash chromatography Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 108091005601 modified peptides Proteins 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 238000007296 Stetter synthesis reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
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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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
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- 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
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
- B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
- B01J2231/342—Aldol type reactions, i.e. nucleophilic addition of C-H acidic compounds, their R3Si- or metal complex analogues, to aldehydes or ketones
-
- 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
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a benzimidazole single-functionalized column [5] arene N-heterocyclic carbene catalyst, a preparation method and application thereof, belonging to the field of organic synthesis. The preparation method of the benzimidazole single-functionalized column [5] arene N-heterocyclic carbene catalyst comprises the following steps: (1) Preparing column [5] arene S-I by using 1, 1-dibromo-p-benzene diethyl ether, 1, 4-dimethoxy benzene and paraformaldehyde; (2) The benzimidazole monofunctional column [5] arene N-heterocyclic carbene catalyst I is prepared by reacting column [5] arene S-I with N-methyl benzimidazole. The preparation method of the catalyst has the advantages of high yield, strong operability, novel synthetic route, convenient post-treatment and the like. The benzimidazole single-functional column [5] arene N-heterocyclic carbene catalyst can be successfully applied to benzoin reaction participated by benzaldehyde, and has the advantages of low dosage, mild condition, simplicity and convenience in operation and the like.
Description
Technical Field
The invention discloses a benzimidazole single-functionalized column [5] arene N-heterocyclic carbene catalyst, a preparation method and application thereof, belonging to the technical field of organic synthesis.
Background
As a main body of the fifth generation supermolecule, the column [5] arene is widely applied to various aspects of medicines, chemistry, biology, functional materials and the like. The column [5] arene is a highly symmetrical structure and has a rigid framework and an electron-rich cavity; the two ends of the modified peptide are also provided with 10 derivable sites, which is favorable for carrying out structural and functional modification on the modified peptide, thereby having different chemical or biological activities. If a small organic molecule catalyst is selected for functional modification, the obtained derivatization column [5] arene has good catalytic activity, and gradually becomes a research hotspot of chemists.
Among numerous small organic molecule catalysts, N-heterocyclic carbenes have excellent physical and chemical properties and good selectivity, and are widely applied to various fields of organic synthesis. The N-heterocyclic carbene can effectively catalyze benzoin reaction, stetter reaction, nucleophilic substitution reaction and the like to involve carbon-carbon bond construction conversion, and provides a new catalytic means and a synthesis thought for various reactions requiring carbon chain extension, but the N-heterocyclic carbene catalyst which has better effect and is widely used at present has fewer types and needs larger catalyst amount. In view of the good performance of the column [5] arene catalysts in some reactions and the important role of N-heterocyclic carbenes in organic synthesis, the novel column [5] arene N-heterocyclic carbenes catalysts are synthesized through efficient, convenient and mild-condition routes and have important application values in researching the catalytic performance of the novel column [5] arene N-heterocyclic carbenes catalysts.
Disclosure of Invention
The invention aims to solve the problems of less types, large dosage and the like of the existing N-heterocyclic carbene catalysts, design and synthesize a novel N-heterocyclic carbene catalyst and research the catalytic performance of the novel N-heterocyclic carbene catalyst.
In order to achieve the aim, the invention provides an efficient, convenient and mild-condition benzimidazole single-functionalized column [5] arene N-heterocyclic carbene catalyst, and the catalytic performance of the benzimidazole single-functionalized column [5] arene N-heterocyclic carbene catalyst in benzoin reaction participated by benzaldehyde is researched. The benzimidazole single-functionalized column [5] arene N-heterocyclic carbene catalyst has a structure shown in a formula I:
the preparation method is shown in the formula II:
the present invention will be described in detail in the following steps, namely, each step in the above formula will be described in detail step by step in order.
The first step is the preparation of column [5] arene S-I:
Putting paraformaldehyde into a mortar, fully grinding, adding into a three-neck flask, adding 1, 1-dibromo-p-phenylene diethyl ether, 1, 4-dimethoxy benzene and magneton into the three-neck flask, degassing the mixture in the three-neck flask for three times by pumping and ventilating, adding 1, 2-dichloroethane under nitrogen environment, vigorously stirring the reaction system for 30 minutes at room temperature, adding boron trifluoride and diethyl ether into the reaction system, reacting for 1 hour at room temperature, adding methanol for quenching, pumping and filtering the system, evaporating filtrate under reduced pressure, purifying the reaction mixture by virtue of rapid column chromatography, and eluting with dichloromethane: petroleum ether=1:1 to obtain corresponding column arene S-I. The reaction formula of this step is as follows:
the second step is the preparation of benzimidazole single-functionalized column [5] arene N-heterocyclic carbene catalyst I:
Adding the column [5] arene S-I and a magneton into a round bottom flask, adding acetonitrile to dissolve the mixture, adding N-methylbenzimidazole at a reflux temperature, carrying out a reaction overnight, then evaporating the solvent under reduced pressure, adding methyl tertiary butyl ether into the reaction system, carrying out ultrasonic treatment for 30 minutes, standing the reaction system after stopping ultrasonic treatment until precipitation is completely separated from supernatant fluid, filtering, adding methyl tertiary butyl ether into the obtained solid, carrying out ultrasonic treatment again, and repeating the above operation until the N-methylbenzimidazole is completely removed, thus obtaining the benzimidazole monofunctional column [5] arene N-heterocyclic carbene catalyst I. The reaction formula of this step is as follows:
the molar ratio of 1, 1-dibromo-p-phenetole, 1, 4-dimethoxybenzene, paraformaldehyde and boron trifluoride diethyl etherate in the first step is 1:2:5:5.
In the second step, the mol ratio of the S-I aromatic hydrocarbon to the N-methyl benzimidazole in the column [5] is 1:1.
The benzimidazole single-functional column [5] arene N-heterocyclic carbene catalyst I is applied to catalyze benzoin reaction participated by benzaldehyde.
Compared with the traditional method, the invention has the beneficial effects that:
(1) The invention designs and synthesizes benzimidazole single-functional column [5] arene N-heterocyclic carbene catalysts, and the preparation method of the related catalysts has the advantages of high yield, strong operability, novel synthetic route, convenient post-treatment and the like;
(2) The benzimidazole single-functional column [5] arene N-heterocyclic carbene catalyst can be successfully applied to benzoin reaction participated by benzaldehyde, and has the advantages of low dosage, mild condition, simplicity and convenience in operation and the like.
Drawings
FIG. 1 is a 1 H NMR spectrum of compound (I) prepared in example 1;
FIG. 2 is a 1 H NMR spectrum of compound (2) prepared in example 2;
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 modification, equivalent substitution, improvement, etc. within the scope of the technical idea of the present invention should be included in the scope of the present invention.
Example 1:
the invention provides a method for preparing benzimidazole single-functionalized column [5] arene N-heterocyclic carbene catalysts, which comprises the following steps:
The first step is the preparation of column [5] arene S-I: 2.4g of paraformaldehyde is put into a mortar, fully crushed and added into a 250mL three-neck flask, then 5g of 1, 1-dibromo-p-phenylene diethyl ether, 4.26g of 1, 4-dimethoxy benzene and magneton are added into the three-neck flask, the mixture in the three-neck flask is degassed three times by pumping and air exchanging, 154mL of 1, 2-dichloroethane is added under nitrogen environment, 4.9mL of boron trifluoride diethyl ether is added after the reaction system, methanol is added for quenching after the reaction is carried out for 1 hour, the system is pumped and filtered, the reaction mixture is purified by flash column chromatography after the filtrate is evaporated under reduced pressure, and the corresponding column arene S-I is obtained by eluting with methylene dichloride: petroleum ether=1:1. The yield of compound S-I was 62%. The compound is a known compound, and 1H NMR、13 C NMR is consistent with a standard spectrum.
The second step is the preparation of benzimidazole single-functionalized column [5] arene N-heterocyclic carbene catalyst I: 240mg of column arene and magneton are added into a 50mL round bottom flask, 4mL of acetonitrile is added to dissolve the column arene and magneton, 34mg of N-methylbenzimidazole is added at a reflux temperature, the solvent is decompressed and evaporated after overnight reaction, then methyl tertiary butyl ether is added into the reaction system and is subjected to ultrasonic treatment for 30 minutes, the reaction system is kept stand until precipitation is completely separated from supernatant fluid and is filtered after ultrasonic treatment is stopped, the obtained solid is added with methyl tertiary butyl ether and is subjected to ultrasonic treatment again, and the operation is repeatedly carried out until the N-methylbenzimidazole is completely removed, so that the benzimidazole monofunctional column [5] arene N-heterocyclic carbene catalyst I is obtained. The yield of compound I was 68%.
The nuclear magnetic data of I are as follows:
1H NMR(500MHz,DMSO-d6):δ9.82(s,1H),8.23-8.21(m,1H),8.04-8.02(m,1H),6.86-6.68(m,11H),6.44(s,1H),4.97(t,J＝5.0Hz,2H),4.41(t,J＝5.0Hz,2H),4.04-4.01(m,4H),3.69-3.62(m,34H),3.51(s,3H)ppm.
Example 2
The invention also researches the catalytic performance of the benzimidazole single-functionalized column [5] arene N-heterocyclic carbene catalyst I in benzoin reaction participated by benzaldehyde, and the reaction equation is as follows:
compound 1 (0.25 mmol), benzimidazole monofunctional column [5] arene N-heterocyclic carbene catalyst I (0.025 mmol) and potassium tert-butoxide (0.1 mmol) were added sequentially to the reactor under nitrogen atmosphere, ethanol 4mL was added, and the reaction was carried out at room temperature for 14 hours. After the reaction is completed, pure 2 is obtained through column chromatography separation. The yield of compound 2 was 86%. The compound is a known compound, and 1H NMR、13 C NMR is consistent with a standard spectrum.
In the above examples, g represents "gram"; mg stands for "milligram", mmol stands for "millimole"; mL stands for "milliliter"; h represents "hours"; (HCHO) n represents "paraformaldehyde"; BF 3·OEt2 represents "boron trifluoride diethyl etherate"; DCE stands for "1, 2-dichloroethane"; meCN stands for "acetonitrile"; t-BuOK represents potassium tert-butoxide; NHC stands for benzimidazole single-functionalized column [5] arene N-heterocyclic carbene catalyst; etOH stands for "ethanol"; rt stands for "room temperature"; rt represents room temperature.
According to the embodiment, the method for synthesizing the benzimidazole single-functionalized column [5] arene N-heterocyclic carbene catalyst can be used for efficiently and conveniently obtaining a target product under mild conditions. The benzimidazole single-functionalized column [5] arene N-heterocyclic carbene catalyst can be successfully applied to benzoin reaction, and has the advantages of low dosage, mild condition, simplicity and convenience in operation and the like.
Claims (3)
1. The benzimidazole single-functionalized column [5] arene N-heterocyclic carbene catalyst is characterized by having a structure shown in a formula I:
2. the method for preparing the benzimidazole mono-functionalized column [5] arene N-heterocyclic carbene type catalyst according to claim 1, which is characterized by comprising the following steps of the formula II:
The first step is the preparation of column [5] arene S-I:
Placing paraformaldehyde into a mortar, fully grinding, adding into a three-neck flask, adding 1, 1-dibromo-p-phenylene diethyl ether, 1, 4-dimethoxy benzene and magnetons into the three-neck flask, degassing the mixture in the three-neck flask for three times by pumping and air changing, adding 1, 2-dichloroethane under nitrogen environment, vigorously stirring a reaction system at room temperature for 30 minutes, adding 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, evaporating filtrate under reduced pressure, purifying the reaction mixture by virtue of flash column chromatography, and eluting with dichloromethane: petroleum ether=1:1 to obtain corresponding column arene S-I;
the second step is the preparation of benzimidazole single-functionalized column [5] arene N-heterocyclic carbene catalyst I:
Adding column [5] arene S-I and magneton into a round bottom flask, adding acetonitrile to dissolve the mixture, adding N-methylbenzimidazole at a reflux temperature, carrying out overnight reaction, then decompressing and evaporating the solvent, adding methyl tertiary butyl ether into the reaction system, carrying out ultrasonic treatment for 30 minutes, standing the reaction system after stopping ultrasonic treatment until precipitation is completely separated from supernatant fluid, filtering, adding methyl tertiary butyl ether into the obtained solid, carrying out ultrasonic treatment again, and repeating the above operation until the N-methylbenzimidazole is completely removed to obtain a benzimidazole monofunctional column [5] arene N-heterocyclic carbene catalyst I;
Wherein the molar ratio of the 1, 1-dibromo-p-phenylene diethyl ether to the 1, 4-dimethoxy benzene to the paraformaldehyde to the boron trifluoride diethyl etherate is 1:2:5:5;
Wherein the mole ratio of the S-I aromatic hydrocarbon to the N-methyl benzimidazole in the column [5] is 1:1.
3. The use of a benzimidazole mono-functionalized column [5] arene N-heterocyclic carbene based catalyst according to claim 1, wherein the catalyst is used for catalyzing benzoin reactions involving benzaldehyde.
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