CN114751872A - Column [5] arene N-heterocyclic carbene catalyst and preparation method and application thereof - Google Patents
Column [5] arene N-heterocyclic carbene catalyst and preparation method and application thereof Download PDFInfo
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- CN114751872A CN114751872A CN202210492606.6A CN202210492606A CN114751872A CN 114751872 A CN114751872 A CN 114751872A CN 202210492606 A CN202210492606 A CN 202210492606A CN 114751872 A CN114751872 A CN 114751872A
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 47
- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- 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
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 16
- OHBQPCCCRFSCAX-UHFFFAOYSA-N 1,4-Dimethoxybenzene Chemical compound COC1=CC=C(OC)C=C1 OHBQPCCCRFSCAX-UHFFFAOYSA-N 0.000 claims abstract description 12
- BKAWJIRCKVUVED-UHFFFAOYSA-N 5-(2-hydroxyethyl)-4-methylthiazole Chemical compound CC=1N=CSC=1CCO BKAWJIRCKVUVED-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 6
- 238000007296 Stetter synthesis reaction Methods 0.000 claims abstract description 6
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 239000011541 reaction mixture Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- PIAOLBVUVDXHHL-UHFFFAOYSA-N 2-nitroethenylbenzene Chemical compound [O-][N+](=O)C=CC1=CC=CC=C1 PIAOLBVUVDXHHL-UHFFFAOYSA-N 0.000 claims description 4
- 238000003818 flash chromatography Methods 0.000 claims description 4
- 229940054441 o-phthalaldehyde Drugs 0.000 claims description 4
- ZWLUXSQADUDCSB-UHFFFAOYSA-N phthalaldehyde Chemical compound O=CC1=CC=CC=C1C=O ZWLUXSQADUDCSB-UHFFFAOYSA-N 0.000 claims description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 3
- 238000004440 column chromatography Methods 0.000 claims description 3
- 238000007872 degassing Methods 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 239000007789 gas 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
- 238000010791 quenching Methods 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- 230000000171 quenching effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 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
- 238000001212 derivatisation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010926 purge Methods 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
- 238000001228 spectrum Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
- C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D277/22—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D277/24—Radicals substituted by oxygen atoms
-
- 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
-
- 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
- B01J31/0271—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0231
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C46/00—Preparation of quinones
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/04—One of the condensed rings being a six-membered aromatic ring
- C07C2602/10—One of the condensed rings being a six-membered aromatic ring the other ring being six-membered, e.g. tetraline
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Thiazole And Isothizaole Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a column [5], belonging to the field of organic synthesis]An aromatic hydrocarbon N-heterocyclic carbene catalyst and a preparation method and application thereof. The column [5]]The preparation method of the aromatic hydrocarbon N-heterocyclic carbene catalyst comprises the following steps: (1) preparation of column [5] using 1, 1-dibromo-p-phenyl-diethyl ether, 1, 4-dimethoxybenzene and paraformaldehyde]An aromatic hydrocarbon S-I; (2) using a column [5]]Preparation of column [5] by reaction of aromatic hydrocarbon and 4-methyl-5-thiazole ethanol]An aromatic hydrocarbon N-heterocyclic carbene catalyst I. The preparation method of the catalyst has the advantages of high yield, strong operability, novel synthetic route, convenient post-treatment and the like. Column [5] according to the invention]The aromatic hydrocarbon N-heterocyclic carbene catalysts can be successfully appliedThe method has the advantages of low consumption, mild conditions, simple operation, high yield and the like in the Stetter reaction.
Description
Technical Field
The invention discloses a column [5] arene N-heterocyclic carbene catalyst, and a preparation method and application thereof, belonging to the technical field of organic synthesis.
Background
The column [5] arene is a highly symmetrical structure, has a rigid framework and an electron-rich cavity, and can complex various guest molecules. In addition, both ends of the column [5] arene skeleton are provided with 10 derivatization sites, so that the structure and functional modification of the column [5] arene skeleton are facilitated. Due to the unique structural advantage and the more excellent identification performance of the column [5] arene, the column [5] arene becomes a fifth-generation supermolecule main body after crown ether, cyclodextrin, calixarene and cucurbituril, and is widely applied to various aspects of medicine and biology, pollutant separation, ion channels, chemical and biological sensing, functional materials and the like.
In recent years, N-heterocyclic carbene attracts the wide attention of organic synthesis workers due to excellent physical and chemical properties and good selectivity of N-heterocyclic carbene, and is widely applied to various fields of organic synthesis. However, the currently used N-heterocyclic carbene catalysts are few in types, most of the N-heterocyclic carbene catalysts need larger catalyst amount, and some reactions even need equivalent N-heterocyclic carbene to participate. In view of the important role of the catalyst in organic synthesis, a novel column [5] arene N-heterocyclic carbene catalyst is synthesized through a high-efficiency, convenient and mild-condition route, and the research on the catalytic performance of the catalyst has important application value.
Disclosure of Invention
The invention aims to overcome the problems of less types, larger 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 purpose, the invention provides a method for synthesizing a column [5] arene N-heterocyclic carbene catalyst with high efficiency, convenience and mild conditions, and researches the catalytic performance of the catalyst in the Stetter reaction of o-phthalaldehyde and nitrostyrene. The column [5] arene N-heterocyclic carbene catalyst 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, adding into a three-neck flask, adding 1, 1-dibromo-p-phenyl diethyl ether, 1, 4-dimethoxybenzene and magnetons into the three-neck flask, degassing the mixture in the three-neck flask for three times by using a pumping gas, adding 1, 2-dichloroethane in a nitrogen environment, 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 the filtrate under reduced pressure, purifying the reaction mixture by using a fast column chromatography, and eluting with dichloromethane, petroleum ether (2: 1) to obtain the corresponding column aromatic hydrocarbon S-I. The reaction formula of this step is as follows:
the second step is the preparation of column [5] arene N-heterocyclic carbene catalyst I:
adding column [5] arene S-I and magnetons into a round-bottom flask, adding acetonitrile to dissolve the mixture, adding 4-methyl-5-thiazole ethanol at a reflux temperature, reacting overnight, evaporating the solvent under reduced pressure, purifying the reaction mixture by flash column chromatography, and eluting with dichloromethane and methanol at a ratio of 20:1 to obtain column [5] arene N-heterocyclic carbene catalyst I. The reaction formula of this step is as follows:
in the first step, the molar ratio of the 1, 1-dibromo-p-phenyl diethyl ether to the 1, 4-dimethoxybenzene to the paraformaldehyde to the boron trifluoride diethyl ether is 1:2:5: 5.
In the second step, the molar ratio of the arene S-I of the cyclo [5] and the 4-methyl-5-thiazole ethanol is 1: 2.
the column [5] arene N-heterocyclic carbene catalyst I is applied to catalyzing a Stetter reaction of o-phthalaldehyde and nitrostyrene.
Compared with the traditional method, the method has the beneficial effects that:
(1) the invention designs and synthesizes a novel column [5] arene N-heterocyclic carbene catalyst, and the related catalyst preparation method has the advantages of high yield, strong operability, novel synthetic route, convenient post-treatment and the like;
(2) the column [5] arene N-heterocyclic carbene catalyst can be successfully applied to Stetter reaction, and has the advantages of low consumption, mild conditions, simple and convenient operation, high yield and the like.
Drawings
FIG. 1 is a diagram of Compound (I) prepared in example 11H NMR spectrum;
FIG. 2 is a diagram of Compound (3) prepared in example 21H NMR spectrum;
Detailed Description
The method of the present invention is described herein by way of examples, but the present invention is not limited thereto, and any modifications, equivalents, improvements, etc. within the technical spirit of the present invention should be included in the scope of the present invention.
Example 1:
the invention provides a method for preparing a column [5] arene N-heterocyclic carbene catalyst, which comprises the following steps:
the first step is a column [5]]Preparation of aromatic hydrocarbon S-I: 2.4g of paraformaldehyde was put into a mortar, sufficiently crushed and charged into a 250mL three-necked flask, 5g of 1, 1-dibromop-phenyl diethyl ether and 4.26g of 1, 4-dimethoxybenzene were then charged into the three-necked flask, and after degassing the mixture in the three-necked flask three times with a purge gas, 154mL of 1, 2-dichloroethane was added under nitrogen, 4.9mL of boron trifluoride ethyl ether was added after the reaction was carried out for 1 hour, and methanol was added to quench the reaction mixture, and the reaction system was put into a jarAnd (3) carrying out suction filtration, evaporating the filtrate under reduced pressure, purifying the reaction mixture by using flash column chromatography, and eluting with dichloromethane and petroleum ether in a ratio of 2:1 to obtain the corresponding pillared aromatic hydrocarbon S-I. The yield of compound S-I was 62%. The compound is a known compound which is a compound having a structure,1H NMR、13c NMR was consistent with the standard spectrum.
The second step is the preparation of column [5] arene N-heterocyclic carbene catalyst I: adding 240mg of column arene and magneton into a 50mL round-bottom flask, adding 4mL of acetonitrile to dissolve the column arene and magneton, adding 60 mu L of 4-methyl-5-thiazole ethanol at the reflux temperature, reacting overnight, then evaporating the solvent under reduced pressure, purifying the reaction mixture by flash column chromatography, and eluting with dichloromethane, methanol, 20:1 to obtain a column [5] arene N-heterocyclic carbene catalyst I. The yield of compound I was 65%.
Nuclear magnetic data for I are as follows:
1H NMR(500MHz,CDCl3)δ10.59(s,1H),6.80(s,1H),6.78(s,1H),6.78-6.75(m,3H),6.70(s,1H),6.67(s,1H),6.65(s,1H),6.43(s,1H),6.28(s,1H),5.36-5.33(m,1H),4.98-4.94(m,2H),4.40-4.36(m,2H),3.87-3.76(m,17H),3.72-3.66(m,19H),3.57(s,2H),3.26(t,J＝5.0Hz,2H),3.00-2.97(m,2H),2.58(s,3H)ppm.
example 2
The invention also researches the catalytic performance of the column [5] arene N-heterocyclic carbene catalyst I in the Steeter reaction of o-phthalaldehyde and nitrostyrene, and the reaction equation is as follows:
mixing compound 1(5mmol), 2(7.5mmol), and column [5]]Arene N-heterocyclic carbene catalyst I (0.5mmol), triethylamine (5mmol),
And sequentially adding the molecular sieves into the reactor under the inert gas atmosphere, adding 25mL of dimethyl sulfoxide, and reacting for 12 hours at room temperature. After the reaction is finished, pure 3 is obtained through column chromatography separation. The yield of compound 3 was 88%.
The nuclear magnetic data for 3 are as follows:
1H NMR(500MHz,CDCl3)δ8.22-8.18(m,1H),8.15-8.11(m,1H),7.81-7.77(m,2H),7.59-7.57(m,2H),7.50-7.47(m,3H),7.09(s,1H).
in the above examples, g represents "g"; mg for "mg", mmol for "mmol"; mL represents "mL"; h represents "hour"; DEG C stands for "centigrade"; μ L for "microliter"; et (Et)3N represents triethylamine; NHC stands for "column [5]Aromatic N-heterocyclic carbene-based catalysts "; MS stands for "molecular sieves"; DMSO represents dimethyl sulfoxide; rt represents room temperature.
The embodiment shows that the method for synthesizing the column [5] arene N-heterocyclic carbene catalyst can efficiently and conveniently obtain a target product under mild conditions. The column [5] arene N-heterocyclic carbene catalyst can be successfully applied to the Stetter reaction, and has the advantages of low consumption, mild conditions, simplicity and convenience in operation, high yield and the like.
Claims (4)
1. A column [5] arene N-heterocyclic carbene catalyst and a preparation method and application thereof, wherein the column [5] arene N-heterocyclic carbene catalyst 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-neck flask, adding 1, 1-dibromo-p-phenyl diethyl ether, 1, 4-dimethoxybenzene and magnetons into the three-neck flask, degassing the mixture in the three-neck flask for three times by using a pumping gas, adding 1, 2-dichloroethane in a nitrogen environment, adding boron trifluoride-diethyl ether into a reaction system, reacting at room temperature for 1 hour, adding methanol for quenching, carrying out suction filtration on the system, evaporating a filtrate under reduced pressure, purifying the reaction mixture by using a fast column chromatography, and eluting with dichloromethane, petroleum ether 2:1 to obtain corresponding column aromatic hydrocarbon S-I;
the second step is the preparation of column [5] arene N-heterocyclic carbene catalyst I:
adding column [5] arene S-I and magnetons into a round-bottom flask, adding acetonitrile to dissolve the mixture, adding 4-methyl-5-thiazole ethanol at a reflux temperature, reacting overnight, evaporating the solvent under reduced pressure, purifying the reaction mixture by flash column chromatography, and eluting with dichloromethane and methanol at a ratio of 20:1 to obtain column [5] arene N-heterocyclic carbene catalyst I.
2. The method for producing a column [5] arene S-I according to claim 1, wherein a molar ratio of the 1, 1-dibromo-p-phenyl-diethyl ether, the 1, 4-dimethoxybenzene, the paraformaldehyde and the boron trifluoride diethyl etherate is 1:2:5: 5.
3. The preparation method of the column [5] arene N-heterocyclic carbene-based catalyst I according to claim 1, wherein the molar ratio of the column [5] arene S-I to the 4-methyl-5-thiazoleethanol is 1: 2.
4. the use of the pillared [5] arene N-heterocyclic carbene catalysts I of claim 1 to catalyze the Stetter reaction of o-phthalaldehyde with nitrostyrene.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115385786A (en) * | 2022-09-16 | 2022-11-25 | 新拓洋生物工程有限公司 | Method for synthesizing vitamin K2 |
| CN115477614A (en) * | 2022-10-20 | 2022-12-16 | 青岛科技大学 | Benzimidazole column [5] arene N-heterocyclic carbene ligand and preparation method and application thereof |
| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN115477614A (en) * | 2022-10-20 | 2022-12-16 | 青岛科技大学 | Benzimidazole column [5] arene N-heterocyclic carbene ligand and preparation method and application thereof |
| 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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