CN114751872B - 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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- CN114751872B CN114751872B CN202210492606.6A CN202210492606A CN114751872B CN 114751872 B CN114751872 B CN 114751872B CN 202210492606 A CN202210492606 A CN 202210492606A CN 114751872 B CN114751872 B CN 114751872B
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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 42
- 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 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 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 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 8
- 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
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 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
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 6
- 239000011541 reaction mixture Substances 0.000 claims description 6
- 238000003818 flash chromatography Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000005086 pumping Methods 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
- 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
- 239000000706 filtrate 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
- 230000000171 quenching effect Effects 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000004440 column chromatography Methods 0.000 claims description 2
- 238000007872 degassing Methods 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 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
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000011160 research Methods 0.000 description 3
- 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
- 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
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- 102000004310 Ion Channels Human genes 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
- 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
- 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
- 231100000719 pollutant Toxicity 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
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- 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
Abstract
The invention discloses a column [5] belonging to the field of organic synthesis]Aromatic hydrocarbon N-heterocyclic carbene catalyst, and preparation method and application thereof. Said column [5]]The preparation method of the arene N-heterocyclic carbene catalyst comprises the following steps: (1) Preparation of column [5] using 1, 1-dibromo-p-phenylene diethyl ether, 1, 4-dimethoxybenzene and paraformaldehyde]Aromatic hydrocarbon S-I; (2) Using columns [5]]Preparation of column [5] by reaction of aromatic hydrocarbon with 4-methyl-5-thiazole ethanol]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. The column [5] according to the invention]The arene N-heterocyclic carbene catalyst can be successfully applied to the Stetter reaction and has the advantages of low dosage, mild condition, simple and convenient operation, high yield and the like.
Description
Technical Field
The invention discloses a column [5] arene N-heterocyclic carbene catalyst, 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 a plurality of guest molecules. In addition, 10 derivable sites are arranged at two ends of the aromatic hydrocarbon skeleton of the column [5], so that the structure and the functional modification of the aromatic hydrocarbon skeleton are facilitated. Because of the unique structural advantage and better recognition 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 carbenes attract the wide attention of organic synthesis workers due to excellent physical and chemical properties and good selectivity, are widely applied to various fields of organic synthesis, and become an important catalytic means for modern organic chemical synthesis by taking N-heterocyclic carbenes as a catalytic strategy of an organic micromolecular catalyst. However, the N-heterocyclic carbene catalysts used at present are few in types, and most of the catalysts need larger catalyst amount, and some reactions even need equivalent N-heterocyclic carbene participation. In view of the important role of the catalyst in organic synthesis, the novel column [5] arene N-heterocyclic carbene catalyst is synthesized through a route with high efficiency, convenience and mild conditions, and the catalyst performance is researched to have important application value.
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 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 phthalic dicarboxaldehyde and nitrostyrene. The 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:
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 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, adding boron trifluoride diethyl ether into the reaction system, reacting for 1 hour at room temperature, adding methanol for quenching, pumping and filtering the system, decompressing and evaporating filtrate, purifying the reaction mixture by flash column chromatography, eluting with dichloromethane: petroleum ether=2:1, and obtaining corresponding column arene S-I. The reaction formula of this step is as follows:
the second step is the preparation of the column [5] arene N-heterocyclic carbene catalyst I:
column [5] arene S-I and magneton are added into a round bottom flask, acetonitrile is added to dissolve the mixture, 4-methyl-5-thiazolyl ethanol is added at reflux temperature, the solvent is evaporated under reduced pressure after overnight reaction, the reaction mixture is purified by flash column chromatography and eluted with methylene dichloride: methanol=20:1, and the column [5] arene N-heterocyclic carbene catalyst I is obtained. 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 mole ratio of the S-I of the [5] arene to the 4-methyl-5-thiazole ethanol is 1:2.
the application of the column [5] arene N-heterocyclic carbene catalyst I is to catalyze the Stetter reaction of phthalic dicarboxaldehyde and nitrostyrene.
Compared with the traditional method, the invention has the beneficial effects that:
(1) The invention designs and synthesizes a novel column [5] arene N-heterocyclic carbene catalyst, and the preparation method of the catalyst 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 the Stetter reaction, and has the advantages of low dosage, mild condition, simple and convenient operation, high yield and the like.
Drawings
FIG. 1 shows the compound (I) prepared in example 1 1 H NMR spectrum;
FIG. 2 shows the compound (3) prepared in example 2 1 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 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 a column [5] arene N-heterocyclic carbene catalyst, which comprises the following steps:
the first step is a column [5]]Preparation of aromatic 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=2:1. The yield of compound S-I was 62%. The compound is a known compound which, 1 H NMR、 13 c NMR was consistent with the standard spectrum.
The second step is the preparation of the column [5] arene N-heterocyclic carbene catalyst I: to a 50mL round bottom flask was added 240mg of column arene and magneton, after which 4mL of acetonitrile was added to dissolve it, 60 μl of 4-methyl-5-thiazolyl ethanol was added at reflux temperature, after overnight reaction the solvent was evaporated under reduced pressure and the reaction mixture was purified by flash column chromatography eluting with dichloromethane: methanol=20:1 to give column [5] arene N-heterocyclic carbene type catalyst I. The yield of compound I was 65%.
The nuclear magnetic data of I are as follows:
1 H NMR(500MHz,CDCl 3 )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 phthalic dicarboxaldehyde and nitrostyrene, and the reaction equation is as follows:
compounds 1 (5 mmol), 2 (7.5 mmol), column [5]]Aromatic hydrocarbon N-heterocyclic carbene catalyst I (0.5 mmol), triethylamine (5 mmol),Molecular sieves were added sequentially to the reactor under an inert gas atmosphere, 25mL of dimethyl sulfoxide was added, and the reaction was carried out at room temperature for 12 hours. After the reaction is completed, pure 3 is obtained by column chromatography separation. The yield of compound 3 was 88%.
The nuclear magnetic data of 3 are as follows:
1 H NMR(500MHz,CDCl 3 )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 "gram"; mg stands for "milligram", mmol stands for "millimole"; mL stands for "milliliter"; h represents "hours"; DEG C stands for "degrees Celsius"; mu L stands for "microliter"; et (Et) 3 N represents triethylamine; NHC stands for "column [5]]Aromatic hydrocarbon N-heterocyclic carbene catalyst "; MS stands for "molecular sieve"; DMSO represents dimethyl sulfoxide; rt represents room temperature.
According to the embodiment, the method for synthesizing the column [5] arene N-heterocyclic carbene catalyst can be used for efficiently and conveniently obtaining the 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 dosage, mild condition, simple and convenient operation, high yield and the like.
Claims (4)
1. A preparation method of a column [5] arene N-heterocyclic carbene catalyst, wherein the column [5] arene N-heterocyclic carbene catalyst has a structure shown in a formula I:
the preparation method comprises the following steps of:
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 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, adding boron trifluoride diethyl ether into the reaction system, reacting for 1 hour at room temperature, adding methanol for quenching, pumping and filtering the system, decompressing and evaporating filtrate, purifying the reaction mixture by fast column chromatography, eluting with dichloromethane: petroleum ether=2:1, and obtaining corresponding column arene S-I;
the second step is the preparation of the column [5] arene N-heterocyclic carbene catalyst I:
column [5] arene S-I and magneton are added into a round bottom flask, acetonitrile is added to dissolve the mixture, 4-methyl-5-thiazolyl ethanol is added at reflux temperature, the solvent is evaporated under reduced pressure after overnight reaction, the reaction mixture is purified by flash column chromatography and eluted with methylene dichloride: methanol=20:1, and the column [5] arene N-heterocyclic carbene catalyst I is obtained.
2. The method for preparing a column [5] arene N-heterocyclic carbene-based catalyst according to claim 1, wherein the molar ratio of the 1, 1-dibromo-p-phenylene diethyl ether, the 1, 4-dimethoxybenzene, the paraformaldehyde and the boron trifluoride diethyl ether is 1:2:5:5.
3. The method for preparing a column [5] arene N-heterocyclic carbene-based catalyst according to claim 1, wherein the molar ratio of the column [5] arene S-I to the 4-methyl-5-thiazolyl ethanol is 1:2.
4. use of a column [5] arene N-heterocyclic carbene based catalyst according to claim 1, for catalyzing Stetter reactions of phthalaldehyde with nitrostyrene.
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| CN103396298A (en) * | 2013-08-22 | 2013-11-20 | 吉林大学 | Preparation of functionalized pillar(n)arene derivatives |
| CN110483618A (en) * | 2019-09-11 | 2019-11-22 | 青岛科技大学 | Miscellaneous [4] arene derivatives and its preparation and application |
| CN113336721A (en) * | 2021-06-28 | 2021-09-03 | 成都大学 | Chiral N-heterocyclic carbene catalyst and preparation method and application thereof |
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