Alkaline pillararene catalyst and application thereof in efficient catalysis of Knoevenagel condensation reaction and Michael addition reaction

Abstract

The invention discloses a basic column aromatic hydrocarbon catalyst and application thereof in efficient catalysis of a Knoevenagel condensation reaction and a Michael addition reaction, belongs to the technical field of catalysts, and particularly discloses a basic column [5] aromatic hydrocarbon catalyst (Interdazole-P [5] A) which efficiently catalyzes aldehyde ketone and active methylene to generate a methylene malononitrile compound in the aspect of the Knoevenagel condensation reaction. In the aspect of Michael addition reaction, the catalyst efficiently catalyzes alpha, beta-unsaturated nitro or carboxyl or ester compounds and active methylene to generate corresponding addition products; meanwhile, the catalyst is also successfully applied to a'one-pot two-step method 'reaction of a Knoevenagel condensation reaction and a Michael addition reaction. According to the catalyst, the defects that a traditional alkaline homogeneous catalyst pollutes the environment and is difficult to recycle are overcome.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of catalysts, and relates to a basic pillar[5]arene catalyst and application thereof in catalyzing Knoevenagel condensation reaction and Michael addition reaction. BACKGROUND

[0002] Pillararene is a kind of symmetrical supramolecular host compound, which is formed by para-bridging of hydroquinone or hydroquinone ether through methylene. Due to the stability of five-membered ring and six-membered ring, the bridging units are mostly 5 and 6, forming pillar[5]arene and pillar[6]arene. When the bridging unit is less than 5 or more than 6, the yield of pillararene will be significantly reduced. Pillararene has a cavity structure, which makes it have unique host-guest properties, and can complex with different compounds, metal ions and small molecules, thereby playing multiple roles. In addition, the modifiability of the edge groups of pillararene enables it to introduce different substituent groups, showing diverse chemical properties and having potential application value in various chemical reactions.

[0003]

[0004] As a new type of supramolecular macrocyclic compound, pillararene will exhibit different properties and characteristics such as acidity and alkalinity, hydrophilicity and hydrophobicity when the edge sites of the basic structural skeleton are substituted by different groups. Researchers have synthesized many types of pillararene catalysts with different catalytic effects by utilizing the tunable properties of pillararene. These catalysts have been widely used in various chemical reactions such as reduction-oxidation reaction, coupling reaction and photocatalytic reaction.

[0005] Knoevenagel condensation reaction is one of the classic reactions for forming C-C bond in organic chemistry. Generally, the active methylene is activated under the action of basic catalyst, and then the activated active methylene reacts with carbonyl group through nucleophilic addition reaction, followed by dehydration to form C-C bond. In 1894, Emil Knoevenagel first discovered the condensation reaction of aliphatic formaldehyde and diethyl malonate. This reaction is considered to be a pioneering research in the field of C-C bond construction, so this kind of reaction is named as Knoevenagel condensation reaction. The products of this reaction are widely used as intermediates for synthesizing special chemicals and fine chemicals, such as carbocyclic compounds, substituted alkenes, bioactive compounds, therapeutic drugs, calcium antagonists, natural products, functional polymers, coumarin derivatives, flavorings and fragrances, etc.

[0006] Michael addition reactions, first discovered by A. Michael in 1887, are one of the most important reactions in organic chemistry for carbon chain elongation. This reaction typically involves compounds with active methylene groups (such as malononitrile, malonic acid, and diethyl malonate), which are activated by a basic catalyst (such as organic bases like sodium ethoxide and sodium hydride, and inorganic bases like potassium carbonate and sodium hydroxide) to form carbanions. α , β- Unsaturated aldehydes, ketones, carboxylic acids, nitro compounds, etc., undergo conjugate addition reactions. The products of Michael addition reactions have wide applications in the pharmaceutical field, such as the synthesis of drugs for the treatment of mantle cell lymphoma, breast cancer, and advanced lung cancer, as well as the synthesis of analgesics and nonsteroidal anti-inflammatory drugs.

[0007] Traditional Knoevenagel condensation and Michael addition reactions are typically carried out under homogeneous conditions using acid or basic catalysts. However, compared to heterogeneous catalytic systems, homogeneous catalytic systems have significant drawbacks, such as difficulties in catalyst recovery, complex post-processing leading to product contamination, higher reaction temperatures limiting industrial applications, and large solvent consumption causing environmental pollution. Therefore, heterogeneous catalysts have become an important research direction in academia and industry. In recent years, to address these issues while retaining the advantages of active sites in homogeneous catalysts, researchers have developed various heterogeneous catalysts, such as zeolites, metal-organic frameworks, ionic liquids, functionalized mesoporous silica, and carbon-based materials, and have successfully applied them to various chemical reactions. Summary of the Invention

[0008] To overcome the problems of environmental pollution and difficulty in recycling traditional basic homogeneous catalysts, as well as the relatively harsh reaction conditions, long reaction times, and complex preparation and characterization of existing heterogeneous catalysts, this invention provides a basic pillar aromatic hydrocarbon catalyst and a method for using it to catalyze Knoevenagel condensation and Michael addition reactions to generate the corresponding target compounds. This type of catalyst is environmentally friendly and has a relatively simple preparation process. Furthermore, this method also has the advantages of high catalytic efficiency, mild reaction conditions, simple post-reaction processing, and the recyclability of the catalytic system, showing good application potential in industrial production.

[0009] This invention is achieved through the following technical solution: This invention provides a basic columnar aromatic catalyst, which is composed of a columnar aromatic skeleton and basic groups.

[0010] Furthermore, the alkaline column aromatic catalyst is an imidazole column[5] aromatic catalyst (Imidazole-P[5]A), and its preparation method mainly adopts the strategy of first synthesizing structural units and then cyclizing them.

[0011]

[0012] The synthetic route is as follows:

[0013] In the route, first, compound 2 is obtained by reacting hydroquinone and dibromoethane, which is a structural unit of the pillararene catalyst, then the pillararene skeleton P[5]A is obtained by a cyclization reaction, and finally the basic imidazole pillar[5]arene catalyst Imidazole-P[5]A is prepared by introducing an imidazole group at the end of P[5]A.

[0014] Further, in the preparation of compound 2, the reagent used includes tetrabutylammonium bromide (Tetrabutylammonium bromide, TBAB); in the preparation of the pillararene skeleton P[5]A, the reagent used includes boron trifluoride ether complex.

[0015] The basic pillararene catalyst of the application is used to catalyze Knoevenagel condensation reaction and Michael addition reaction.

[0016] Further, the reaction conditions of Knoevenagel condensation reaction and Michael addition reaction are both solvent-free reaction or solvent reaction; when the reaction condition is solvent reaction, the solvent is one or a mixture of several of water, methanol, ethanol, ethyl acetate, N , N dimethylformamide, dimethyl sulfoxide, dichloromethane, acetonitrile or isopropanol.

[0017] Further, after the reaction is completed, the catalyst is recovered by filtration, and the recovered catalyst is in the form of a powder solid; the solvent used in the process of recovering the catalyst is one or a mixture of several of ethyl acetate, dichloromethane, chloroform or acetone.

[0018] In terms of Knoevenagel condensation reaction, the application provides a method for generating methylene malonitrile compounds by using an alkaline pillararene catalyst to catalyze the condensation reaction of aldehyde ketone compounds and active methylene to generate methylene malonitrile compounds, and the reaction route is as follows:

[0019] Comprising the following steps: Using aldehyde ketone compounds and active methylene as substrates, using alkaline pillararene as catalyst (Alkaline-P[n]A), forming a reaction system under solvent-free or solvent (Neat / Solvent) conditions, reacting at 25-80℃ for 1-30min to obtain methylene malonitrile compounds.

[0020] Further, the molar ratio of the basic columnar aromatic hydrocarbon catalyst: aldehyde ketone compound: active methylene group is (0.3-6):(100-2000):(120-2400).

[0021] The aldehyde ketone compound is selected from one of a mono-aryl aldehyde compound, a mono-arylhetero aldehyde compound, an aliphatic aldehyde compound, a bis-aryl ketone compound, a bis-arylhetero ketone compound, a mono-aryl-alkyl ketone compound, a mono-arylhetero-alkyl ketone compound, and an aliphatic ketone compound; and the active methylene group is selected from one of malononitrile, ethyl cyanoacetate, cyanoacetic acid, and diethyl cyanoacetamide. N N Further, the mono-aryl aldehyde compound and the mono-arylhetero aldehyde compound have the following structural formula:

[0022] Further, the bis-aryl ketone compound and the bis-arylhetero ketone compound have the following structural formula:

[0023] wherein Ar 1 is selected from one of an aryl group, an aryhetero group, and a fused ring.

[0024] Further, the mono-aryl-alkyl ketone compound and the mono-arylhetero-alkyl ketone compound have the following structural formula:

[0025] wherein Ar 2 , Ar 3 are each independently selected from one of an aryl group, an aryhetero group, and a fused ring.

[0026] Further, the mono-aryl-alkyl ketone compound and the mono-arylhetero-alkyl ketone compound have the following structural formula:

[0027] wherein Ar 4 is selected from one of an aryl group, an aryhetero group, and a fused ring; and R 1 is a C1-C8 alkyl group, a C1-C8 cycloalkyl group, or a C1-C8 alkoxy group.

[0028] In the above structural formula, when Ar 1 , Ar 2 , Ar 3 , Ar 4 is an aryl group, the aryl group is selected from a substituted or unsubstituted five- or six-membered aryl ring; and the substituent group of the aryl group is one or more selected from H, a C1-C8 alkyl group, a C1-C8 alkoxy group, a halogenated group (a group in which a single halogen atom is substituted), OH, CF3, NO2, CN, and CHO.

[0029] When Ar​1 , Ar 2 , Ar 3 , Ar 4 is an aromatic hetero group, the aromatic hetero group is a substituted or unsubstituted five- or six-membered aromatic hetero ring, the hetero atom in the aromatic hetero ring is one or more of N, S, and O; the substituent of the aromatic hetero group is one or more selected from one or more of CH3, Et, tBu, OCH3, F, Cl, Br, CF3, NO2, CN, and CHO.

[0030] Further, the structure of the aliphatic aldehyde compound is as follows:

[0031] wherein R 2 is selected from one of H, C1-C8 alkyl, C1-C8 cycloalkyl, C1-C8 alkoxy, halogen, OH, CF3, NO2, CN, and CHO.

[0032] Further, the structure of the aliphatic ketone compound is as follows:

[0033] wherein R 3 , R 4 are independently selected from C1-C8 alkyl, C1-C8 cycloalkyl, and C1-C8 alkoxy.

[0034] Further, the structure of the active methylene is as follows:

[0035] wherein EWG 1 is a cyano group; EWG 2 is one of a cyano group, an ethyl formate group, a carboxyl group, and N , N a diethyl amide group.

[0036] This route provides a simple, inexpensive, and efficient route for Knoevenagel condensation reaction.

[0037] In terms of Michael addition reaction, the present application provides a method for catalyzing the condensation reaction between an active methylene and an unsaturated nitro or carboxyl or ester compound to generate a methylene malononitrile compound by using a basic columnar arene catalyst, and the reaction route is as follows: α , β

[0038] comprising the following steps: with α , β ​Unsaturated nitro or carboxyl or ester group compounds and active methylene as substrate, with basic columnar aromatic hydrocarbon as catalyst, under solvent-free or solvent conditions, to form a reaction system, at 25-100°C for 1 min-720 min to obtain the corresponding addition product.

[0039] Further, the basic columnar aromatic hydrocarbon catalyst is in a molar ratio of: α , β Unsaturated nitro or carboxyl or ester group compounds: active methylene = (1-20): (100-2000): (200-4000).

[0040] The α , β Unsaturated nitro or carboxyl or ester group compounds are selected from one of mononuclear aryl β nitrostyrene compounds, mononuclear arylhetero β nitrostyrene compounds, mononuclear aryl β carboxystyrene compounds and mononuclear aryl β esterstyrene compounds; and the active methylene is selected from one of malononitrile, ethyl cyanoacetate, cyanoacetic acid and N , N diethyl cyanoacetamide.

[0041] Further, the mononuclear aryl β nitrostyrene compounds, mononuclear arylhetero β nitrostyrene compounds have the following structural formula:

[0042] wherein Ar 5 is selected from one of aryl, arylhetero, fused ring.

[0043] Further, the mononuclear aryl β carboxystyrene compounds, mononuclear aryl β esterstyrene compounds have the following structural formula:

[0044] wherein Ar 6 is aryl; R 6 is carboxyl or ester group-containing structure.

[0045] Further, the active methylene has the following structural formula:

[0046] wherein EWG 3 is cyano; EWG 4 is cyano, ethyl formate group, carboxyl and N, N - one of diethylamido.

[0047] This route provides a simple, inexpensive and efficient route for Michael addition reaction.

[0048] In the "one-pot two-step method" of Knoevenagel condensation reaction and Michael addition reaction, the present application provides a method using basic column aromatic hydrocarbon catalyst, first catalyzing the Knoevenagel condensation of aldehyde ketone compound and active methylene to form methylene malonitrile compound, and then the Michael addition reaction of the methylene malonitrile compound and nitromethane to form the corresponding addition product, the reaction general formula is as shown below:

[0049] Comprising the following steps: First, using aldehyde ketone compound and active methylene as substrates, using basic column aromatic hydrocarbon as catalyst, forming a reaction system under solvent-free conditions, reacting at 25-80°C for 1-30 min to obtain methylene malonitrile intermediate, and then the intermediate and nitromethane are subjected to Michael addition reaction at 25-100°C to obtain the corresponding addition product.

[0050] Further, the molar ratio of basic column aromatic hydrocarbon catalyst: aldehyde ketone compound: active methylene: nitromethane is (1-20):(100-2000):(200-4000):(500-10000).

[0051] The aldehyde ketone compound is selected from one of monoaryl aldehyde compound, monoaromatic heteroaldehyde compound, aliphatic aldehyde compound and aliphatic ketone compound; the active methylene is selected from malonitrile, ethyl cyanoacetate, cyanoacetic acid and N , N - one of diethyl cyanoacetamide.

[0052] Further, the structure of the monoaryl aldehyde compound and the monoaromatic heteroaldehyde compound is as follows:

[0053] Wherein, Ar 1 is selected from one of aryl, aromatic heteroaryl, fused ring.

[0054] Further, the structure of the aliphatic aldehyde compound is as follows:

[0055] Wherein, R 2one of H, C1-C8 alkyl, C1-C8 cycloalkyl, C1-C8 alkoxy, halogen, OH, CF3, NO2, CN, CHO.

[0056] Further, the structure of the aliphatic ketone compound is as follows:

[0057] wherein R 3 , R 4 are independently selected from C1-C8 alkyl, C1-C8 cycloalkyl, C1-C8 alkoxy.

[0058] Further, the structure of the active methylene is as follows:

[0059] wherein EWG 1 is cyano; EWG 2 is cyano, ethyl formate group, carboxyl and N , N diethyl amide.

[0060] The route provides a simple, inexpensive and efficient route for the "one-pot two-step method" of Knoevenagel condensation reaction and Michael addition reaction.

[0061] Compared with the prior art, the present application has the following advantages: (1) The present application proves by experiments that the basic column aromatic hydrocarbon catalyst has high catalytic activity for Knoevenagel condensation reaction and Michael addition reaction, wherein the separation yield of Knoevenagel condensation reaction is as high as 95%, the separation yield of Michael addition reaction is as high as 97%, and the recovered catalyst can be reused.

[0062] (2) The present application uses basic column aromatic hydrocarbon for Knoevenagel condensation reaction and Michael addition reaction, which avoids the disadvantages of traditional basic catalysts, such as environmental pollution and difficulty in recycling and reuse, and eliminates the synthesis, purification and characterization process of heterogeneous catalysts, so that the catalytic system is simple to operate and has universal practicality, and can be used by ordinary experimental operators. The present application provides a simple, inexpensive and efficient route for Knoevenagel condensation reaction and Michael addition reaction.

[0063] (3) The present application provides a synthesis method of methylene malononitrile compound catalyzed by basic column aromatic hydrocarbon, which is used for the condensation of aldehyde ketone compound and active methylene and α , βThe addition of unsaturated nitro, carboxyl, or ester compounds to active methylene groups has excellent catalytic effects, short reaction time, and a yield of up to 99%; it has the advantages of being simple, inexpensive, and highly efficient.

[0064] (4) This invention provides a basic columnar aromatic catalyst for the condensation of aldehydes and ketones with active methylene groups to prepare methylene malononitriles, and α , β - A method for preparing the corresponding compound by addition of an unsaturated nitro, carboxyl, or ester group compound with an active methylene group, wherein the substrate conversion rate is ≥95%. Attached Figure Description

[0065] Figure 1 The columnar aromatic skeleton (P[5]A) prepared in Example 1 of this invention 1 H NMR spectrum.

[0066] Figure 2 The imidazole column[5]arene (Imidazole-P[5]A) prepared in Example 1 of this invention 1 H NMR spectrum.

[0067] Figure 3 The imidazole column[5]arene (Imidazole-P[5]A) prepared in Example 1 of this invention 1 C NMR spectrum.

[0068] Figure 4 The phenylmethylene malononitrile prepared in Example 2 of this invention 1 H NMR spectrum.

[0069] Figure 5 The 2-fluorophenylmethylene malononitrile prepared in Example 8 of this invention 1 H NMR spectrum.

[0070] Figure 6 3-Fluorophenylmethylene malononitrile prepared in Example 9 of this invention 1 H NMR spectrum.

[0071] Figure 7 2-Chlorophenylmethylene malononitrile prepared in Example 10 of this invention 1 H NMR spectrum.

[0072] Figure 8 2-Methoxyphenylmethylene malononitrile prepared in Example 11 of this invention 1 H NMR spectrum.

[0073] Figure 9 2-Nitrophenylmethylene malononitrile prepared in Example 12 of this invention 1 H NMR spectrum.

[0074] Figure 10 2-naphthylmethylmalononitrile prepared for Example 13 of the present invention 1 H NMR chart.

[0075] Figure 11 2-(furan-2-ylmethyl)malononitrile prepared for Example 14 of the present invention 1 H NMR chart.

[0076] Figure 12 2-(thiophene-2-ylmethyl)malononitrile prepared for Example 15 of the present invention 1 H NMR chart.

[0077] Figure 13 2-cyclohexylidenemalononitrile prepared for Example 16 of the present invention 1 H NMR chart.

[0078] Figure 14 2-(2-nitro-l-phenylethyl)malononitrile prepared for Example 17 of the present invention 1 H NMR chart.

[0079] Figure 15 2-[l-(2-chlorophenyl)-2-nitroethyl]malononitrile prepared for Example 23 of the present invention 1 H NMR chart.

[0080] Figure 16 2-[l-(4-bromophenyl)-2-nitroethyl]malononitrile prepared for Example 24 of the present invention 1 H NMR chart.

[0081] Figure 17 2-[4-nitro-l-(2-nitrophenyl)ethyl]malononitrile prepared for Example 25 of the present invention 1 H NMR chart.

[0082] Figure 18 2-[l-(3-methoxyphenyl)-2-nitroethyl]malononitrile prepared for Example 26 of the present invention 1 H NMR chart.

[0083] Figure 19 2-[l-(4-cyanophenyl)-2-nitroethyl]malononitrile prepared for Example 27 of the present invention 1 H NMR chart.

[0084] Figure 20 2-[l-(2,4-dichlorophenyl)-2-nitroethyl]malononitrile prepared for Example 28 of the present invention 1 H NMR chart. Detailed Implementation

[0085] The following embodiments will help to understand the purpose, features, advantages, and technical methods of the present invention, but should not be construed as limiting the scope of the invention. The implementation conditions used in the embodiments can be further adjusted according to different requirements of specific applications, and the implementation conditions not specified are those in conventional experiments.

[0086] In the following embodiments, 1 H NMR and 13 The test solvent used for C NMR is CDCl3- d Or DMSO- d 6.

[0087] In the following examples, the recovered catalyst was detected using an infrared spectrometer (FI-IR).

[0088] Example 1: Preparation of Imidazole-P[5]A:

[0089] Step 1: Synthesis of columnar aromatic structural unit 2; In a 250 mL round-bottom flask, hydroquinone (2.00 g, 18.2 mmol) and 1,2-dibromoethane (40.0 mL, 464.2 mmol) were added. NaOH (4.36 g, 109.0 mmol) and tetrabutylammonium bromide (0.29 g, 0.9 mmol) were dissolved in water and added to the flask. The reaction was carried out at 80 °C for 12 h, and the reaction was monitored for completeness using thin-layer chromatography. After the reaction was complete, the aqueous and organic layers were separated. The organic layer was rotary evaporated to remove 1,2-dibromoethane. The remaining solid was added to water and extracted with dichloromethane (25.0 mL × 3). The organic layers were combined, washed with saturated brine, dried over anhydrous Na₂SO₄, filtered to remove the drying agent, and the solvent was evaporated to obtain a brown solid. Separation was performed using a silica gel column chromatography with DCM:MeOH = 40:1 as the eluent, and the solvent was evaporated to obtain white crystals. Mp: 114 °C.

[0090] Step 2: Synthesis of the columnar aromatic skeleton (P[5]A); In a 100.0 mL three-necked flask, structural unit 2 (2.00 g, 6.2 mmol) and paraformaldehyde (0.56 g, 18.5 mmol based on a formaldehyde monomer molar mass of 30.03 g / mol) were added, followed by the addition of dichloromethane to completely dissolve structural unit 2. Under nitrogen protection, boron trifluoride diethyl ether complex (1.6 mL, 6.0 mmol) was added dropwise to the system, and the reaction was carried out at room temperature for 3 h. The system gradually changed from colorless to dark green, and the reaction was confirmed to be complete by thin-layer chromatography. After the reaction was completed, the boron trifluoride diethyl ether complex was quenched with water, and the mixture was extracted with dichloromethane (25.0 mL × 3). The organic layers were combined, washed with saturated brine, dried over anhydrous Na₂SO₄, filtered to remove the drying agent, and the solvent was evaporated to obtain a light green solid. The solid was separated by silica gel column chromatography using PE:DCM = 1:2 as the eluent, and the solvent was evaporated to obtain 1.74 g of a white powdery solid, yield: 84%.

[0091] 1 H NMR (600 MHz, Chloroform- d δ 6.91 (s, 10H), 4.22 (t, J = 5.7 Hz, 20H), 3.84 (s, 10H), 3.63 (t, J = 5.7 Hz, 20H), its 1H NMR spectrum is shown in [reference needed]. Figure 1 .

[0092] Step 3: Synthesis of basic imidazole column[5] aromatic hydrocarbon (Imidazole-P[5]A); In a 100.0 mL round-bottom flask, imidazole (0.48 g, 7.1 mmol) and KOH (1.59 g, 28.3 mmol) were added, and DMF was added to completely dissolve the imidazole. The mixture was stirred at room temperature for 30 min. After stirring, P[5]A (1.00 g, 0.6 mmol) was added to the system, and DMF was added to completely dissolve the P[5]A. The mixture was reacted at room temperature for 24 h. After the reaction was completed, 10 times the amount of DMF in water was added to the system, and the mixture was allowed to stand until the solid precipitated. The filter cake was filtered and dried under vacuum to obtain 0.61 g of a pale yellow powdery solid. The yield was 66%.

[0093] 1 H NMR (600 MHz, Chloroform- d The δ values ​​were 7.54 (s, 10H), 6.99 (d, J = 19.2 Hz, 20H), 6.37 (s, 10H), 4.14 (t, J = 4.9 Hz, 20H), 3.82 (t, J = 5.0 Hz, 20H), and 3.54 (s, 10H). Its 1H NMR spectrum is shown in [reference needed]. Figure 2 ; 13C NMR (101 MHz, Chloroform- d ) δ 149.81, 137.47, 137.45, 129.47,129.04, 119.34, 115.86, 68.58, 46.80, 29.55, its nuclear magnetic carbon spectrum is shown in Figure 3 .

[0094] In the basic column aromatic catalytic Knoevenagel condensation reaction, the specific implementation is as follows: Table 1 Knoevenagel condensation reaction, catalyst dosage and solvent investigation

[0095] Reaction conditions: 25-30°C reaction. a Yield is determined by liquid chromatography.

[0096] Example 2: Preparation of phenyl methylene malonitrile (solvent-free condition)

[0097] In a 10.0 mL round-bottom flask, add benzaldehyde (1.0 equiv.) and imidazole-P[5]A (1.0 mol%), stir at 30°C. Heat the malonitrile (1.2 equiv.) to a molten state, suck into the reaction system, keep the reaction temperature, continue to stir until the reaction system solidifies, stop the reaction. After the reaction is completed, add an appropriate amount of ethyl acetate to dissolve the product. Since the catalyst is insoluble in ethyl acetate, it will be suspended in the system. Remove the insoluble catalyst by filtration, add an appropriate amount of distilled water to the obtained filtrate, extract with ethyl acetate (5.0 mL x 3). Combine the organic layers, wash with saturated brine, dry over anhydrous Na2SO4, filter off the drying agent, evaporate the solvent to obtain a solid product, recrystallize with ethanol to obtain a white solid. 1 H NMR (600 MHz, DMSO- d 6) δ 8.55 (s, 1H), 8.01-7.92 (m, 2H), 7.75-7.57 (m, 3H). Its nuclear magnetic hydrogen spectrum is shown in Figure 4 .

[0098] Example 3: Preparation of phenyl methylene malonitrile (DMF as solvent) In a 10.0 mL round bottom flask, add benzaldehyde (1.0 equiv.), malononitrile (1.2 equiv.), Imidazole-P[5]A (1.0 mol%) and 1.5 mL N,N-dimethylformamide, stir the reaction at room temperature, monitor the reaction completion by thin layer chromatography. After the reaction is completed, remove the solvent under reduced pressure, add appropriate amount of ethyl acetate to the system to dissolve the product. Since the catalyst is insoluble in ethyl acetate, it will be suspended in the system. Remove the insoluble catalyst by filtration, add appropriate amount of distilled water to the obtained filtrate, extract with ethyl acetate (5.0 mL x 3). Combine the organic layers, wash with saturated brine, dry over anhydrous Na2SO4, filter off the drying agent, and evaporate the solvent to obtain a solid product, which is purified by recrystallization in ethanol to obtain a white solid.

[0099] Example 4: Preparation of phenylmethylidenemalononitrile (DMSO as solvent) The operation is as shown in the preparation method of Example 3, except that dimethyl sulfoxide is selected as the solvent.

[0100] Example 5: Preparation of phenylmethylidenemalononitrile (MeOH as solvent) The operation is as shown in the preparation method of Example 3, except that methanol is selected as the solvent.

[0101] Example 6: Preparation of phenylmethylidenemalononitrile (H2O as solvent) The operation is as shown in the preparation method of Example 3, except that water is selected as the solvent.

[0102] Example 7: Preparation of phenylmethylidenemalononitrile (DCM as solvent) The operation is as shown in the preparation method of Example 3, except that dichloromethane is selected as the solvent.

[0103] Comparative Example 1 A method for catalyzing the condensation of aldehydes and ketones with active methylene to generate methylene malononitrile compounds, the operation is as shown in Example 2, except that the amount of Imidazole-P[5]A is 0.8 mol%, as shown in Table 1. As can be seen from Table 1, the amount of catalyst is reduced, and compared with Example 2, the reaction time is not significantly prolonged, and the yield is not significantly reduced.

[0104] Comparative Example 2 A method for catalyzing the condensation of aldehydes and ketones with active methylene to generate methylene malononitrile compounds, the operation is as shown in Example 2, except that the amount of Imidazole-P[5]A is 0.6 mol%, as shown in Table 1. As can be seen from Table 1, the amount of catalyst is reduced, and compared with Example 2, the reaction time is not significantly prolonged, and the yield is not significantly reduced.

[0105] Comparative Example 3 A method for catalyzing condensation of aldehyde ketone and active methylene to generate methylene malonitrile compound, operation is shown in the method of example 2, difference is shown in table 1, the dosage of Imidazole-P[5]A is 0.3mol%, through table 1, it can be seen that the dosage of catalyst is reduced, compared with example 2, the reaction time is not obviously prolonged, and the yield is not obviously reduced.

[0106] Comparative example 4 A method for catalyzing condensation of aldehyde ketone and active methylene to generate methylene malonitrile compound, operation is shown in the method of example 2, difference is shown in table 1, the dosage of Imidazole-P[5]A is 0.2mol%, through table 1, it can be seen that the dosage of catalyst is reduced, compared with example 2, the reaction time is prolonged to 10min, and the yield is not obviously reduced.

[0107] Comparative example 5 A method for catalyzing condensation of aldehyde ketone and active methylene to generate methylene malonitrile compound, operation is shown in the method of example 2, difference is shown in table 1, the dosage of Imidazole-P[5]A is 0.1mol%, through table 1, it can be seen that the dosage of catalyst is reduced, compared with example 2, the reaction time is prolonged to 20min, and the yield is not obviously reduced.

[0108] Comparative example 6 A method for catalyzing condensation of aldehyde ketone and active methylene to generate methylene malonitrile compound, operation is shown in the method of example 2, difference is shown in table 1, without adding Imidazole-P[5]A, through table 1, it can be seen that without adding catalyst, compared with example 2, the reaction time is obviously prolonged, and the yield is obviously reduced.

[0109] Example 8: Preparation of 2-fluorophenyl methylene malonitrile

[0110] 2-fluorobenzaldehyde as raw material, under solvent-free conditions, the method of example 2 is used, the difference is that the dosage of Imidazole-P[5]A is 0.3mol%, and white solid is obtained. 1 H NMR (600 MHz, DMSO- d 6) δ 8.60 (s,1H), 8.07 (m, 1H), 7.76 (m, 1H), 7.50-7.43 (m, 2H). The nuclear magnetic hydrogen spectrum is shown in Figure 5 .

[0111] Example 9: Preparation of 3-fluorophenyl methylene malonitrile

[0112] Using 3-fluorobenzaldehyde as raw material, under solvent-free conditions, the method of Example 2 was used to prepare a white solid. The difference was that the amount of Imidazole-P[5]A was 0.3 mol%. 1 H NMR (600 MHz, DMSO- d 6) δ 8.57 (s, 1H), 7.83–7.77 (m, 1H), 7.74 (m, 1H), 7.70 (m, 1H), 7.58 (m, 1H), its 1H NMR spectrum is shown in [reference needed]. Figure 6 .

[0113] Example 10: Preparation of 2-chlorophenylmethylene malononitrile

[0114] Using 2-chlorobenzaldehyde as raw material, under solvent-free conditions, the method of Example 2 was used to prepare a yellow solid. The difference was that the amount of Imidazole-P[5]A was 0.3 mol%. 1 H NMR (600 MHz, DMSO- d 6) δ 8.68 (s, 1H), 8.03 (m, 1H), 7.75–7.65 (m, 2H), 7.62–7.56 (m, 1H), its 1H NMR spectrum is shown in [reference needed]. Figure 7 .

[0115] Example 11: Preparation of 2-methoxyphenylmethylene malononitrile

[0116] Using 2-methoxybenzaldehyde as raw material, under solvent-free conditions, the method of Example 2 was used to prepare a yellow solid, the difference being that the amount of Imidazole-P[5]A was 0.3 mol%. 1 H NMR (600 MHz, DMSO- d 6) δ 8.48 (s, 1H), 7.97 (m, 1H), 7.68 (m, 1H), 7.24 (m, 1H), 7.18–7.12 (m, 1H), 3.91 (s, 3H), its 1H NMR spectrum is shown in [reference needed]. Figure 8 .

[0117] Example 12: Preparation of 2-nitrophenylmethylene malononitrile

[0118] Using 2-nitrobenzaldehyde as starting material, the compound was prepared under solvent-free condition by the method of Example 2, except that the amount of Imidazole-P[5]A was 0.3 mol%, to give a yellow solid. 1 H NMR (600 MHz, DMSO- d 6) δ 8.98 (s,1H), 8.35 (dd, J = 8.2, 1.2 Hz, 1H), 8.02 (td, J = 7.5, 1.2 Hz, 1H), 7.96 (dt,J = 7.6, 1.1 Hz, 1H), 7.94-7.87 (m, 1H),its nuclear magnetic hydrogen spectrum is shown in Figure 9 .

[0119] Example 13: Preparation of 2-naphthylmethylmalononitrile

[0120] Using 2-naphthaldehyde as starting material, the compound was prepared under solvent-free condition by the method of Example 2, except that the amount of Imidazole-P[5]A was 0.3 mol%, to give a yellow solid. 1 H NMR (600 MHz, DMSO- d 6) δ 8.68 (s,1H), 8.51-8.47 (m, 1H), 8.14 (m, 1H), 8.11-8.06 (m, 2H), 8.04 (m, 1H), 7.75(m, 1H), 7.68 (m, 1H),its nuclear magnetic hydrogen spectrum is shown in Figure 10 .

[0121] Example 14: Preparation of 2-(furan-2-ylmethyl)malononitrile

[0122] Using 2-furaldehyde (furfural) as starting material, the compound was prepared under solvent-free condition by the method of Example 2, except that the amount of Imidazole-P[5]A was 0.3 mol%, to give a brown solid. 1 H NMR (400 MHz, Chloroform- d )δ 7.80 (d, J = 1.7 Hz, 1H), 7.51 (s, 1H), 7.37 (d, J = 3.7 Hz, 1H), 6.72 (dd, J =(3.8, 1.7 Hz, 1H), its 1H NMR spectrum is shown in [reference needed]. Figure 11 .

[0123] Example 15: Preparation of 2-(thiophene-2-ylmethylene)malononitrile

[0124] Using 2-thiophenecaraldehyde (furfural) as raw material, under solvent-free conditions, the method of Example 2 was used to prepare a brown solid. The difference was that the amount of Imidazole-P[5]A was 0.3 mol%. 1 H NMR (400 MHz, Chloroform- d )δ 7.88 (d, J = 6.1 Hz, 2H), 7.81 (d, J = 3.3 Hz, 1H), 7.30–7.26 m, 1H. Its 1H NMR spectrum is shown below. Figure 12 .

[0125] Example 16: Preparation of 2-cyclohexylmalononitrile

[0126] Using cyclohexanone as a raw material, the preparation was carried out under solvent-free conditions using the method of Example 2, except that the amount of Imidazole-P[5]A was 0.3 mol%, resulting in a colorless liquid. 1 H NMR (400 MHz, Chloroform- d ) δ2.66 (t, J = 6.3 Hz (4H), 1.80 (m, 4H), 1.68 (m, 2H). Its 1H NMR spectrum is shown below. Figure 13 .

[0127] The specific implementation method for the Michael addition reaction catalyzed by basic columnar aromatics is as follows: Table 2. Investigation of Michael addition reaction, catalyst dosage and solvent.

[0128] Reaction conditions: 30℃. a The yield was determined by liquid chromatography.

[0129] Example 17: Preparation of 2-(2-nitro-1-phenylethyl)malononitrile (solvent-free conditions)

[0130] In a 10.0 mL round-bottom flask, add βNitrostyrene (1.0 equiv.) and Imidazole-P[5]A (1.0 mol%) were stirred at 30 °C. Malononitrile (2.0 equiv.) was heated to a molten state and added to the reaction system. The reaction temperature was maintained and the mixture was stirred continuously. The reaction was monitored by TLC until it was complete. Ethyl acetate was added to the system to completely dissolve the product. The insoluble catalyst was removed by filtration, and the filtrate was extracted with ethyl acetate (5.0 mL × 3). The organic layers were combined, washed with saturated brine, dried with anhydrous Na2SO4, the desiccant was removed by filtration, and the solvent was evaporated to remove the colorless liquid. 1 H NMR (600 MHz, Chloroform- d δ 7.47–7.41 (m, 3H), 7.37–7.30 (m, 2H), 4.94 (dd, J = 14.3, 7.8 Hz, 1H), 4.87 (dd, J = 14.3, 6.4 Hz, 1H), 4.40 (d, J = 6.0 Hz, 1H), 4.11–4.07 (m, 1H). Its 1H NMR spectrum is shown below. Figure 14 .

[0131] Example 18: Preparation of 2-(2-nitro-1-phenylethyl)malononitrile (EA as solvent) In a 10.0 mL round-bottom flask, add β - Nitrostyrene (1.0 equiv.), malononitrile (2.0 equiv.), Imidazole-P[5]A (1.0 mol%) and 1.5 mL of ethyl acetate were stirred at room temperature and the reaction was monitored by thin-layer chromatography to ensure complete reaction. After the reaction was completed, the solvent was removed by vacuum distillation, and an appropriate amount of ethyl acetate was added to the system to dissolve the product. Since the catalyst is insoluble in ethyl acetate, it will be suspended in the system. The insoluble catalyst was removed by filtration, and an appropriate amount of distilled water was added to the filtrate. The filtrate was extracted with ethyl acetate (5.0 mL × 3). The organic layers were combined, washed with saturated brine, dried with anhydrous Na2SO4, the drying agent was removed by filtration, and the solvent was evaporated to obtain a colorless liquid.

[0132] Example 19: Preparation of 2-(2-nitro-1-phenylethyl)malononitrile (MeOH as solvent) The method of Example 18 was used, with methanol as the solvent.

[0133] Example 20: Preparation of 2-(2-nitro-1-phenylethyl)malononitrile (EtOH as solvent) The method of Example 18 was used, with ethanol as the solvent.

[0134] Example 21: Preparation of 2-(2-nitro-1-phenylethyl)malononitrile (DCM as solvent) The procedure of Example 18 was followed using dichloromethane as the solvent.

[0135] Example 22: Preparation of 2-(2-nitro-l-phenylethyl)propanedinitrile (MeCN as solvent) The procedure of Example 18 was followed using acetonitrile as the solvent.

[0136] Comparative Example 7 A catalytic α , β The procedure of Example 17 was followed with the exception that the amount of Imidazole-P[5]A was 0.3 mol% and the results are shown in Table 2. As can be seen from Table 2, the amount of catalyst was reduced and the reaction time was significantly increased compared to Example 17 without a significant decrease in yield.

[0137] Comparative Example 8 A catalytic α , β The procedure of Example 17 was followed with the exception that the amount of Imidazole-P[5]A was 0.5 mol% and the results are shown in Table 2. As can be seen from Table 2, the amount of catalyst was reduced and the reaction time was significantly increased compared to Example 17 without a significant decrease in yield.

[0138] Comparative Example 9 A catalytic α , β The procedure of Example 17 was followed with the exception that the amount of Imidazole-P[5]A was 1.5 mol% and the results are shown in Table 2. As can be seen from Table 2, the amount of catalyst was reduced and the reaction time was not significantly decreased compared to Example 17 without a significant decrease in yield.

[0139] Comparative Example 10 A catalytic α , β The procedure of Example 17 was followed with the exception that the amount of Imidazole-P[5]A was 2.0 mol% and the results are shown in Table 2. As can be seen from Table 2, the amount of catalyst was reduced and the reaction time was not significantly decreased compared to Example 17 without a significant decrease in yield.

[0140] Comparative Example 11 A catalytic α , β- The method of condensing unsaturated nitro, carboxyl or ester compounds with active methylene groups to generate related products is as shown in Example 17. The difference is shown in Table 2. The amount of Imidazole-P[5]A is 3.0 mol%. As can be seen from Table 2, the amount of catalyst is reduced. Compared with Example 17, the reaction time is not significantly shortened and the yield is not significantly reduced.

[0141] Comparative Example 12 A catalyst α , β - The method of condensing unsaturated nitro, carboxyl or ester compounds with active methylene groups to generate related products is as shown in Example 17, with the difference shown in Table 2. Imidazole-P[5]A is not added. As can be seen from Table 2, the reaction time is significantly longer and the yield is significantly lower than that in Example 17 without the addition of a catalyst.

[0142] Example 23: Preparation of 2-[1-(2-chlorophenyl)-2-nitroethyl]malononitrile

[0143] With 2-chloro- β Using nitrostyrene as a raw material, a pale yellow solid was prepared under solvent-free conditions using the method of Example 17. 1 H NMR (600 MHz, Chloroform- d δ 7.56–7.53 (m, 1H), 7.44–7.40 (m, 3H), 5.04–4.95 (m, 2H), 4.80–4.76 (m, 1H), 4.54 (d, J = 6.7 Hz, 1H). Its 1H NMR spectrum is shown below. Figure 15 .

[0144] Example 24: Preparation of 2-[1-(4-bromophenyl)-2-nitroethyl]malononitrile

[0145] With 4-bromo- β Using nitrostyrene as a raw material, a pale yellow solid was prepared under solvent-free conditions using the method of Example 17. 1 H NMR (600 MHz, DMSO- d 6) δ 7.70–7.64 (m, 2H), 7.49–7.43 (m, 2H), 5.37 (dd, J = 14.0, 7.7 Hz, 1H), 5.20 (d, J = 7.4 Hz, 2H), 4.49–4.45 (m, 1H). Its 1H NMR spectrum is shown below.Figure 16 .

[0146] Example 25: Preparation of 2-[4-nitro-l-(2-nitrophenyl)ethyl]propanedinitrile

[0147] Prepared from 4-dinitrostyrene as starting material, under solvent-free condition, using the method of Example 17, as a light yellow solid. 1 H NMR (400 MHz, DMSO- d 6) δ 8.32 (d, J = 8.8 Hz, 2H), 7.82 (d, J = 8.8 Hz,2H), 5.47 (d, J = 7.7 Hz, 1H), 5.38 – 5.22 (m, 2H), 4.74-4.64 (m, 1H). The nuclear magnetic hydrogen spectrum is shown in Figure 17 .

[0148] Example 26: Preparation of 2-[l-(3-methoxyphenyl)-2-nitroethyl]propanedinitrile

[0149] Prepared from 3-methoxy- β -nitrostyrene as starting material, under solvent-free condition, using the method of Example 17, as a light yellow solid. 1 H NMR (600 MHz, Chloroform- d ) δ 7.38 (t, J = 8.0 Hz, 1H), 7.01-6.96 (m, 1H), 6.92 (dd, J = 7.7, 1.8 Hz, 1H), 6.86 (t, J = 2.2 Hz, 1H), 4.97(dd, J = 14.3, 8.1 Hz, 1H), 4.90 (dd, J = 14.3, 6.1 Hz, 1H), 4.42 (d, J = 5.3Hz, 1H), 4.10-4.06 (m, 1H), 3.83 (s, 3H). The nuclear magnetic hydrogen spectrum is shown in Figure 18 .

[0150] Example 27: Preparation of 2-[l-(4-cyanophenyl)-2-nitroethyl]propanedinitrile

[0151] Prepared from trans-4-(2-nitrovinyl)benzonitrile as starting material, under solvent-free condition, using the method of Example 17, as a light yellow solid. 1H NMR (600 MHz, DMSO- d 6) δ 7.99–7.94 (m, 2H), 7.76–7.71 (m, 2H), 5.44 (d, J = 7.7 Hz, 1H), 5.28 (d, J = 7.3 Hz, 2H), 4.65–4.58 (m, 1H). Its 1H NMR spectrum is shown below. Figure 19 .

[0152] Example 28: Preparation of 2-[1-(2,4-dichlorophenyl)-2-nitroethyl]malononitrile

[0153] With trans-2,4-dichloro- β Using nitrostyrene as a raw material, a colorless solid was prepared under solvent-free conditions using the method of Example 17. 1 H NMR (600 MHz, DMSO- d 6) δ 7.80 (d, J = 2.2 Hz, 1H), 7.75 (d, J = 8.5 Hz, 1H), 7.61 (dd, J = 8.5, 2.2 Hz, 1H), 5.42 (d, J = 7.9 Hz, 1H), 5.32 (dd, J = 14.7, 9.2 Hz, 1H), 5.24 (dd, J = 14.7, 5.3 Hz, 1H), 4.90–4.83 (m, 1H). Its 1H NMR spectrum is shown in [reference needed]. Figure 20 .

[0154] Regarding the "one-pot, two-step" method for the Knoevenagel condensation and Michael addition reactions catalyzed by basic columnar aromatics, the specific implementation method is as follows: Since the optimal reaction conditions for the first step of the "one-pot, two-step" process, the Knoevenagel condensation reaction, have been determined, the substrate for the second step, the Michael addition reaction, is... β - Nitro, carboxyl, or ester styrene compounds are converted into benzylmalonium compounds, so the following work mainly investigates the conditions of the Michael addition reaction.

[0155] Table 3. Investigation of catalyst dosage and temperature in the "one-pot two-step" reaction.

[0156] Reaction conditions: benzyl allonitrile (1.0 mmol), nitromethane (5.0 mmol), reaction at 30℃-100℃. a The yield was determined by liquid chromatography.

[0157] Example 29: Preparation of 2-(2-nitro-1-phenylethyl)malononitrile (reaction temperature 30°C)

[0158] In a 10.0 mL round-bottom flask, benzaldehyde (1.0 equiv.) and Imidazole-P[5]A (0.02 g, 1.0 mol%) were added and stirred at 30 °C. Malononitrile (1.2 equiv.) was heated to a molten state and transferred to the reaction system. The reaction temperature was maintained and the mixture was stirred continuously until the reaction system solidified. The reaction was then stopped. The reaction temperature was maintained at 30 °C, and nitromethane (5.0 equiv.) was added to the reaction system. The reaction temperature was maintained and the mixture was stirred continuously. The reaction was monitored by TLC until it was complete. Ethyl acetate was added to the system to completely dissolve the product. The insoluble catalyst was removed by filtration, and the filtrate was extracted with ethyl acetate (5.0 mL × 3). The organic layers were combined, washed with saturated brine, dried with anhydrous Na2SO4, the drying agent was removed by filtration, and the solvent was evaporated to obtain a colorless liquid. 1 H NMR (600MHz, Chloroform- d δ 7.47–7.41 (m, 3H), 7.37–7.30 (m, 2H), 4.94 (dd, J = 14.3, 7.8 Hz, 1H), 4.87 (dd, J = 14.3, 6.4 Hz, 1H), 4.40 (d, J = 6.0 Hz, 1H), 4.11–4.07 (m, 1H). Its 1H NMR spectrum is shown below. Figure 14 .

[0159] Example 30: Preparation of 2-(2-nitro-1-phenylethyl)malononitrile (reaction temperature 50°C) The operation method is the same as in Example 29, except that the temperature of the second Michael addition reaction is 50°C, the total reaction time is shortened to 8 hours, and the yield is 92%.

[0160] Example 31: Preparation of 2-(2-nitro-1-phenylethyl)malononitrile (reaction temperature 70°C) The operation method is the same as in Example 29, except that the temperature of the second Michael addition reaction is 70°C, the total reaction time is shortened to 2 hours, and the yield is 99%.

[0161] Example 32: Preparation of 2-(2-nitro-1-phenylethyl)malononitrile (reaction temperature 90°C) The operation method is the same as in Example 29, except that the temperature of the second Michael addition reaction is 90°C, the total reaction time is shortened to 2 hours, and the yield is 95%.

[0162] Example 33: Preparation of 2-(2-nitro-l-phenylethyl)propanedinitrile (reaction temperature is 100 °C) The operation method is the same as that in Example 29, except that the temperature of the second step Michael addition reaction is 100 °C, the total reaction time is shortened to 2 h, and the yield is 91%.

[0163] It can be seen that when the catalyst is Imidazole-P[5]A (1.0 mol%), the suitable temperature range of the second step Michael addition reaction is 50-90 °C.

[0164] Comparative Example 13 A method for catalyzing a "one-pot two-step" reaction to generate a related product, the operation is shown in the method of Example 31, the difference is shown in Table 3, and Imidazole-P[5]A is not added. As can be seen from Table 3, compared with Example 31, the reaction time is significantly prolonged and the yield is significantly reduced without adding a catalyst.

[0165] Comparative Example 14 A method for catalyzing a "one-pot two-step" reaction to generate a related product, the operation is shown in the method of Example 31, the difference is shown in Table 3, and the amount of Imidazole-P[5]A is 0.5 mol%. As can be seen from Table 3, compared with Example 31, the reaction time is significantly prolonged and the yield is not significantly reduced.

[0166] Comparative Example 15 A method for catalyzing a "one-pot two-step" reaction to generate a related product, the operation is shown in the method of Example 31, the difference is shown in Table 3, and the amount of Imidazole-P[5]A is 1.5 mol%. As can be seen from Table 3, compared with Example 31, the reaction time is not significantly shortened and the yield is not significantly reduced.

[0167] Comparative Example 16 A method for catalyzing a "one-pot two-step" reaction to generate a related product, the operation is shown in the method of Example 31, the difference is shown in Table 3, and the amount of Imidazole-P[5]A is 2.0 mol%. As can be seen from Table 3, compared with Example 31, the reaction time is not significantly shortened and the yield is not significantly reduced.

Claims

1. A basic columnar aromatic catalyst, characterized in that, It consists of a columnar aromatic skeleton and basic groups, with the following structural formula: 。 2. The method for preparing the basic columnar aromatic catalyst according to claim 1, characterized in that, The strategy of first synthesizing structural units and then performing cycloforming includes the following methods: First, compound 2 is obtained by reacting hydroquinone with dibromoethane. It is the structural unit of the columnar aromatic catalyst. Then, it is cyclized to obtain the columnar aromatic skeleton P[5]A. Finally, by introducing an imidazole group at the end of P[5]A, the basic imidazole columnar aromatic catalyst, namely Imidazole-P[5]A, is obtained.

3. The application of the basic columnar aromatic catalyst according to claim 1 in the catalytic Knoevenagel condensation reaction, characterized in that, The Knoevenagel condensation reaction is as follows: using aldehydes and ketones and active methylene groups as substrates, and basic columnar aromatics as catalysts, a reaction system is formed under solvent-free or solvent-containing conditions, and the reaction is carried out at 25℃-80℃ for 1 min-30 min to obtain methylene malononitriles; the molar ratio of basic columnar aromatics catalyst: aldehydes and ketones: active methylene groups is (0.3-6): (100-2000): (120-2400).

4. The application according to claim 3, characterized in that, The aldehydes and ketones mentioned are selected from one of the following: monoaryl aldehydes, monoaryl heterol aldehydes, aliphatic aldehydes, diaryl ketones, diaryl heterol ketones, monoaryl-alkyl ketones, monoaryl heterol-alkyl ketones, and aliphatic ketones; the active methylene group is selected from malononitrile, ethyl cyanoacetate, cyanoacetic acid, and... N , N One of diethylcyanoacetamide; The structural formulas of the monoaryl aldehyde compounds and monoaryl heterol aldehyde compounds are as follows: Among them, Ar 1 Selected from one of aryl, aromatic heterol, and fused rings; The structural formulas of the aforementioned diaryl ketones and diaryl heterol ketones are as follows: Among them, Ar 2 Ar 3 Each is independently selected from one of aryl, aryl heterol, or fused ring; The structural formulas of the monoaryl-alkyl ketone compounds and monoaryl heterol-alkyl ketone compounds are as follows: Among them, Ar 4 Selected from one of aryl, aryl heterol, and fused rings; R 1 It is a C1-C8 alkyl, C1-C8 cycloalkyl, or C1-C8 alkoxy; In the above structural formula, when Ar 1 Ar 2 Ar 3 Ar 4 When the aryl group is aryl, the aryl group is selected from substituted or unsubstituted five- or six-membered aromatic rings; the substituents of the aryl group are one or more, selected from H, C1-C8 alkyl, C1-C8 alkoxy, halogroup, OH, CF3, NO2, CN and CHO; When Ar 1 Ar 2 Ar 3 Ar 4 When it is an aromatic heterogroup, the aromatic heterogroup is a substituted or unsubstituted five- or six-membered aromatic heterocycle, and the heteroatom on the aromatic heterocycle is one or more of N, S, and O; the substituents of the aromatic heterogroup are one or more, selected from CH3, Et, tBu, OCH3, F, Cl, Br, CF3, NO2, CN, and CHO. The structural formulas of the aliphatic aldehyde compounds are as follows: Among them, R 2 It is selected from one of H, C1-C8 alkyl, C1-C8 cycloalkyl, C1-C8 alkoxy, halogenated group, OH, CF3, NO2, CN, and CHO; The structural formulas of the aliphatic ketone compounds are as follows: Among them, R 3 R 4 Each is independently selected from C1-C8 alkyl, C1-C8 cycloalkyl, and C1-C8 alkoxy groups; The active methylene group has the following structural formula: Among them, EWG 1 It is cyano; EWG 2 It consists of cyano, ethyl formate, carboxyl, and N , N- One of the diethylamide groups.

5. The application of the basic columnar aromatic catalyst according to claim 1 in the catalytic Michael addition reaction, characterized in that, The Michael addition reaction is as follows: α , β - Unsaturated nitro, carboxyl, or ester compounds, with active methylene groups as substrates and basic columnar aromatics as catalysts, form a reaction system under solvent-free or solvent-containing conditions. The reaction is carried out at 25℃-100℃ for 1 min-720 min to obtain the corresponding addition products. The molar ratio of the basic columnar aromatic catalyst is: α , β - Unsaturated nitro, carboxyl, or ester compounds: active methylene group = (1-20): (100-2000): (200-4000).

6. The application according to claim 5, characterized in that, The aforementioned α , β -Unsaturated nitro, carboxyl, or ester compounds are selected from monoaryl compounds. β - Nitrostyrene compounds, monoaryl hetero compounds β - Nitrostyrene compounds, monoaryl β -Carboxystyrene compounds and monoaryl compounds β - One of the ester-based styrene compounds; the active methylene group is selected from malononitrile, ethyl cyanoacetate, and cyanoacetic acid. N , N One of diethylcyanoacetamide; The monoaryl β -Nitrostyrene compounds, monoaryl heteromethyl β The structural formulas of nitrostyrene compounds are as follows: Among them, Ar 5 Selected from one of aryl, aromatic heterol, and fused rings; The monoaryl β -Carboxystyrene compounds, monoaryl β The structural formulas of ester-based styrene compounds are as follows: Among them, Ar 6 It is aryl; R 6 It has a carboxyl group or an ester-containing structure; The active methylene group has the following structural formula: Among them, EWG 3 It is cyano; EWG 4 It consists of cyano, ethyl formate, carboxyl, and N , N One of the diethylamide groups.

7. The application of the basic columnar aromatic catalyst according to claim 1 in a one-pot, two-step catalytic reaction of Knoevenagel condensation and Michael addition, characterized in that, The first step of this method is a Knoevenagel condensation reaction, and the second step is a Michael addition reaction. First, using aldehydes and ketones as substrates and active methylene groups as catalysts, a reaction system is formed under solvent-free conditions. The reaction is carried out at 25℃-80℃ for 1 min-30 min to obtain a methylene malononitrile intermediate. Subsequently, this intermediate undergoes a Michael addition reaction with nitromethane at 25℃-100℃ to obtain the corresponding addition product. Molar ratio, basic columnar aromatic catalyst: aldehydes and ketones: active methylene: nitromethane = (1-20): (100-2000): (200-4000): (500-10000).

8. The application according to claim 7, characterized in that, The aldehydes and ketones mentioned are selected from monoaryl aldehydes, monoaryl heterol aldehydes, aliphatic aldehydes, and aliphatic ketones; the active methylene group is selected from malononitrile, ethyl cyanoacetate, cyanoacetic acid, and... N , N One of diethylcyanoacetamide; The structural formulas of the monoaryl aldehyde compounds and monoaryl heterol aldehyde compounds are as follows: Among them, Ar 1 Selected from one of aryl, aromatic heterol, and fused rings; The structural formulas of the aliphatic aldehyde compounds are as follows: Among them, R 2 It is selected from one of H, C1-C8 alkyl, C1-C8 cycloalkyl, C1-C8 alkoxy, halogenated group, OH, CF3, NO2, CN, and CHO; The structural formulas of the aliphatic ketone compounds are as follows: Among them, R 3 R 4 Each is independently selected from C1-C8 alkyl, C1-C8 cycloalkyl, and C1-C8 alkoxy groups; The active methylene group has the following structural formula: Among them, EWG 1 It is cyano; EWG 2 It consists of cyano, ethyl formate, carboxyl, and N , N One of the diethylamide groups.

9. The application according to any one of claims 3-6, characterized in that, When the reaction condition involves a solvent, the solvent can be water, methanol, ethanol, ethyl acetate, etc. N , N - One or a mixture of several of dimethylformamide, dimethyl sulfoxide, dichloromethane, acetonitrile, or isopropanol.

10. The application according to any one of claims 3-8, characterized in that, After the reaction is completed, the basic columnar aromatic catalyst is recovered by filtration. The recovered catalyst is a powder solid. The solvent used in the catalyst recovery process is one or a mixture of several of ethyl acetate, dichloromethane, chloroform or acetone.

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