A secondary aromatic amine-based macrocyclic arene compound, and a preparation method and application thereof

Abstract

The present application relates to the technical field of macrocyclic aromatic hydrocarbons, and discloses a macrocyclic aromatic hydrocarbon compound based on a secondary aromatic amine, a preparation method and application thereof.The macrocyclic aromatic hydrocarbon compound has a structure as shown in formula I.The present application strengthens the molecular rigidity and the porosity of an organic small molecule material through intramolecular hydrogen bonds, and designs and synthesizes a kind of macrocyclic aromatic hydrocarbon which strengthens the molecular rigidity and the porosity of the material through intramolecular hydrogen bonds.This kind of novel macrocyclic aromatic hydrocarbon is obtained by introducing intramolecular hydrogen bonds into the skeleton and monomer ring closure synthesis, and has the advantages of low synthesis cost and easy mass production.It is found that the specific surface area of the macrocyclic aromatic hydrocarbon material is high, and the macrocyclic aromatic hydrocarbon material can be processed into various porous materials for gas adsorption.

Description

Technical Field

[0001] This invention relates to the field of macrocyclic aromatic hydrocarbon technology, specifically to a macrocyclic aromatic hydrocarbon compound based on secondary aromatic amines, its preparation method, and its application. Background Technology

[0002] Macrocyclic aromatic hydrocarbons (MAHs) are a class of host molecules composed of rigid aromatic units and flexible methylene groups. Their pre-organized cavities and multiple non-covalent interaction sites make them important building blocks for molecular recognition and supramolecular assembly. MAHs have wide applications in molecular machines, biomedicine, molecular recognition, and assembly research. With the rapid development of macrocyclic and supramolecular chemistry, novel and functionally unique macrocyclic aromatic hydrocarbons have become one of the most important and widely studied categories in the synthesis of macrocyclic hosts. Compared with other macrocyclic hosts (such as calixarenes and pillararenes), macrocyclic aromatic hydrocarbons (MAHs) have the advantages of flexible and well-defined conformations and a large number of binding sites.

[0003] CN115490583 A discloses a macrocyclic aromatic compound, its preparation method, and its application. The structure of the macrocyclic aromatic compound is shown in Figure a:

[0004] This macrocyclic aromatic compound can form a host-guest complex with cyclohexanone and has no interaction with cyclohexanol. Therefore, this compound can selectively adsorb cyclohexanone from cyclohexanol, thereby achieving the separation of cyclohexanol and cyclohexanone. At the same time, the adsorbed compound can be regenerated by heating, releasing high-purity cyclohexanone, thus achieving the preparation of ultra-high purity cyclohexanone and cyclohexanol.

[0005] CN110642684A discloses a class of macrocyclic and cage-like molecules based on biphenyl aromatics, their derivatives, and their synthetic methods and applications. It mainly involves reacting bis-(2,4-dialkoxyphenyl)aromatics (naphthalene, anthracene, pyrene, porphyrin, etc.) or tri-(2,4-dialkoxyphenyl)aromatics (benzene, tribenzo[a]benzene) with paraformaldehyde under Lewis acid catalysis to obtain a series of new macrocyclic compounds in high yield. Furthermore, demethylation yields perhydroxyl biphenyl aromatics (tetraphenyl trimer, naphthalene dimer, etc.), and further modification yields various water-soluble derivatives exhibiting good bonding ability to guest molecules (violin, etc.). Moreover, the functional groups introduced into the skeleton endow biphenyl aromatics with excellent adsorption and separation capabilities as well as photophysical properties.

[0006] However, due to their flexible structure, their cavities and assembly structures respond to the shape and size of the adsorbate, making it difficult to form stable and ordered porous materials. Therefore, most macrocyclic aromatic hydrocarbon-based porous materials suffer from poor structural stability, lack of pores, or low adsorption capacity, greatly limiting their applications in adsorption, separation, and drug loading. Furthermore, although they possess inherent cavities capable of recognizing and adsorbing guest molecules, their structural flexibility and assembly diversity make it difficult to form ordered and stable porous materials; they typically form nonporous adaptive crystals (NACs). Summary of the Invention

[0007] To overcome the shortcomings of macrocyclic aromatic hydrocarbons in terms of structural flexibility, non-porous nature, and poor stability, this invention provides a macrocyclic aromatic hydrocarbon compound based on secondary aromatic amines. By introducing intramolecular hydrogen bonds into the framework to enhance molecular rigidity, it achieves porosity and a high specific surface area while retaining the good processability and regenerability of macrocyclic aromatic hydrocarbon crystal materials.

[0008] To achieve the above objectives, the technical solution adopted by the present invention is as follows: A macrocyclic aromatic compound based on a secondary aromatic amine has the structure shown in Formula I: (I) in, Indicates intramolecular hydrogen bond, Y=COR, COOR or CONHR, R is alkyl, alkenyl or aromatic, n is 1, 2 or 3; and For the same or different structures, each group is independently selected from any of the following groups: .

[0009] This invention employs a strategy of enhancing molecular rigidity and porosity of small organic molecule materials through intramolecular hydrogen bonding, and designs and synthesizes a class of macrocyclic aromatic hydrocarbons that combine these enhancements. These novel macrocyclic aromatic hydrocarbons are prepared by introducing intramolecular hydrogen bonds into the framework and synthesizing monomers through ring closure, offering advantages such as low synthesis cost and ease of large-scale production. Furthermore, studies have revealed that these macrocyclic aromatic hydrocarbon materials have high specific surface areas and can be processed into various porous materials for gas adsorption.

[0010] Preferably, R is any one of a C1-C8 straight-chain or branched alkyl group, a C6-C15 aryl group, or a substituted aryl group.

[0011] More preferably, R is any one of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, tert-butyl, phenyl, or substituted phenyl.

[0012] This invention also provides a method for preparing the macrocyclic aromatic compounds based on secondary aromatic amines, when... and When the structures are the same, the preparation of the macrocyclic aromatic compounds includes the following steps: Step 1: The aromatic compound shown in Formula A and the halide shown in Formula B are coupled together to obtain the intermediate shown in Formula C. Step 2: The intermediate shown in Formula C and paraformaldehyde are subjected to Friedel-Crafts alkylation reaction under acid to obtain the macrocyclic aromatic compound shown in Formula I. ; Where R1 = Cl, Br, or I; As described in claim 1; when and When the macrocyclic aromatic compounds have different structures, the preparation of the macrocyclic aromatic compounds includes the following steps: Step 1-1: The aromatic compound shown in Formula A and the halide shown in Formula B are coupled together to obtain the intermediate shown in Formula C. Step 2-1: The aromatic compound shown in Formula A and the halide shown in Formula B1 are coupled together to obtain the intermediate shown in Formula C1. Step 3-1: After mixing the intermediates shown in formula C and C1, the mixture is subjected to a Friedel-Crafts alkylation reaction with paraformaldehyde under acidic conditions to obtain the macrocyclic aromatic compound shown in formula I.

[0013] Where R1 = Cl, Br, or I; As described in claim 1.

[0014] The reaction formula in step 3-1 is as follows:

[0015] Preferably, in step 1, step 1-1, or step 2-1, the ratio of aromatic compound A to halide B / B1 is 2-3:1. The coupling reaction is carried out at a temperature of 80-110 °C for 12-24 hours.

[0016] The coupling reaction also includes a catalyst, a base, a ligand, and a solvent; The catalyst comprises one or more of Pd(OAc)2, PdCl2, PdCl2(MeCN)2, [PdCl(allyl)]2 and Pd2(dba)3, Pd(PPh3)4, and the amount of catalyst is 1%-10% of the amount of halide shown in Formula B; The alkali includes NaO. tOne or more of Bu, Cs2CO3, K3PO4, K2CO3, NaOPh, NaOTMS, and DBU, wherein the amount of base is 2-3 times the amount of halide shown in Formula B; The ligands include one or more of XantPhos (4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene), BINAP (2,2'-bis(diphenylphosphine)-1,1'-binaphthyl), dppf (1,1'-bis(diphenylphosphine)ferrocene), DPEPhos (bis[(2-diphenylphosphine)phenyl] ether), P(t-Bu)3 (tri-tert-butylphosphine), SPhos (2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl), XPhos (2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl), and TTBP HBF4 (tri-tert-butylphosphine tetrafluoroborate), wherein the amount of the ligand is 1%-10% of the amount of the halide shown in Formula B; The solvent includes one or more of toluene, tetrahydrofuran, and dioxane.

[0017] Preferably, the molar ratio of the intermediate shown in Formula C or the mixture of intermediates shown in Formula C and C1 to paraformaldehyde is 1:2-5; the molar ratio of the intermediates shown in Formula C and C1 in step 3-1 is 1:1. Preferably, the Friedel-Crafts alkylation reaction further includes an acid, which includes one or more of trifluoromethanesulfonic acid, trifluoroacetic acid, methanesulfonic acid, boron trifluoride ether, ferric chloride, and aluminum trichloride, and the amount of the acid added is 5-100% of the amount of the intermediate. The Friedel-Crafts alkylation reaction was carried out at a temperature of 20-30°C. o The time for C is 0.3-2 hours; The solvents used in the Friedel-Crafts alkylation reaction include one or more of dichloromethane, trichloromethane, 1,2-dichloroethane, chlorobenzene, and acetonitrile.

[0018] The present invention also provides the application of the macrocyclic aromatic compounds based on secondary aromatic amines in the preparation of porous adsorption materials.

[0019] The present invention also provides a porous material for adsorbing and separating gases, wherein the porous material comprises the macrocyclic aromatic compounds based on secondary aromatic amines.

[0020] The materials used for adsorbing and separating gases include one or more of the following: hydrogen, nitrogen, carbon dioxide, methane, ethane, propane, ethylene, acetylene, propyne, sulfur dioxide, ammonia, benzene, toluene, xylene, and cyclohexane.

[0021] For example, it can be used in scenarios such as carbon dioxide capture, natural gas purification, pollutant adsorption, gas adsorption / separation and storage, flue gas desulfurization and sulfur dioxide recovery.

[0022] Examples include carbon dioxide capture, natural gas purification, pollutant adsorption, gas adsorption / separation and storage, flue gas desulfurization, and sulfur dioxide recovery.

[0023] Compared with the prior art, the present invention has the following beneficial effects: (1) This invention effectively improves the rigidity of the macrocyclic skeleton by introducing internal hydrogen bonds into the molecule to constrain each building block of the macrocycle and reducing the rotation of the methylene bridge connecting two building blocks. The increased rigidity of the macrocycle also enhances the interaction and stacking of aromatic groups between macrocycles, thereby improving the rigidity of the organic material. Both of these factors contribute to increased porosity of the organic material, solving the problem of insufficient porosity while retaining its ease of processing.

[0024] (2) The synthesis of macrocyclic aromatic compounds in this invention incorporates building blocks containing hydrogen bond donor and acceptor structures, which has good technical operability and the preparation method can achieve high yield and low cost synthesis. Attached Figure Description

[0025] Figure 1 The NMR spectrum of the three-membered macrocyclic compound I-1 prepared in Example 1 is shown.

[0026] Figure 2 The image shows the NMR spectrum of the binary macrocyclic compound I-2 prepared in Example 2.

[0027] Figure 3 The image shows the NMR spectrum of the binary macrocyclic compound I-3 prepared in Example 2.

[0028] Figure 4 The NMR spectrum of the binary macrocyclic compound I-4 prepared in Example 3 is shown.

[0029] Figure 5 The NMR spectrum of the four-membered macrocyclic compound I-5 prepared in Example 3 is shown.

[0030] Figure 6 The NMR spectrum of the three-membered macrocyclic compound I-6 prepared in Example 4 is shown.

[0031] Figure 7 The NMR spectrum of the four-membered macrocyclic compound I-7 prepared in Example 4 is shown.

[0032] Figure 8 This is a crystal packing structure diagram of the ternary macrocyclic compound I-1 prepared in Example 1.

[0033] Figure 9 This is a SEM image of the porous gel of the ternary macrocyclic compound I-6 prepared in Example 4.

[0034] Figure 10 The image shows the nitrogen adsorption isotherm of the porous crystal material prepared in Example 1 at 77K.

[0035] Figure 11 The image shows the carbon dioxide adsorption isotherm at 195 K for the porous gel prepared in Example 4.

[0036] Figure 12 The adsorption isotherm diagram of the main components of natural gas by the porous crystalline material in Application Example 1 is shown.

[0037] Figure 13 The image shows the adsorption isotherm of sulfur dioxide in flue gas by the porous gel material in Example 2. Detailed Implementation

[0038] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention. Modifications or equivalent substitutions made by those skilled in the art based on their understanding of the technical solutions of this invention, without departing from the spirit and scope of the invention, should be covered within the protection scope of this invention.

[0039] All raw materials used in the following specific implementation methods were purchased from the market.

[0040] Example 1 The preparation of macrocyclic aromatic compound I-1 is as follows: Step 1: In a 250 mL round-bottom flask, ethyl 2-aminobenzoate (7.27 g, 44.0 mmol), 1,4-dibromotetrafluorobenzene (6.16 g, 20.0 mmol), Pd₂(dba)₃ catalyst (tris(dibenzylacetone)palladium, 0.36 g, 0.39 mmol), cesium carbonate (20.0 g, 61.4 mmol), tri-tert-butylphosphine tetrafluoroborate (0.362 g, 1.25 mmol), and 60 mL of toluene were added. The mixture was heated at 110 °C for 24 hours under a nitrogen atmosphere with electromagnetic stirring. After the reaction was complete, toluene was removed by rotary evaporation. The residue was separated by silica gel column chromatography using a 2:1 ratio of dichloromethane and petroleum ether as eluent to give 8.54 g of a white solid product, with a yield of 94%.

[0041] Step 2: The product obtained in the previous step (0.908 g, 2.0 mmol) was dissolved in 200 mL of dichloromethane. Paraformaldehyde (0.18 g, 6 mmol) and 0.1 mL of trifluoromethanesulfonic acid were added as catalysts, and the mixture was stirred electromagnetically for 30 minutes at room temperature. The reaction was quenched by adding 200 mL of saturated sodium bicarbonate solution. After separation, the organic phase was washed with saturated sodium bicarbonate solution and saturated brine. The organic phase was dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation. The residue was separated by silica gel column chromatography, eluted with a 1:1 volume ratio of dichloromethane and petroleum ether as eluent, to obtain a three-membered macrocyclic compound, 0.21 g of white solid, yield 23%. Its NMR spectrum is shown below. Figure 1 As shown.

[0042] The overall reaction formula is as follows: .

[0043] Example 2 The preparation of macrocyclic aromatic compounds I-2 and I-3 is as follows: Step 1: In a 250 mL round-bottom flask, ethyl 2-aminobenzoate (7.27 g, 44.0 mmol), 1,4-dibromobenzene (4.72 g, 20.0 mmol), Pd₂(dba)₃ catalyst (tris(dibenzylacetone)palladium, 0.36 g, 0.39 mmol), cesium carbonate (20.0 g, 61.4 mmol), tri-tert-butylphosphine tetrafluoroborate (0.362 g, 1.25 mmol), and 80 mL of toluene were added. The mixture was heated at 110 °C for 12 hours under a nitrogen atmosphere with electromagnetic stirring. After the reaction was complete, the mixture was cooled and filtered. The filtrate was removed by evaporation, and the product was recrystallized from ethanol. Filtering yielded 7.35 g of a white solid product, with a yield of 91%.

[0044] Step 2: The product obtained in the previous step (0.808 g, 2.0 mmol) was dissolved in 200 mL of dichloromethane. Paraformaldehyde (0.18 g, 6 mmol) and 0.1 mL of trifluoromethanesulfonic acid were added as catalysts, and the mixture was stirred electromagnetically for 20 minutes at room temperature. The reaction was quenched by adding 200 mL of saturated sodium bicarbonate solution. After separation, the organic phase was washed with saturated sodium bicarbonate solution and saturated brine. The organic phase was dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation. The residue was separated by silica gel column chromatography using a gradient elution with dichloromethane and petroleum ether at volume ratios of 1:1, 2:1, and 3:1 to obtain macrocyclic compounds. Among these, the binary macrocyclic compound (n=1) was a white solid, weighing 0.23 g, with a yield of 28%. Its NMR spectrum is shown below. Figure 2 As shown; 0.092 g of a white solid, a three-membered macrocyclic compound (n=2), with a yield of 11%, has the following NMR spectrum: Figure 3 As shown.

[0045] The overall reaction formula is as follows: .

[0046] Example 3 The preparation of macrocyclic aromatic compounds I-4 and I-5 is as follows: Step 1: In a 250 mL round-bottom flask, ethyl 2-aminobenzoate (7.27 g, 44.0 mmol), 4,4'-dibromobenzophenone (6.80 g, 20.0 mmol), Pd2(dba)3 catalyst (tris(dibenzylacetone)dipalladium, 0.36 g, 0.39 mmol), cesium carbonate (20.0 g, 61.4 mmol), tri-tert-butylphosphine tetrafluoroborate (0.362 g, 1.25 mmol), and 80 mL of toluene were added. The mixture was heated at 110 °C for 18 hours under a nitrogen atmosphere with electromagnetic stirring. After the reaction was complete, the mixture was cooled and filtered. The filtrate was removed by evaporation, and the product was recrystallized from ethanol. Filtering yielded 9.45 g of a white solid product, with a yield of 93%.

[0047] Step 2: The product obtained in the previous step (1.016 g, 2.0 mmol) was dissolved in 180 mL of dichloromethane. Paraformaldehyde (0.18 g, 6 mmol) and 0.1 mL of trifluoromethanesulfonic acid were added as catalysts, and the mixture was stirred electromagnetically for 40 minutes at room temperature. The reaction was quenched by adding 180 mL of saturated sodium bicarbonate solution. After separation, the organic phase was washed with saturated sodium bicarbonate solution and saturated brine. The organic phase was dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation. The residue was separated by silica gel column chromatography, using a gradient elution of dichloromethane and ethyl acetate at volume ratios of 10:1 and 5:1 to obtain macrocyclic compounds. The dicyclic macrocyclic compound (n=1) was a white solid, weighing 0.417 g, with a yield of 41%. Its NMR spectrum is shown below. Figure 4 As shown; 0.041 g of a white solid, a three-membered macrocyclic compound (n=2), with a yield of 6%, has the following NMR spectrum: Figure 5 As shown.

[0048] The overall reaction formula is as follows: .

[0049] Example 4 The preparation of macrocyclic aromatic compounds I-6 and I-7 is as follows: Step 1: In a 250 mL round-bottom flask, ethyl 2-aminobenzoate (7.27 g, 44.0 mmol), 1,4-dibromotetrafluorobenzene (6.16 g, 20.0 mmol), Pd2(dba)3 catalyst (tris(dibenzylacetone)palladium, 0.36 g, 0.39 mmol), cesium carbonate (20.0 g, 61.4 mmol), tri-tert-butylphosphine tetrafluoroborate (0.362 g, 1.25 mmol), and 80 mL of toluene were added. The mixture was heated at 110 °C for 18 hours under a nitrogen atmosphere with electromagnetic stirring. After the reaction was complete, benzene was removed by rotary evaporation. The residue was separated by silica gel column chromatography using a 1:1 eluent of dichloromethane and petroleum ether to give 9.04 g of a white solid product, with a yield of 95%.

[0050] Step 2: The product obtained in the previous step (0.952 g, 2.0 mmol) was dissolved in 180 mL of dichloromethane. Paraformaldehyde (0.18 g, 6 mmol) and 0.1 mL of trifluoromethanesulfonic acid were added as catalysts, and the mixture was stirred electromagnetically for 40 minutes at room temperature. The reaction was quenched by adding 180 mL of saturated sodium bicarbonate solution. After separation, the organic phase was washed with saturated sodium bicarbonate solution and saturated brine. The organic phase was dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation. The residue was separated by silica gel column chromatography, using a gradient elution of dichloromethane and petroleum ether at volume ratios of 1:1 and 3:1 to obtain macrocyclic compounds. The three-membered macrocyclic compound (n=1) yielded 0.41 g of a white solid, with a yield of 42%. Its NMR spectrum is shown below. Figure 6 As shown; a four-membered macrocyclic compound (n=2) was obtained as a white solid, weighing 0.117 g, with a yield of 12%. Its NMR spectrum is shown below. Figure 7 As shown.

[0051] The overall reaction formula is as follows: .

[0052] Performance Characterization The ternary macrocyclic compound I-1 prepared in Example 1 was used to form a porous crystal material, and the ternary macrocyclic compound I-6 prepared in Example 4 was used to form a porous gel material, thereby characterizing their porous properties and adsorption capacity.

[0053] 100 mg of a macrocyclic compound was dissolved in a 1:1 mixture of toluene and chloroform at room temperature. The solution was filtered, and the clarified filtrate was allowed to stand at room temperature for 3-5 days to obtain macrocyclic crystals suitable for single-crystal X-ray diffraction analysis. Subsequently, the solvent was removed by heating in a vacuum oven to obtain porous macrocyclic crystal materials. The crystal packing structure of macrocyclic compound I-1 is shown below. Figure 8 As shown, this indicates that it has formed a porous framework structure.

[0054] 500 mg of macrocyclic compound I-6 was dissolved in toluene solution by heating, filtered, and then the resulting clear solution was slowly cooled to room temperature. After standing at room temperature for 2-3 days, a macrocyclic gel was obtained. This gel was then heated in a vacuum oven to remove solvent molecules, yielding a porous macrocyclic gel material. A scanning electron microscope (SEM) image of the gel material is shown below. Figure 9 As shown, the large ring is assembled into a rod-shaped structure.

[0055] The prepared porous crystalline material and gel material were subjected to Brunauer-Emmett-Teller (BET) gas adsorption experiments, and the results are as follows: Figure 10 and Figure 11 As shown, the porous crystal material prepared by the ternary macrocyclic compound in Example 1 and the porous gel material prepared by the ternary macrocyclic compound in Example 4 have specific surface areas as high as 842 m³ / g (m²). 2 / g) and cubic meters / gram (418 m 2 / g), reaching the level of specific surface area of ​​framework porous materials.

[0056] Application Example 1 The ternary macrocyclic compound I-1 prepared in Example 1 was formed into a porous crystal material for gas adsorption testing. The static adsorption isotherm was measured using a gas adsorption analyzer, with a test pressure range of 0-1 bar. The dead volume was determined using helium. Before testing, the sample needed to be degassed and activated at 120 °C under vacuum for 24 h to fully remove solvent molecules and attached impurities from the pores.

[0057] Figure 12 The adsorption isotherms of the prepared porous crystalline material for methane, ethane, and propane are shown, with adsorption capacities for ethane and propane reaching 45 cm⁻¹, respectively. 3 / g and 62 cm 3 / g, with an adsorption capacity of only 3.5 cm for methane. 3 / g, this difference in adsorption capacity indicates its potential application in natural gas purification.

[0058] Application Example 2 The ternary macrocyclic compound I-6 prepared in Example 4 was used to form a porous gel material. Gas adsorption tests were performed on the gas. The static adsorption isotherm was measured using a gas adsorption analyzer. The test pressure range was 0-1 bar, and the dead volume was determined using helium. Before testing, the sample needed to be degassed and activated at 120°C under vacuum for 24 h to fully remove solvent molecules and attached impurities from the pores. Figure 13 The adsorption isotherm of the prepared porous gel material for sulfur dioxide (SO2) is shown, with an adsorption capacity of 56 cm⁻¹. 3 / g indicates its potential application in sulfur dioxide recovery.

Claims

1. A macrocyclic aromatic compound based on secondary aromatic amines, characterized in that, It has the structure shown in Equation I: （I） in, Indicates intramolecular hydrogen bond, Y=COR, COOR or CONHR, R is alkyl, alkenyl or aromatic, n is 1, 2 or 3; and For the same or different structures, each group is independently selected from any of the following groups: 。 2. The macrocyclic aromatic compound based on secondary aromatic amines according to claim 1, characterized in that, R is any one of C1-C8 straight-chain or branched alkyl, C6-C15 aryl or substituted aryl.

3. The macrocyclic aromatic compound based on secondary aromatic amines according to claim 1, characterized in that, R is any one of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, tert-butyl, phenyl, or substituted phenyl.

4. The method for preparing macrocyclic aromatic compounds based on secondary aromatic amines according to claim 1, characterized in that, when and When the structures are the same, the preparation of the macrocyclic aromatic compounds includes the following steps: Step 1: The aromatic compound shown in Formula A and the halide shown in Formula B are coupled together to obtain the intermediate shown in Formula C. Step 2: The intermediate shown in Formula C and paraformaldehyde are subjected to Friedel-Crafts alkylation reaction under acid to obtain the macrocyclic aromatic compound shown in Formula I. ； Where R1 = Cl, Br, or I; As described in claim 1; when and When the macrocyclic aromatic compounds have different structures, the preparation of the macrocyclic aromatic compounds includes the following steps: Step 1-1: The aromatic compound shown in Formula A and the halide shown in Formula B are coupled together to obtain the intermediate shown in Formula C. Step 2-1: The aromatic compound shown in Formula A and the halide shown in Formula B1 are coupled together to obtain the intermediate shown in Formula C1. Step 3-1: After mixing the intermediates shown in formula C and C1, the mixture is subjected to a Friedel-Crafts alkylation reaction with paraformaldehyde under acidic conditions to obtain the macrocyclic aromatic compound shown in formula I. Where R1 = Cl, Br, or I; As described in claim 1.

5. The method for preparing macrocyclic aromatic compounds based on secondary aromatic amines according to claim 3, characterized in that, In step 1, step 1-1, or step 2-1, the molar ratio of the aromatic compound shown in formula A to the halide shown in formula B / B1 is 2-3:

1. The coupling reaction is carried out at a temperature of 80-110 °C for 12-24 hours.

6. The method for preparing macrocyclic aromatic compounds based on secondary aromatic amines according to claim 1, characterized in that, The coupling reaction also includes a catalyst, a base, a ligand, and a solvent; The catalyst comprises one or more of Pd(OAc)2, PdCl2, PdCl2(MeCN)2, [PdCl(allyl)]2 and Pd2(dba)3, Pd(PPh3)4, and the amount of catalyst is 1%-10% of the amount of halide shown in Formula B; The alkali includes NaO. t One or more of Bu, Cs2CO3, K3PO4, K2CO3, NaOPh, NaOTMS, and DBU, wherein the amount of base is 2-5 times the amount of halide shown in Formula B; The ligand comprises one or more of 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene, 2,2'-bis(diphenylphosphine)-1,1'-binaphthyl, 1,1'-bis(diphenylphosphine)ferrocene, bis[(2-diphenylphosphine)phenyl] ether, tri-tert-butylphosphine, 2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl, 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl, and tri-tert-butylphosphine tetrafluoroborate, wherein the amount of the ligand is 1%-10% of the amount of the halide shown in Formula B; The solvent includes one or more of toluene, tetrahydrofuran, and dioxane.

7. The method for preparing macrocyclic aromatic compounds based on secondary aromatic amines according to claim 1, characterized in that, The molar ratio of the intermediate shown in Formula C or the mixture of intermediates shown in Formula C and C1 to paraformaldehyde is 1:2-5; the molar ratio of the intermediates shown in Formula C and C1 in step 3-1 is 1:

1. The Friedel-Crafts alkylation reaction further includes an acid, which includes one or more of trifluoromethanesulfonic acid, trifluoroacetic acid, methanesulfonic acid, boron trifluoride ether, ferric chloride, and aluminum trichloride, and the amount of the acid added is 5-100% of the amount of the intermediate. The Friedel-Crafts alkylation reaction was carried out at a temperature of 20-30°C. o The time for C is 0.3-2 hours; The solvents used in the Friedel-Crafts alkylation reaction include one or more of dichloromethane, trichloromethane, 1,2-dichloroethane, chlorobenzene, and acetonitrile.

8. The application of the macrocyclic aromatic compounds based on secondary aromatic amines according to claim 1 or 2 in the preparation of porous adsorption materials.

9. A porous material for adsorbing and separating gases, characterized in that, The porous material includes the macrocyclic aromatic compounds based on secondary aromatic amines as described in claim 1 or 2.

10. The porous material for adsorbing and separating gases according to claim 9, characterized in that, The materials used for adsorbing and separating gases include one or more of the following: hydrogen, nitrogen, carbon dioxide, methane, ethane, propane, ethylene, acetylene, propyne, sulfur dioxide, ammonia, benzene, toluene, xylene, and cyclohexane.

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