A carbazole and carbene iridium dual-functionalized super-crosslinked porous organic polymer and its preparation method and application

Abstract

The present invention discloses a carbazole and carbene iridium bifunctionalized hypercrosslinked porous organic polymer, a preparation method, and an application thereof. The present invention uses a carbazole and IPr-HCl bifunctionalized hypercrosslinked porous organic polymer (HCP-CzIPr-HCl) as a catalyst precursor. Under the action of an appropriate amount of base LiHMDS, HCP-CzIPr-HCl coordinates with [Ir(COD)Cl]2 to generate HCP-CzIPr-Ir. In a 4.0 MPa mixed gas of CO2 and H2 (volume ratio of 1:1), the catalyst exhibits good catalytic activity in catalyzing the N-formylation reaction of organic amines. Furthermore, the HCP-CzIPr-Ir also has good stability and can be continuously recycled for more than eight times after separation and recovery while still maintaining considerable catalytic activity.

Description

Technical Field

[0001] The present invention relates to the technical field of heterogeneous transition metal catalysts in organic chemical industry, and in particular to a hyper-crosslinked porous organic polymer of carbazole and carbene iridium complex (HCP-CzIPr-Ir) and a preparation method thereof, as well as application of the polymer in catalyzing the reaction of organic amines with CO2 and H2 to prepare N-formamide compounds. Background Art

[0002] N-Formamides are important organic chemical raw materials, widely used in pharmaceuticals, pesticides, and functional materials. For example, N,N-dimethylformamide (DMF) is one of the most commonly used organic solvents. Traditionally, there are two main methods for producing N-formamides: one is the N-formylation reaction of organic amines with CO under base catalysis. This method requires the highly toxic raw material CO, harsh reaction conditions, and low yields; the other is the aminolysis reaction of organic amines with formic acid or methyl formate. This method requires expensive formic acid and methyl formate, resulting in high production costs. Therefore, the development of green, environmentally friendly, and low-cost methods for the synthesis of N-formamides has attracted widespread attention.

[0003] CO2 is one of the basic components of the atmosphere. Using H2 as a reducing agent, the N-formylation reaction of CO2 with organic amines is the most ideal method for preparing N-formamide. Compared with traditional synthesis methods, this method has the following significant advantages: (1) CO2 and H2 are both common bulk chemical raw materials in industry, available in large quantities and inexpensive; (2) Water is the only by-product of the reaction, which has almost no impact on the environment; (3) CO2 is converted into useful chemical products to achieve carbon recycling. Due to the stability and chemical inertness of CO2 and H2, the reaction requires the action of a catalyst. Among them, Ir-containing organic complexes are one of the commonly used catalysts for this reaction, with advantages such as high catalytic activity and good selectivity. However, the preparation process of these Ir-containing organic complexes is complicated, the production cost is high, and the price is expensive. In addition, removing these catalysts after the reaction is completed is also a difficult problem. By heterogenizing organic transition metal complexes, the catalyst separation is simple, and it is easy to recover and reuse multiple times, which can overcome the limitations of the above-mentioned homogeneous catalysts and better meet the actual application needs of industrial production. So far, the literature has reported the preparation of some Ir-functionalized heterogeneous catalysts and their application in catalyzing the reaction of organic amines with CO2 and H2 to prepare N-formamide compounds.

[0004] For example, Reference 1 (Chemical Communication, 2014, 50, 9138-9140) uses a deposition-precipitation method to load metallic Ir onto the surface of HSA-TiO2 to prepare Ir / HSA-TiO2. Under the conditions of a reaction temperature of 140°C, a pressure of 6.0 MPa (pH2: pCO2 = 1:1), and a reaction time of 16 h, it catalyzes the N-formylation of dimethylamine to produce DMF with a yield of 93% and a DMF production efficiency of 882 mmol / g. -1 h -1 , Ir / HSA-TiO2 can be reused more than 5 times.

[0005] Reference 2 (Carbon, 2016, 100, 632-640) uses a solid surface chemical modification method to load a [(bpy)2Ir(S-benzimidazole)] complex onto the surface of graphene oxide (GO) to prepare GO-Ir. Under the conditions of 0.03 mol% catalyst, 100°C reaction temperature, 6.0 MPa pressure (pH2:pCO2=1:1), and 3 h reaction time, GO-Ir catalyzed the N-formylation of dimethylamine to produce DMF with an 87% yield. GO-Ir can be reused more than six times. However, neither GO-Ir nor Ir / HSA-TiO2 has been used to catalyze the synthesis of other N-formamide compounds besides DMF.

[0006] Reference 3 (Chemistry - An Asian Journal, 2018, 13, 3018-3021) reported the preparation of a poly(bisbenzimidazole) carbene Ir-functionalized solid catalyst HNC-Ir using a self-assembly method. Using 0.1 mol% catalyst, methanol as the reaction medium, a temperature of 100°C, a pressure of 6.0 MPa (pH 2:pCO 2 = 1:1), and a reaction time of 20 h, the catalyst catalyzed the N-formylation of 23 functionalized fatty amines. Yields of the corresponding N-formamide products ranged from 53% to 97%, and the catalyst was reusable for more than 10 times.

[0007] Document 4 (Angewandte Chemie International Edition, 2021, 60, 4125-4132) improved the preparation method of the catalyst based on Document 3, and obtained a solid catalyst POMP-NHC-Ir functionalized with polybisbenzimidazole carbene Ir with a porous structure. In the catalytic N-formylation reaction of various functionalized fatty amines, the catalytic activity of POMP-NHC-Ir is about 10 times that of NHC-Ir, and it can be reused 12 times. Compared with Ir / HSA-TiO2 and GO-Ir, POMP-NHC-Ir and NHC-Ir have a wider range of applications. However, these two carbene Ir heterogeneous catalysts are also limited to catalyzing the N-formylation reaction of fatty amines.

[0008] In summary, heterogeneous Ir metal catalysts have shown significant potential for the N-formylation of amines with CO₂ / H₂. However, existing heterogeneous Ir metal catalysts still suffer from drawbacks such as the high CO₂ and H₂ pressures required (6.0 MPa) and their limited use in the preparation of fatty formamides. Summary of the Invention

[0009] In view of the shortcomings of the existing technology, the present invention provides a carbazole and carbene iridium bifunctionalized hyper-crosslinked porous organic polymer (HCP-CzIPr-Ir) and its preparation method, as well as its application in catalyzing the reaction of organic amines with CO2 and H2 to prepare organic formamides.

[0010] This invention uses a hypercrosslinked porous organic polymer (HCP-CzIPr-HCl) functionalized with carbazole and IPr-HCl as a catalyst precursor. In the presence of an appropriate amount of the base LiHMDS, HCP-CzIPr-HCl coordinates with [Ir(COD)Cl]2 to form HCP-CzIPr-Ir. In a 4.0 MPa mixture of CO2 and H2 (1:1 by volume), the catalyst exhibits excellent catalytic activity in the N-formylation of aliphatic and aromatic amines. Furthermore, HCP-CzIPr-Ir exhibits excellent stability and can be recycled over eight times after separation and recovery while maintaining substantial catalytic activity.

[0011] The technical solutions of the present invention are as follows:

[0012] A carbazole and carbene iridium dual-functionalized hyper-crosslinked porous organic polymer, referred to as HCP-CzIPr-Ir, has a structural formula shown in Formula 6:

[0013]

[0014] Wavy lines indicate junction sites.

[0015] The preparation method of the carbazole and carbene iridium bifunctionalized hypercrosslinked porous organic polymer (HCP-CzIPr-Ir) of the present invention is as follows:

[0016] Under a protective atmosphere (preferably nitrogen), HCP-CzIPr-HCl, [Ir(COD)Cl]2, LiHMDS and an organic solvent as shown in Formula 5 are mixed, stirred at 50-120°C (preferably 80°C) for 12-36 hours (preferably 24 hours), and post-treated to obtain HCP-CzIPr-Ir;

[0017] in,

[0018] The molar ratio of HCP-CzIPr-HCl to [Ir(COD)Cl]2 is 1.0:0.5-2.0, preferably 1.0:1.1;

[0019] The molar ratio of HCP-CzIPr-HCl to LiHMDS is 1.0:1.0 to 3.0, preferably 1.0:2.0;

[0020] The organic solvent is selected from 1,4-dioxane, THF, DMSO, DMAc, DMF, NMP, etc., preferably DMF;

[0021] The volume mass ratio of the organic solvent to HCP-CzIPr-HCl is 15.0 to 40.0:1, mL / g, preferably 20.0:1, mL / g;

[0022] The specific post-treatment method is as follows: after the reaction is completed, cool to room temperature, filter, wash the solid product with THF, and dry in vacuo at 80°C for 6 h to obtain HCP-CzIPr-Ir;

[0023] In the present invention, the catalyst precursor HCP-CzIPr-HCl can be synthesized according to the prior application CN116730989A of this research group. The structural formula of HCP-CzIPr-HCl is shown in Formula 5:

[0024]

[0025] Wavy lines indicate junction sites.

[0026] The Ir loading in HCP-CzIPr-Ir was determined to be 0.47 mmol / g by ICP-MS. The specific surface area of ​​HCP-CzIPr-Ir was determined to be 460 m 2 / g, pore volume is 0.38cm 3 / g, with pore sizes of 0.73nm, 1.39nm and 2.71nm; characteristic peaks of carbazole and isopropyl can be seen through infrared characterization; solid-state nuclear magnetic resonance can prove that HCP-CzIPr-Ir contains aromatic, isopropyl and carbene carbon functional groups; SEM and TEM can show that HCP-CzIPr-Ir has abundant mesopores and micropores, indicating that HCP-CzIPr-Ir is a hyper-cross-linked polymer with a micro-mesoporous structure.

[0027] The carbazole and carbene iridium bifunctionalized hypercrosslinked porous organic polymer (HCP-CzIPr-Ir) described in the present invention can be used as a heterogeneous catalyst in the N-formylation reaction of organic amines with CO2 and H2. The specific application method is as follows:

[0028] HCP-CzIPr-Ir, organic amine, and 1,2-dimethylimidazolidinone (DMI) were added to a reactor, and the gas in the reactor was replaced with CO2. The reactor was then pressurized to 2.0 MPa, and 2.0 MPa of H2 was introduced. The temperature was raised to 120°C and the reaction was carried out for 24 hours. The reaction solution was then post-treated to obtain an N-formylation product.

[0029] The organic amine is selected from: aliphatic amine, aromatic amine, or heteroaromatic amine containing nitrogen atoms;

[0030] The preferred molar ratio of HCP-CzIPr-Ir and organic amine is 0.1:100;

[0031] The specific post-treatment method is as follows: after the reaction is completed, the mixture is cooled to room temperature, dichloromethane is added to the system, centrifuged to separate the upper liquid layer and the lower catalyst solid layer, the catalyst is washed with dichloromethane, the organic phases are combined, and the mixture is concentrated under reduced pressure and then purified by column chromatography (200-300 mesh silica gel, ethyl acetate / petroleum ether as eluent) to obtain the N-formylation product.

[0032] The beneficial effects of the present invention are:

[0033] (1) The heterogeneous catalyst of the present invention can catalyze the N-formylation reaction of organic amines under a relatively low pressure of 2.0 MPa CO2 and 2.0 MPa H2.

[0034] (2) The heterogeneous catalyst of the present invention has high catalytic activity, requires little catalyst, and has a TON greater than 1000.

[0035] (3) After the reaction, the catalyst can be used continuously for more than 8 times through simple post-treatment and still maintain excellent catalytic activity. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 :Monomer CzIPr-HCl 1 H NMR spectrum (400 MHz).

[0037] Figure 2 :Monomer CzIPr-HCl 13 C NMR spectrum (100 MHz).

[0038] Figure 3 : IR spectra of monomer CzIPr-HCl, catalyst precursor HCP-CzIPr-HCl and catalyst HCP-CzIPr-Ir.

[0039] Figure 4 :Solid state of catalyst HCP-CzIPr-Ir 13 C NMR spectrum (100 MHz, rotation speed 8000 Hz).

[0040] Figure 5 : TGA diagram of catalyst HCP-CzIPr-Ir.

[0041] Figure 6 : Nitrogen adsorption-desorption isotherm of catalyst HCP-CzIPr-Ir.

[0042] Figure 7 : Pore size distribution diagram of catalyst HCP-CzIPr-Ir.

[0043] Figure 8 : SEM image of catalyst HCP-CzIPr-Ir.

[0044] Figure 9 : TEM image of catalyst HCP-CzIPr-Ir.

[0045] Figure 10 : Actual sample photos of catalyst precursor HCP-CzIPr-HCl and catalyst HCP-CzIPr-Ir.

[0046] Figure 11 : Catalytic effect diagram of 8 consecutive cycle experiments. DETAILED DESCRIPTION

[0047] The present invention is further described below by means of specific examples, but the protection scope of the present invention is not limited thereto.

[0048] Example 1: Preparation of catalyst HCP-CzIPr-Ir

[0049] Preparation of intermediate 1 (2,6-diisopropyl-4-iodoaniline): In a 1L four-necked flask, 2,6-diisopropylaniline (15.0g, 85mmol), 30mL of methyl tert-butyl ether and 250mL of saturated sodium bicarbonate solution were added in sequence. Under stirring at room temperature, 140mL of methyl tert-butyl ether solution containing iodine (23.6g, 93mmol) was added dropwise over 2h. After the addition, stirring was continued at room temperature for 5h. After the reaction was completed, sodium thiosulfate (2.4g, 15mmol) was added to remove excess iodine in the reaction solution. The reaction solution was extracted with 60mL×3 methyl tert-butyl ether, the extracts were combined, dried over anhydrous sodium sulfate, filtered, and the organic solvent was recovered by vacuum rotary evaporation to obtain 24.9g of a yellow oily liquid with a yield of 97.1%. The product is characterized as follows: 1 H NMR (500MHz, CDCl3) δ = 7.30 (s, 2H), 3.75 (s, 2H), 1.26 (d, J = 6.9Hz, 12H) ppm; 13 C NMR (125MHz, CDCl3) δ=140.1, 135.1, 131.8, 81.1, 77.3, 77.1, 76.9, 27.9, 22.3ppm.

[0050] Preparation of Intermediate 2 (2,6-diisopropyl-4-carbazolylaniline): To a 50 mL single-necked flask, intermediate 1 (3.0 g, 10 mmol), carbazole (1.7 g, 10 mmol), CuCl (0.3 g, 3 mmol), o-phenanthroline (0.6 g, 3 mmol), KOH (2.2 g, 40 mmol), and 20 mL of toluene were added in sequence. The mixture was stirred at 140°C for 36 h. After the reaction was completed, 20 mL of 25% aqueous ammonia was added and stirred for 6 h. The toluene layer was separated, washed with water until neutral, dried over anhydrous sodium sulfate, and the solvent was recovered by vacuum rotary evaporation. The residue was slurried in 50 mL of methanol, filtered, and dried at room temperature to obtain 3.3 g of a gray solid with a yield of 96.4%. Melting point: 300.3°C. The product was characterized as follows: 1 H NMR (400MHz, CDCl3) δ = 8.23 ​​(d, J = 7.72Hz, 2H), 7.50-7.42 (m, 4H), 7.36-7.30 (m , 2H), 7.26 (s, 2H), 4.06 (s, 2H), 3.13-3.07 (m, 2H), 1.38 (d, J=3.4Hz, 12H)ppm; 13 C NMR (100MHz, CDCl3) δ=141.5, 139.4, 133.9, 128.5, 125.7, 122.9, 121.9, 120.2, 119.3, 109.9, 28.2, 22.5ppm.

[0051] Preparation of Intermediate 3 (N,N'-bis(2,6-diisopropylphenyl-4-carbazolyl)-1,4-diazabutadiene): To a 150 mL single-necked flask were added Intermediate 2 (9.9 g, 29 mmol), aqueous glyoxal solution (2.7 mL, 15 mmol), formic acid (0.4 mL), and 30 mL of DMF. The mixture was stirred at room temperature (25°C) for 24 hours, then heated to 40°C for an additional 12 hours. After completion of the reaction, the mixture was filtered, and the filter cake was washed with 50 mL of DMF and 50 mL of methyl tert-butyl ether, followed by drying under vacuum at 60°C for 1 hour to obtain 8.2 g of a yellow solid with a yield of 80.0%. Melting point: >400°C (decomposition). The product was characterized as follows: 1 H NMR (400MHz, CDCl3) δ8.23 (s, 2H), 8.09 (d, J = 8.0Hz, 2H), 7.39-7.32 (m, 12H), 7.24-7.14 (m, 6H), 3.06-2.99 (m, 4H), 1.21 (d, J = 8.0Hz, 24H) ppm; 13 C NMR (100MHz, CDCl3) δ=163.5, 146.9, 141.0, 138.8, 134.8, 126.0, 123.3, 122.0, 120.4, 119.9, 109.9, 28.4, 23.5ppm.

[0052] Preparation of monomer CzIPr-HCl4 (1,3-bis(2,6-diisopropylphenyl-4-carbazolyl)imidazole chloride): To a 250 mL single-necked round-bottom flask, the above-mentioned intermediate 3 (8.5 g, 12 mmol), paraformaldehyde (0.4 g, 13 mmol), and 240 mL of ethyl acetate were added sequentially. The mixture was stirred at 70°C for 1 hour, and then trimethylsilyl chloride (1.8 mL, 13 mmol) was added in three batches over the same hour. The reaction was stirred at this temperature for 12 hours. After the reaction was completed, the mixture was cooled to room temperature and filtered. The filter cake was washed with 50 mL of ethyl acetate and then vacuum-dried at 60°C for 1 hour to obtain 6.3 g of a white solid with a yield of 70.5%. Melting point: greater than 400°C (decomposition). The product was characterized as follows: 1 H NMR (400MHz, CDCl3) δ = 11.20 (s, 1H), 8.16-8.14 (m, 6H), 7.59 (s, 4H), 7.52-7.50 (m, 4 H), 7.46-7.43(m, 4H), 7.33-7.30(m, 4H), 2.62-2.59(m, 4H), 1.37-1.33(m, 24H)ppm; 13C NMR (100MHz, CDCl3) δ=147.4, 141.4, 140.7, 140.2, 128.3, 126.4, 123.8, 122.9, 120.7, 120.5, 109.8, 29.6, 24.7, 23.8ppm.

[0053] Preparation of Catalyst Precursor 5 (HCP-CzIPr-HCl): Under nitrogen, CzIPr-HCl monomer (0.8 g, 1 mmol), FDA (1.5 g, 20.0 mmol), and 20 mL of dichloroethane were added sequentially to a 50 mL single-necked flask. After stirring, FeCl3 (3.2 g, 20.0 mmol) was added and the mixture was stirred at 45°C for 5 h. The temperature was then raised to 80°C and the reaction continued for 48 h. After the reaction was completed, the mixture was cooled to room temperature. The resulting polymer was washed with 20 mL of water and then 20 mL of methanol. The mixture was then transferred to a Soxhlet extractor and washed with methanol for 24 h. Finally, the mixture was vacuum dried at 80°C for 12 h to obtain 1.0 g of a black solid, which was then ground into powder.

[0054] Preparation of Catalyst 6 (HCP-CzIPr-Ir): Under nitrogen, HCP-CzIPr-HCl (234 mg), LiHMDS (66.8 mg, 0.4 mmol), [Ir(COD)Cl]2 (73.9 mg, 0.11 mmol), and 10.0 mL of DMF were added sequentially to an 80 mL reaction tube and stirred at 80°C for 24 h. The mixture was filtered, washed with 20.0 mL of THF, and dried under vacuum at 80°C for 6 h to obtain a brown solid. ICP-MS determined the Ir metal content in the catalyst to be 0.47 mmol / g.

[0055] The synthetic route is as follows:

[0056]

[0057] Example 2: HCP-CzIPr-Ir catalyzes N-formylation of organic amines with CO2 and H2

[0058] Taking the N-formylation reaction of morpholine catalyzed by HCP-CzIPr-Ir with CO2 and H2 as an example, HCP-CzIPr-Ir (21.2 mg), morpholine (871 mg, 10 mmol), and 2.0 mL of 1,2-dimethylimidazolidinone (DMI) were sequentially added to a 50 mL pressure reactor. The atmosphere in the reactor was replaced with carbon dioxide three times, then pressurized to 2.0 MPa. Hydrogen was then introduced into the reactor at 2.0 MPa. The temperature was raised to 120°C and the reaction was continued for 24 h. After the reaction, 5.0 mL of dichloromethane was added, and the mixture was transferred to a centrifuge tube and centrifuged. The supernatant was separated and the remaining catalyst in the centrifuge tube was washed with 3.0 mL of dichloromethane twice. The dichloromethane washings were combined and the solvent was recovered by vacuum rotary evaporation. The residue was purified by column chromatography (200-300 mesh silica gel, ethyl acetate / petroleum ether as eluent) to obtain N-formylmorpholine in a yield of 99%. Colorless liquid, 1 H NMR (500MHz, CDCl3) δ = 8.00 (s, 1H), 3.66-3.63 (m, 2H), 3.62-3.59 (m, 2H), 3.53-3.50 (m, 2H), 3.37-3.33 (m, 2H)ppm; 13 C NMR (125MHz, CDCl3) δ=160.8, 67.2, 66.4, 45.8, 40.6ppm.

[0059] The N-formylation reaction results of different organic amines are shown in Table 1.

[0060] Table 1

[0061]

[0062]

[0063] Characterization data of the product:

[0064] 1: N-formylaniline

[0065] Yellow solid, melting point: 47.1℃, 1 H NMR (500MHz, CDCl3) δ = 8.75-8.69 (m, 1H), 8.36 (s, 0.5H), 7.79 (s, 0.5H), 7.55 (d, J = 8.1Hz, 1H), 7.37-7.30 (m, 2H), 7.20-7.09 (m, 2H)ppm; 13 CNMR (125MHz, CDCl3) δ=162.9, 159.2, 136.9, 136.8, 129.7, 129.1, 125.2, 124.8, 120.0, 118.8ppm.

[0066] 2: N-methyl-N-formylaniline

[0067] Colorless liquid, 1 H NMR (500MHz, CDCl3) δ=8.46 (s, 1H), 7.42-7.38 (m, 2H), 7.26 (t, J=7.4Hz, 1H), 7.16 (d, J=7.5Hz, 2H), 3.30 (s, 3H)ppm; 13 C NMR (125MHz, CDCl3) δ=162.3, 142.2, 129.6, 126.4, 122.3, 32.0ppm.

[0068] 3: N-ethyl-N-formylaniline

[0069] Colorless liquid, 1 H NMR (500MHz, CDCl3) δ = 8.34 (s, H), 7.40 (t, J = 7.7Hz, 2H), 7.29 (t, J = 7.4Hz, 1H), 7.16 (d, J = 7.7Hz, 2H), 3.87-3.83 (m, 2H), 1.15 (t, J = 7.1Hz, 3H) ppm; 13 C NMR (125MHz, CDCl3) δ=161.9, 140.8, 129.6, 126.8, 124.2, 40.0, 3.0ppm.

[0070] 4: N-formyl-4-methylaniline

[0071] White solid, melting point: 56.5℃, 1 H NMR (500MHz, CDCl3) δ=8.63 (d, J=11.5Hz, 0.5H), 8.46 (s, 0.5H), 8.33 (d, J=1.6Hz, 0.5H), 7.56 (s, 0.5H), 7.42 (d, J = 8.4Hz, 1H), 7.14 (m, 2H), 6.99 (d, J = 8.3Hz, 1H), 2.32 (d, J = 9.3Hz, 3H) ppm; 13 C NMR (125MHz, CDCl3) δ=162.9, 159.0, 135.1, 134.4, 134.1, 130.2, 129.5, 120.0, 119.1, 20.9, 20.8ppm.

[0072] 5: N-formyl-4-methoxyaniline

[0073] Light yellow liquid, 1H NMR (500MHz, CDCl3) δ = 8.50 (d, J = 10.0Hz, 0.5H), 8.30 (s, 1H), 7.56 (s, 0.5H), 7.44 (d, J=10.0Hz, 1H), 7.03 (d, J=10.0Hz, 1H), 6.86 (m, 2H), 3.79 (d, J=10.0Hz, 3H)ppm; 13 C NMR (125MHz, CDCl3) δ=163.1, 159.0, 157.6, 156.7, 129.9, 129.5, 121.8, 121.6, 114.9, 114.2, 55.5, 55.4ppm.

[0074] 6: N-formyl-4-fluoroaniline

[0075] Light yellow liquid, 1 H NMR (500MHz, CDCl3) δ=8.63 (s, 1H), 8.34 (d, J=1.5Hz, 0.5H), 7.64 (s, 0.5H), 7.48 (d, J=8.8Hz, 1H), 7.32-7.25 (m, 2H), 7.01-6.98 (m, J=8.7Hz, 1H)ppm; 13 C NMR (125MHz, CDCl3) δ=63.0, 161.4, 160.5, 159.4, 159.2, 158.6, 132.8, 132.7, 132.6, 21.8, 121.7, 121.1, 121.0, 116.6, 116.4, 115.8, 115.6ppm.

[0076] 7: N-Formyl-4-chloroaniline

[0077] White solid, melting point: 105.4℃, 1 H NMR (500MHz, CDCl3) δ = 8.63 (s, 1H), 8.34 (d, J = 1.5Hz, 0.5H), 7.64 (s, 0.5H), 7.48 (d, J = 8.8Hz, 1H), 7.32-7.25 (m, 2H), 7.02 (d, J = 8.7Hz, 1H) ppm; 13 C NMR (125MHz, CDCl3) δ=162.6, 159.1, 135.4, 135.3, 130.8, 129.9, 129.1, 121.2, 120.1ppm.

[0078] 8: N-formyl-4-bromoaniline

[0079] White solid, melting point: 117.3℃, 1H NMR (500MHz, CDCl3) δ = 8.66 (d, J = 11.3Hz, 0.5H), 8.37 (d, J = 1.4Hz, 0.5H), 7.48-7.43 (m, 4H), 6.98 (d, J = 8.7Hz, 1H) ppm; 13 C NMR (125MHz, CDCl3) δ=162.4, 159.0, 135.8, 135.7, 132.8, 132.1, 121.5, 120.3, 118.3, 117.5ppm.

[0080] 10: N-formylpyrrole

[0081] Colorless liquid, 1 H NMR (500MHz, CDCl3) δ = 8.19 (s, 1H), 3.43-3.41 (m, 2H), 3.35-3.32 (m, 2H), 1.87-1.81 (m, 4H)ppm; 13 C NMR (125MHz, CDCl3) δ=160.8, 45.9, 43.0, 24.8, 24.2ppm.

[0082] 11: N-Formylpiperidine

[0083] Colorless liquid, 1 H NMR (400MHz, CDCl3) δ = 8.00 (s, 1H), 3.49-3.31 (m, 4H), 1.72-1.52 (m, 6H)ppm; 13 C NMR (100MHz, CDCl3) δ=160.8, 46.8, 40.6, 26.6, 25.1, 24.7ppm.

[0084] 12: N,N-di-n-butylformamide

[0085] Colorless liquid, 1 H NMR (500MHz, CDCl3) δ = 7.99 (s, 1H), 3.25-3.22 (m, 2H), 3.16-3.13 (m, 2H), 1.51-1.43 (m, 4H), 1.29-1.24 (m, 4H), 0.90-0.87 (m, 6H)ppm; 13 C NMR (125MHz, CDCl3) δ=162.6, 47.1, 41.8, 30.7, 29.4, 20.1, 19.6, 13.8, 13.6ppm.

[0086] 13: N,N-diethylformamide

[0087] Colorless liquid,1 H NMR (500MHz, CDCl3) δ = 7.98 (s, 1H), 3.29 (q, J = 7.2Hz, 2H), 3.21 (q, J = 7.2Hz, 2H), 1.12 (t, J = 7.2Hz, 3H), 1.06 (t, J = 7.2Hz, 3H) ppm; 13 C NMR (125MHz, CDCl3) δ=162.1, 41.8, 36.5, 14.8, 12.7ppm.

[0088] 14: N-cyclohexylcarboxamide

[0089] Colorless liquid, 1 H NMR (400MHz, CDCl3) δ = .09 (s, 1H), 5.80 (s, 1H), 3.89-3.82 (m, 1H), 1.95-1.59 (m, 5H), 1.39-1.13 (m, 5H)ppm; 13 C NMR (100MHz, CDCl3) δ=163.6, 160.4, 51.0, 47.1, 34.7, 33.0, 25.4, 24.7ppm.

[0090] 15: N,N-dimethylformamide

[0091] Colorless liquid, 1 H NMR (400MHz, CDCl3) δ = 8.01 (s, 1H), 2.97 (s, 3H), 2.88 (s, 3H) ppm; 13 C NMR (100MHz, CDCl3) δ=162.4, 36.4, 31.3ppm.

[0092] 16: N,N-diisopropylformamide

[0093] Colorless liquid, 1 H NMR (400MHz, CDCl3) δ = 8.16 (s, 1H), 4.16-4.12 (m, 1H), 3.61-3.54 (m, 1H), 1.26-1.21 (m, 12H)ppm; 13 C NMR (100MHz, CDCl3) δ=161.6, 46.5, 43.8, 23.5, 20.2ppm.

[0094] 17: N,N'-diformylpyrazine

[0095] White solid, melting point: 127.0℃; 1H NMR (400MHz, CDCl3) δ = 8.07 (s, 2H), 3.58-3.34 (m, 8H)ppm; 13 C NMR (100MHz, CDCl3) δ=160.9, 46.0, 44.9, 40.5, 39.5ppm.

[0096] Example 3: Recovery and Recycling of Catalyst HCP-CzIPr-Ir

[0097] The above-mentioned catalyst HCP-CzIPr-Ir separated by centrifugation was washed with 3.0mL×2THF, vacuum dried at 80℃ for 2h, and then recycled. The recovered catalyst HCP-CzIPr-Ir, morpholine (0.87mL, 10mmol), and 2.0mL 1,2-dimethylimidazolidinone (DMI) were added to a 50mL pressure reactor in sequence. The gas in the reactor was replaced with carbon dioxide three times, then pressurized to 2.0MPa, and then 2.0MPa hydrogen was introduced into the reactor. The temperature was raised to 120℃ and the reaction was carried out for 24h. After the same post-treatment, the separation yield of N-formylmorpholine was 93%. After the catalyst HCP-CzIPr-Ir was washed with THF and vacuum dried, it was continuously recycled for 8 times and still maintained a high catalytic activity. The results are as follows Figure 11 shown.

Claims

1. A carbazole and carbene iridium bifunctionalized hypercrosslinked porous organic polymer, referred to as HCP-CzIPr-Ir, with the structural formula shown in Formula 6: Wavy lines indicate junction sites.

2. The method for preparing the carbazole and carbene iridium dual-functionalized hyper-crosslinked porous organic polymer according to claim 1, wherein: The method is as follows: Under a protective atmosphere, HCP-CzIPr-HCl, [Ir(COD)Cl]2, LiHMDS and an organic solvent as shown in Formula 5 are mixed, stirred at 50-120°C for 12-36 hours, and post-treated to obtain HCP-CzIPr-Ir; The structural formula of HCP-CzIPr-HCl is shown in Formula 5: Wavy lines indicate junction sites.

3. The preparation method according to claim 2, wherein The molar ratio of HCP-CzIPr-HCl to [Ir(COD)Cl]2 is 1.0:0.5~2.

0.

4. The preparation method according to claim 2, wherein The molar ratio of HCP-CzIPr-HCl to LiHMDS is 1.0:1.0-3.

0.

5. The preparation method according to claim 2, wherein The organic solvent is selected from 1,4-dioxane, THF, DMSO, DMAc, DMF or NMP.

6. Use of the carbazole and carbene iridium bifunctionalized hypercrosslinked porous organic polymer as claimed in claim 1 as a heterogeneous catalyst in catalyzing the N-formylation reaction of organic amines with CO2 and H2.

7. The use according to claim 6, characterized in that Here’s how: HCP-CzIPr-Ir, organic amine, and 1,2-dimethylimidazolidinone were added to a reactor, and the gas in the reactor was replaced with CO2. The reactor was then pressurized to 2.0 MPa, and 2.0 MPa of H2 was introduced. The temperature was raised to 120°C and the reaction was allowed to proceed for 24 hours. The reaction solution was then post-treated to obtain an N-formylation product. The organic amine is selected from aliphatic amines, aromatic amines, or heteroaromatic amines containing nitrogen atoms.

8. The use according to claim 7, characterized in that The molar ratio of HCP-CzIPr-Ir and organic amine is 0.1:100.

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