Carbazole and carbene iridium dual-functionalized super-crosslinked porous organic polymer as well as preparation method and application of carbazole and carbene iridium dual-functionalized super-crosslinked porous organic polymer

Abstract

The invention discloses a carbazole and carbene iridium dual-functionalized super-crosslinked porous organic polymer as well as a preparation method and application of the carbazole and carbene iridium dual-functionalized super-crosslinked porous organic polymer. The preparation method comprises the following steps: by taking a carbazole and IPr-HCl dual-functionalized super-crosslinked porous organic polymer (HCP-CzIPr-HCl) as a catalyst precursor, under the action of a proper amount of alkali LiHMDS, carrying out coordination on the HCP-CzIPr-HCl and [Ir (COD) Cl] 2 to generate HCP-CzIPr-Ir; in a mixed gas of CO2 and H2 (the volume ratio is 1: 1) with the pressure of 4.0 MPa, the catalyst shows relatively good catalytic activity in catalysis of an N-formylation reaction of organic amine; meanwhile, the HCP-CzIPr-Ir also has better stability, can be continuously recycled for more than 8 times after being separated and recovered, and still keeps considerable catalytic activity; # imgabs0 #

Description

Technical Field

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

[0002] N-formamide is an important organic chemical raw material, widely used in the fields of medicine, pesticides and functional materials. For example, N,N-dimethylformamide (DMF) is one of the most commonly used organic solvents. There are two main methods for producing traditional N-formamide compounds: one is the N-formylation reaction of organic amines with CO under base catalysis. The raw material CO required in this method is highly toxic, the reaction conditions are harsh, and the yield is low; the other is the aminolysis reaction of organic amines with formic acid or methyl formate. The formic acid and methyl formate required in this method are expensive and the production cost is high. Therefore, the development of green, environmentally friendly and low-cost synthesis methods of N-formamide compounds has received 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 byproduct of the reaction, which has almost no impact on the environment; (3) CO2 is converted into useful chemical products to achieve carbon cycle. Due to the stability and chemical inertness of CO2 and H2, the reaction can only be carried out under 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 thorny problem. The heterogeneous organic transition metal complexes can easily separate the catalysts, and are 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 metal Ir on the surface of HSA-TiO2 to prepare Ir / HSA-TiO2. Under the conditions of reaction temperature of 140°C, pressure of 6.0MPa (pH2: pCO2 = 1: 1), and reaction time of 16h, it catalyzes the N-formylation of dimethylamine to prepare DMF with a yield of 93% and a DMF production efficiency of 882mmolg -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 the [(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 (pH2:pCO2=1:1) and 3 h reaction time, the N-formylation of dimethylamine was catalyzed to prepare DMF with a yield of 87%, and GO-Ir can be reused more than 6 times. However, in addition to DMF, neither GO-Ir nor Ir / HSA-TiO2 has been used to catalyze the synthesis of other N-formamide compounds.

[0006] Reference 3 (Chemistry-An Asian Journal, 2018, 13, 3018-3021) used a self-assembly method to prepare a poly(bisbenzimidazole) carbene Ir functionalized solid catalyst HNC-Ir. Under the conditions of 0.1 mol% catalyst, methanol as the reaction medium, reaction temperature of 100°C, pressure of 6.0 MPa (pH2: pCO2 = 1: 1), and reaction time of 20 h, 23 functionalized fatty amines were catalyzed for N-formylation, and the yield of the corresponding N-formamide product was between 53-97%, and the catalyst could be reused more than 10 times.

[0007] Document 4 (Angewandte Chemie International Edition, 2021, 60, 4125-4132) improved the catalyst preparation method based on Document 3 and obtained a solid catalyst POMP-NHC-Ir functionalized with polybisbenzimidazole carbene Ir having 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, it can be found that heterogeneous Ir metal catalysts have shown important development potential in catalyzing the N-formylation reaction of amines with CO2 / H2. However, existing heterogeneous Ir metal catalysts still have disadvantages such as the high pressure of CO2 and H2 gas required (6.0MPa) and being limited to the preparation of fatty formamides. Summary of the invention

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

[0010] The present invention uses carbazole and IPr-HCl bifunctionalized hyper-crosslinked 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 mixed gas of 4.0MPa CO2 and H2 (volume ratio 1:1), the catalyst shows good catalytic activity in catalyzing the N-formylation reaction of aliphatic amines and aromatic amines. At the same time, HCP-CzIPr-Ir also has good stability and can be continuously recycled for more than 8 times after separation and recovery, and still maintains considerable catalytic activity.

[0011] The technical solution of the present invention is 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 as shown in Formula 6:

[0013]

[0014] Wavy lines indicate junction sites.

[0015] The preparation method of the carbazole and carbene iridium bifunctionalized hyper-crosslinked 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 h (preferably 24 h), 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 vacuum dry at 80°C for 6h 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, and 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 measured to be 0.47 mmol / g by ICP-MS, and the specific surface area of ​​HCP-CzIPr-Ir was measured to be 460 m 2 / g, pore volume is 0.38cm 3 / g, with pore sizes of 0.73nm, 1.39nm and 2.71nm; the 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) of the present invention can be used as a heterogeneous catalyst in catalyzing 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, the gas in the reactor was replaced with CO2, and then the pressure was increased to 2.0 MPa, and then 2.0 MPa H2 was introduced, and the temperature was raised to 120°C for reaction for 24 hours, and then the reaction liquid was post-treated to obtain an N-formylation product;

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

[0030] Preferably, the molar ratio of HCP-CzIPr-Ir to organic amine is 0.1:100;

[0031] The specific post-treatment method is as follows: after the reaction is completed, cool to room temperature, add dichloromethane to the system, centrifuge, separate the upper liquid and the lower catalyst solid, wash the catalyst with dichloromethane, combine the organic phases, concentrate under reduced pressure, and then purify by column chromatography (200-300 mesh silica gel, ethyl acetate / petroleum ether as eluent) to obtain an 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 gas pressure of 2.0 MPa CO2 and 2.0 MPa H2.

[0034] (2) The multiphase catalyst of the present invention has high catalytic activity, small catalyst dosage, and 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] Fig. 9 : TEM image of catalyst HCP-CzIPr-Ir.

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

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

[0047] The present invention is further described below by means of specific embodiments, 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, add 2,6-diisopropylaniline (15.0g, 85mmol), 30mL methyl tert-butyl ether and 250mL saturated sodium bicarbonate solution in sequence. Under room temperature and stirring, add 140mL methyl tert-butyl ether solution containing iodine (23.6g, 93mmol) dropwise within 2h. After the dropwise addition, continue stirring at room temperature for 5h. After the reaction is completed, sodium thiosulfate (2.4g, 15mmol) is added to remove excess iodine in the reaction solution. The reaction solution is extracted with 60mL×3 methyl tert-butyl ether, the extracts are combined, dried over anhydrous sodium sulfate, filtered, and the organic solvent is 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): In a 50mL single-mouth bottle, intermediate 1 (3.0g, 10mmol), carbazole (1.7g, 10mmol), CuCl (0.3g, 3mmol), o-phenanthroline (0.6g, 3mmol), KOH (2.2g, 40mmol) and 20mL toluene were added in sequence. The mixture was stirred at 140°C for 36h. After the reaction was completed, 20mL of 25% ammonia water was added, stirred for 6h, the toluene layer was separated, washed with water until neutral, dried over anhydrous sodium sulfate, and the solvent was recovered by vacuum rotary evaporation. 50mL of methanol was added to the residue for pulping, filtered, and dried at room temperature to obtain 3.3g of gray solid with a yield of 96.4%. Melting point: 300.3°C. The product is 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): In a 150mL single-mouth bottle, intermediate 2 (9.9g, 29mmol), glyoxal aqueous solution (2.7mL, 15mmol), formic acid (0.4mL) and 30mL DMF were added in sequence. The mixture was stirred at room temperature (25°C) for 24h, and then heated to 40°C for 12h. After the reaction was completed, it was filtered, and the filter cake was washed with 50mL DMF and 50mL methyl tert-butyl ether in sequence, and then dried under vacuum at 60°C for 1h to obtain 8.2g of yellow solid with a yield of 80.0%. Melting point: greater than 400°C (decomposition). The product is 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): In a 250mL single-mouth round-bottom flask, the above intermediate 3 (8.5g, 12mmol), paraformaldehyde (0.4g, 13mmol) and 240mL ethyl acetate were added in sequence. The mixture was stirred at 70°C for 1h, and then trimethylsilyl chloride (1.8mL, 13mmol) was added in three batches within 1h. After the addition, the reaction was continued to stir at this temperature for 12h. After the reaction was completed, it was cooled to room temperature, filtered, and the filter cake was slurried with 50mL ethyl acetate, and then vacuum dried at 60°C for 1h to obtain 6.3g of white solid with a yield of 70.5%. Melting point: greater than 400°C (decomposition). The product is 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 protection, CzIPr-HCl monomer (0.8 g, 1 mmol), FDA (1.5 g, 20.0 mmol) and 20 mL of dichloroethane were added to a 50 mL single-necked flask in sequence. After stirring evenly, FeCl3 (3.2 g, 20.0 mmol) was added, and the mixture was stirred at 45 ° C for 5 h, and then heated to 80 ° C for 48 h. After the reaction was completed, it was cooled to room temperature, and the obtained polymer was washed with 20 mL of water and 20 mL of methanol in sequence, and then transferred to a Soxhlet extractor, and washed with methanol as the washing liquid for 24 h. Finally, it was vacuum dried at 80 ° C for 12 h to obtain 1.0 g of black solid, and the polymer was ground into powder.

[0054] Preparation of catalyst 6 (HCP-CzIPr-Ir): Under nitrogen protection, 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 DMF were added to a 80 mL reaction tube in sequence and stirred at 80°C for 24 h. Filter, wash the solid with 20.0 mL THF, and vacuum dry at 80°C for 6 h to obtain a brown solid. The content of metal Ir in the catalyst was 0.47 mmol / g as measured by ICP-MS.

[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] Take 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 1,2-dimethylimidazolinone (DMI) were added to a 50 mL pressure reactor in sequence. The gas in the reactor was replaced with carbon dioxide three times, and then the pressure was increased to 2.0 MPa, and 2.0 MPa of hydrogen was introduced into the reactor. The temperature was raised to 120 ° C and reacted for 24 hours. After the reaction was completed, 5.0 mL of dichloromethane was added to the system, and the mixture was transferred to a centrifuge tube, centrifuged, and the upper liquid was separated. The residual catalyst in the centrifuge tube was washed with 3.0 mL × 2 dichloromethane, and the dichloromethane washings were combined. The solvent was recovered by vacuum rotary evaporation, and the residue was purified by column chromatography (200-300 mesh silica gel, ethyl acetate / petroleum ether as eluent) to obtain N-formylmorpholine with 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 is washed with 3.0mL×2THF, vacuum dried at 80°C for 2h, and can be recycled. The recovered catalyst HCP-CzIPr-Ir, morpholine (0.87mL, 10mmol), and 2.0mL 1,2-dimethylimidazolidinone (DMI) are added to a 50mL pressure reactor in sequence. The gas in the reactor is replaced with carbon dioxide three times, and then the pressure is increased to 2.0MPa, and then 2.0MPa hydrogen is introduced into the reactor. The temperature is raised to 120°C and the reaction is carried out for 24h. After the same post-treatment, the separation yield of N-formylmorpholine is 93%. After the catalyst HCP-CzIPr-Ir is washed with THF and vacuum dried, it can still maintain a high catalytic activity after continuous recycling for 8 times. The results are as follows Fig.11 shown.

Claims

1. A carbazole and carbene iridium bifunctionalized hyper-crosslinked porous organic polymer, referred to as HCP-CzIPr-Ir, with a structural formula as 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, characterized in that: 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, characterized in that: 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, characterized in that: The molar ratio of HCP-CzIPr-HCl to LiHMDS is 1.0:1.0-3.

0.

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

6. Use of the carbazole and carbene iridium bifunctionalized hyper-crosslinked 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 into the reaction kettle, the gas in the reaction kettle was replaced with CO2, and then the pressure was increased to 2.0MPa, and then 2.0MPa H2 was introduced, and the temperature was raised to 120°C for reaction for 24h, and then the reaction liquid was post-treated to obtain the 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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