A carbazolyl biphenyl substituted octafluoro-9h-carbazole derivative, a pi-conjugated porous organic polymer photocatalyst based thereon, and a preparation method and application thereof

Abstract

The present application relates to the technical fields of organic synthesis and photocatalytic material, and discloses a carbazolyl biphenyl substituted octafluoro-9H-carbazole derivative, a pi-conjugated porous organic polymer photocatalyst based on the same, and a preparation method and application thereof.The carbazolyl biphenyl substituted octafluoro-9H-carbazole derivative comprises a biphenyl group, a perfluorocarbazole structural unit and Ar; the photocatalyst comprises a first structural unit and a second structural unit, the first structural unit is derived from the carbazolyl biphenyl substituted octafluoro-9H-carbazole derivative, and the second structural unit is derived from 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyano benzene (4CzIPN) shown in formula (V). The present application also discloses a preparation method of the photocatalyst and application of the photocatalyst in a visible light driven C-N cross coupling reaction of nickel catalyzed aryl halide and amine. The photocatalyst provided by the present application is convenient to separate and recycle, and is suitable for a heterogeneous catalytic system.

Description

Technical Field

[0001] This invention relates to the field of organic synthesis and photocatalytic materials technology, specifically to a carbazole-biphenyl-substituted octafluoro-9H-carbazole derivative, a π-conjugated porous organic polymer photocatalyst based thereon, its preparation method, and its application. Background Technology

[0002] C–N bond formation reactions are an important method for synthesizing aromatic amine compounds and have wide applications in the preparation of drug molecules, fine chemicals and functional materials. Traditional methods such as Buchwald–Hartwig coupling typically rely on palladium catalysts and ligand systems. Although they offer high reaction efficiency, they still suffer from drawbacks such as high cost of precious metals, complex catalytic systems, and stringent requirements for controlling metal residues (Corcoran, EB; Pirnot, MT; Lin, S.; Dreher, SD; DiRocco, DA; Davies, IW; Buchwald, SL; MacMillan, DWC Science, 2016, 353, 279–283.; Oderinde, MS; Jones, NH; Juneau, A.; Frenette, M.; Aquila, B.; Tentarelli, S.; Robbins, DW; Johannes, JW Angew. Chem. Int.Ed., 2016, 55, 13219–13223.). In recent years, the visible light-driven nickel / photoredox dual catalytic strategy has provided a new, mild pathway for the C–N cross-coupling of aryl halides and amines. Related disclosures also include a patent for a method to promote the formation of aryl C–N bonds using light (US11104653B2).

[0003] However, existing visible nickel / photoredox dual-catalytic C–N coupling systems are mostly based on homogeneous photocatalysts, such as Ir, Ru complexes or small-molecule organic photosensitizers. These systems usually suffer from problems such as inconvenient separation and recovery and limited reusability. At the same time, related studies have shown that catalyst deactivation and other factors during dual-catalytic C–N coupling can significantly affect reaction efficiency and applicability (Gisbertz, S.; Reischauer, S.; Pieber, B. Nat. Catal., 2020, 3, 611–620.). To improve catalyst recyclability and develop heterogeneous visible light / Ni dual-catalytic systems, studies have begun to employ solid-state photocatalytic materials or polymer-supported systems. For example, Liu et al. reported a method for achieving C–N and C–O coupling through heterogeneous photoredox / Ni dual catalysis (Liu, Y.-Y.; Liang, D.; Lu, L.-Q.; Xiao, W.-J. Chem.Commun., 2019, 55, 4853–4856.). Furthermore, porous organic polymers, with their high specific surface area, strong structural designability, and good chemical stability, have become an important platform for organic photocatalytic materials. However, existing porous organic polymer photocatalytic systems still generally face the problem of limited photogenerated carrier separation and migration efficiency in organic conversions. On the other hand, the aene–perfluoroarene (AP) interaction, as a classic non-covalent interaction, has been widely used in crystal engineering and molecular assembly research. Related studies have shown that it can affect molecular packing patterns and local electrostatic distribution (Collings, JC; Roscoe, KP; Robins, EG; Batsanov, AS; Stimson, LM; Howard, JAK; Clark, SJ; Marder, TB New J. Chem., 2002, 26, 1740–1746.; Smith, CE; Smith, PS; Thomas, R. Ll.; Robins, EG; Collings, JC; Dai, C.; Scott, AJ; Borwick, S.; Batsanov, AS; Watt, SW; Clark, SJ; Viney, C.; Howard, JAK; Clegg, W.; Marder, TBJ Mater. Chem., 2004, 14, 413–420.).Therefore, it is still necessary to develop a novel recyclable π-conjugated porous organic polymer photocatalyst and its preparation method for use in visible light-driven nickel-catalyzed C–N cross-coupling reactions of aryl halides and amines. Summary of the Invention

[0004] To address the problems of difficulty in recovering homogeneous photocatalysts and limited reusability in existing technologies, as well as the need to improve charge separation and transport efficiency in existing porous organic polymer photocatalytic systems, this invention provides a carbazole-biphenyl-substituted octafluoro-9H-carbazole derivative, a π-conjugated porous organic polymer photocatalyst based thereon, and its preparation method. Furthermore, it provides the application of this photocatalyst in visible light-driven nickel-catalyzed C–N cross-coupling reactions of aryl halides and amines.

[0005] To achieve the above objectives, the present invention adopts the following technical solution: This invention provides a carbazolium-biphenyl-substituted octafluoro-9H-carbazole derivative, wherein the carbazolium-biphenyl-substituted octafluoro-9H-carbazole derivative comprises a biphenyl, a perfluorocarbazole structural unit, and Ar, and has the structure shown in formula (I): Formula (I) Wherein, Ar is 9H-carbazole group; Ar is attached to the ortho, meta, or para position of the benzene ring on the side away from the perfluorocarbazole structural unit in the biphenyl group through its nitrogen atom; the perfluorocarbazole structural unit is 1,2,3,4,5,6,7,8-octafluoro-9H-carbazole structural unit.

[0006] When Ar is located at the ortho, meta, or para position of the benzene ring on the side of the biphenyl ring away from the perfluorocarbazole structural unit, the carbazole-biphenyl-substituted octafluoro-9H-carbazole derivatives are respectively represented as shown in formula (II). o -CBO, as shown in formula (III) m -CBO and formula (IV) are shown p -CBO.

[0007] Equation (II) Equation (III) Formula (IV) The present invention further provides a π-conjugated porous organic polymer photocatalyst, the photocatalyst comprising a first structural unit and a second structural unit, the first structural unit being derived from the carbazolyl biphenyl-substituted octafluoro-9H-carbazole derivative as described in claim 1, and the second structural unit being derived from 1,2,3,5-tetra(carbazo-9-yl)-4,6-dicyanophenyl (4CzIPN) as shown in formula (V); and the first structural unit and the second structural unit are connected by carbon-carbon single bonds on the 9H-carbazole group to form a conjugated network.

[0008] Formula (V) Furthermore, the photocatalyst has three structures: o-CBCP, m-CBCP, or p-CBCP, with structural formulas shown in formulas (VI), (VII), and (VIII), respectively: Formula (VI) Equation (VII) Formula (VIII) Furthermore, the photocatalyst is a solid powder.

[0009] This invention also provides a method for preparing the above-mentioned π-conjugated porous organic polymer photocatalyst, comprising the following steps: Under an inert gas atmosphere, a carbazole-biphenyl-substituted octafluoro-9H-carbazole derivative and 1,2,3,5-tetra(carbazole-9-yl)-4,6-dicyanobenzene are dissolved in an organic solvent to obtain a monomer solution. The obtained monomer solution is added to a ferric chloride dispersion for an oxidative polymerization reaction. After the reaction is completed, the reaction system is quenched, acid-washed, washed, and dried to obtain the π-conjugated porous organic polymer photocatalyst.

[0010] Further, the inert gas is nitrogen; the organic solvent is dichloromethane or chloroform; the reaction temperature of the oxidative polymerization is 20-40 °C, and the reaction time is 48-96 h; the quenching is performed using methanol; the acid washing is performed using hydrochloric acid; and the washing solvent includes water and tetrahydrofuran.

[0011] This invention also provides a visible light-driven nickel-catalyzed C–N cross-coupling reaction method for aryl halides and amines. The method uses the π-conjugated porous organic polymer photocatalyst as a photocatalyst, and under visible light irradiation, uses nickel salt as a metal catalyst to cause the aryl halide and amine to undergo a coupling reaction in a polar aprotic solvent to generate aromatic amine products.

[0012] Further, the aryl halide is an aryl bromide or an aryl iodide; the amine is an aliphatic amine or an aromatic amine; the nickel salt is... The reaction mixture contains one or more of the following: its hydrates or complexes; the polar aprotic solvent is one or more of N,N-dimethylacetamide, N,N-dimethylformamide, and dimethyl sulfoxide; the visible light source is a blue LED light source; the reaction temperature is 25-40 ℃; and the molar ratio of aryl halide: amine: π-conjugated porous organic polymer photocatalyst: nickel salt is 1:2-3:0.00024-0.00049:0.01-0.1.

[0013] Furthermore, when the aryl halide is an aryl iodide and the amine is an aromatic amine, the reaction system further includes an organic base, and the molar ratio of the aryl iodide: aromatic amine: organic base is 1:2:2.

[0014] Furthermore, the organic base is triethylamine.

[0015] Compared with the prior art, the present invention has at least the following beneficial effects: the π-conjugated porous organic polymer photocatalyst provided by the present invention is a solid powder, which is easy to separate and recover from the reaction system; at the same time, this type of photocatalyst can work synergistically with the nickel catalytic system to realize the C-N cross-coupling reaction of aryl halides and amines under visible light irradiation, and has the characteristics of mild conditions, low catalyst dosage and applicability to heterogeneous catalytic systems. Attached Figure Description

[0016] Figure 1 The product prepared in Example 1 p -CBO NMR; Figure 2 The product prepared in Example 1 p -CBO NMR; Figure 3 The product prepared in Example 1 m -CBO NMR; Figure 4 The product prepared in Example 1 m -CBO NMR; Figure 5 The product prepared in Example 1 o -CBO NMR; Figure 6 It is the target aromatic amine product 1 prepared in Example 2. NMR; Figure 7 It is the target aromatic amine product 1 prepared in Example 2. NMR; Figure 8 It is the target aromatic amine product 2 prepared in Example 3. NMR; Figure 9 It is the target aromatic amine product 2 prepared in Example 3. NMR; Figure 10 It is the target aromatic amine product 3 prepared in Example 4. NMR. Detailed Implementation

[0017] The present invention will be further described below with reference to embodiments, but the scope of protection of the present invention is not limited to the following embodiments. Any equivalent substitutions or conventional modifications made by those skilled in the art based on the disclosure of the present invention without departing from the spirit and substance of the invention should fall within the scope of protection of the present invention.

[0018] Example 1 Carbazolylbiphenyl-substituted octafluoro-9H-carbazol derivatives ( o Preparation of -CBO: In a dry flask equipped with a magnetic stirrer, add perfluorinated carbazole borate (0.5 mmol), 9-(2-bromophenyl)-9H-carbazole (1.2 equivalents), (5 mol%) (5 mol%) (3 equivalents) and (3:1, 10 mL). The flask was then evacuated and purged with nitrogen, a process repeated three times. The reaction mixture was stirred in a 70°C oil bath for 12 h. After the reaction was complete, the reaction solution was cooled to room temperature, concentrated under reduced pressure, and purified by rapid column chromatography with a petroleum ether / DCM (dichloromethane) gradient elution (10:1 to 4:1) to give 189 mg of a white solid, 75% yield. Using the same method, replacing the bromide monomer with 9-(3-bromophenyl)-9H-carbazole or 9-(4-bromophenyl)-9H-carbazole, respectively, yielded the following results. m -CBO (75%) and p -CBO (81%).

[0019] Perfluorinated carbazole borate 9-(2-Bromophenyl)-9H-carbazole p -CBO, white solid, 81%.p -CBO NMR spectra as follows Figure 1 As shown, NMR spectra as follows Figure 2 As shown, the NMR data are as follows: NMR (400 MHz, Chloroform-d) δ 8.18 (dt, J = 7.7, 1.0 Hz, 1H), 7.92(d, J = 8.5 Hz, 1H), 7.84 (dd, J = 8.5, 3.9 Hz, 1H), 7.72 (d, J = 8.5 Hz, 1H), 7.61 (d, J = 8.2 Hz, 1H), 7.53 – 7.42 (m, 2H), 7.32 (ddd, J = 7.9, 6.9, 1.2 Hz, 1H). NMR (376 MHz, Chloroform- d ) δ -138.35, -155.87 (t, J = 19.5 Hz), -158.07, -165.08 (d, J = 17.8 Hz). m -CBO, white solid, 75%. m -CBO NMR spectra as follows Figure 3 As shown, NMR spectra as follows Figure 4 As shown, the NMR data are as follows: NMR (400 MHz, Chloroform-d) δ 8.10 (d, J = 7.7 Hz, 2H), 7.82 (s,1H), 7.73 – 7.64 (m, 3H), 7.58 – 7.53 (m, 1H), 7.49 (dt, J = 8.5, 1.3 Hz, 2H),7.44 – 7.34 (m, 4H), 7.25 (ddd, J = 8.0, 6.9, 1.3 Hz, 3H). NMR (376 MHz, Chloroform- d) δ -138.33 – -138.46 (m), -155.87 (t, J = 19.9 Hz), -157.98 (dt, J = 20.8, 6.6 Hz), -165.09 (ddd, J = 20.1, 11.8, 8.2 Hz). o -CBO, white solid, 75%. o -CBO NMR spectra as follows Figure 5 As shown, the NMR data are as follows: NMR (400MHz, Chloroform-d) δ 7.98 (d, J = 7.7 Hz, 2H), 7.74 – 7.67 (m, 1H), 7.62 –7.52 (m, 3H), 7.26 – 7.20 (m, 2H), 7.14 (td, J = 7.5, 1.1 Hz, 2H), 7.06 – 6.99 (m, 4H), 6.98 – 6.93 (m, 2H). π-conjugated porous organic polymer photocatalysts ( o Preparation of CBCP: In a nitrogen atmosphere, o -CBO (125.5 mg, 0.20 mmol) and 4CzIPN (78.9 mg, 0.10 mmol) were dissolved in anhydrous dichloromethane (15 mL) to obtain monomer solutions. Anhydrous... (389.3 mg, 2.40 mmol) was dissolved in dichloromethane (15 mL) to obtain a ferric chloride dispersion. The monomer solution was then added dropwise to the ferric chloride dispersion, and the mixture was stirred at 40 °C for 96 h. The reaction was quenched with methanol (30 mL), and stirring continued for 1 h. The resulting solid was washed with 12 M hydrochloric acid for 2 h, filtered, and then washed three times each with water and tetrahydrofuran (sonicated for 20 min each time). The mixture was then dried under vacuum at 110 °C for 12 h to obtain a yellow powdered polymer. o -CBCP (145 mg, yield approximately 71%). Using the same method, replace the monomer with... m -CBO or p -CBO can be prepared separately. m -CBCP (stirred at 25 ℃ for 72 h, yield: 77%) and p-CBCP (stirred at 20 ℃ for 48 h, quantitative yield).

[0020] Visible light / nickel dual-catalyzed C–N cross-coupling method for aryl bromides and aliphatic amines (Examples 2-19) Example 2 Preparation method of aromatic amine product 1 with the following structural formula: Add 0.20 mmol of 4-bromoacetylbenzene, 0.60 mmol of piperidine, 0.20 mg of o-CBCP, and NiCl2·6H2O (of which 4-bromoacetylbenzene, ...) to a 25 mL Schlenk reaction tube. The molar ratio of o-CBCP was 1:0.05, and N,N-dimethylacetamide (DMAc) (1.0 mL) was added. After ultrasonic dispersion for 30 s, the mixture was evacuated and purged with nitrogen three times. The mixture was then irradiated with a 3 W blue LED (λ=425 nm) at 25 °C and magnetically stirred for 12 h. After the reaction, o-CBCP was recovered by centrifugation and washed. The supernatant was extracted, dried, concentrated, and purified by column chromatography (DCM to DCM / MeOH 40 / 1) to obtain the target aromatic amine product 1, a white solid, 35 mg, 86%.

[0021] Target aromatic amine product 1 NMR spectra as follows Figure 6 As shown, NMR spectra as follows Figure 7 As shown, the NMR data are as follows: NMR (400 MHz, Chloroform-d) δ 7.85 (d, J = 9.0 Hz, 2H), 6.84 (d, J = 9.0 Hz, 2H), 3.35 (m, 4H), 2.50 (s, 3H), 1.66 (m, 6H). NMR (101 MHz, Chloroform-d)δ 196.3, 154.4, 130.5, 126.6, 113.2, 48.6, 26.0, 25.4, 24.4. Example 3 Preparation method of aromatic amine product 2 with the following structural formula: Add 0.20 mmol of 3-bromoacetylbenzene and 0.60 mmol of piperidine to a 25 mL Schlenk reaction tube. o -CBCP (0.20 mg), (including 3-bromoacetylbenzene, The molar ratio of 1:0.05 was used to disperse the product with DMAc (1.0 mL). After ultrasonic dispersion for 30 s, the mixture was evacuated and purged with nitrogen three times. The mixture was then irradiated with a 3 W blue LED (λ=425 nm) at 25 °C and magnetically stirred for 12 h. After the reaction, o-CBCP was recovered by centrifugation and washed. The supernatant was extracted, dried, concentrated, and purified by column chromatography (DCM to DCM / MeOH 40 / 1) to obtain the target aromatic amine product 2, a white solid, 31 mg, 76%.

[0022] Target aromatic amine product 2 NMR spectra as follows Figure 8 As shown, NMR spectra as follows Figure 9 As shown, the NMR data are as follows: NMR (400 MHz, Chloroform-d) δ 7.52 (m, 1H), 7.38 (m, 1H), 7.32 (m, 1H), 7.13(m, 1H), 3.21 (m, 4H), 2.58 (s, 3H), 1.71 (m, 4H), 1.60 (m, 2H). NMR (101MHz, Chloroform-d) δ 198.8, 152.5, 138.1, 129.3, 121.2, 119.4, 115.4, 50.5,26.9, 25.9, 24.4. Example 4: Preparation method of aromatic amine product 3 with the following structural formula: Add 0.20 mmol of 4-bromopropionylbenzene and 0.60 mmol of piperidine to a 25 mL Schlenk reaction tube. o -CBCP (0.20 mg), (including 4-bromopropionylbenzene, The molar ratio of the reagents was 1:0.05, and DMAc (1.0 mL) was added. After ultrasonic dispersion for 30 s, the mixture was evacuated and nitrogen-purged three times. The mixture was then irradiated with a 3 W blue LED (λ=425 nm) at 25 °C and magnetically stirred for 12 h. After the reaction was complete, the product was recovered by centrifugation. o -CBCP and washing; the supernatant was extracted, dried, concentrated and purified by column chromatography (DCM to DCM / MeOH 40 / 1) to obtain the target aromatic amine product 3, white solid, 32 mg, 74%.

[0023] Target aromatic amine product 3 NMR spectra as follows Figure 10As shown, the NMR data are as follows: NMR (400 MHz, Chloroform-d) δ 7.79 (d, J = 9.0 Hz, 2H), 6.77 (m, 2H), 3.27 (t, J = 4.9 Hz, 4H), 2.83 (q, J = 7.3 Hz, 2H), 1.60 (m, 6H), 1.13 (t, J = 7.3 Hz, 3H). NMR(101 MHz, Chloroform-d) δ 199.2, 154.3, 130.1, 126.4, 113.4, 48.7, 31.1,25.4, 24.4, 8.7. Example 5 Preparation method of aromatic amine product 4 with the following structural formula: Add 0.20 mmol of 4-bromobenzoylbenzene and 0.60 mmol of piperidine to a 25 mL Schlenk reaction tube. o -CBCP (0.20 mg), (including 4-bromobenzoylbenzene, The molar ratio of α-CCP to DMAc (1:0.05) was 1:0.05. After ultrasonic dispersion for 30 s, the mixture was evacuated and purged with nitrogen three times. The mixture was then irradiated with a 3 W blue LED (λ=425 nm) at 25 °C and magnetically stirred for 12 h. After the reaction, o-CBCP was recovered by centrifugation and washed. The supernatant was extracted, dried, concentrated, and purified by column chromatography (DCM to DCM / MeOH 40 / 1) to obtain the target aromatic amine product 4, a white solid, 39 mg, 73%.

[0024] The NMR data for target aromatic amine product 4 are as follows: NMR (400 MHz, Chloroform-d) δ 7.76 (m,4H), 7.52 (m, 1H), 7.45 (m, 2H), 6.87 (d, J = 9.0 Hz, 2H), 3.37 (m, 4H), 1.68 (m, 6H). NMR (101 MHz, Chloroform-d) δ 195.2, 154.4, 139.2, 132.8, 131.4,129.6, 128.2, 126.3, 113.3, 48.7, 25.5, 24.5. Example 6 Preparation method of aromatic amine product 5 with the following structural formula: Add methyl p-bromobenzoate (0.20 mmol), piperidine (0.60 mmol), and other reagents to a 25 mL Schlenk reaction tube. o -CBCP (0.20 mg), (including methyl bromobenzoate, The molar ratio of α-CCP to DMAc (1:0.05) was 1:0.05. After ultrasonic dispersion for 30 s, the mixture was evacuated and purged with nitrogen three times. The mixture was then irradiated with a 3 W blue LED (λ=425 nm) at 25 °C and magnetically stirred for 12 h. After the reaction, o-CBCP was recovered by centrifugation and washed. The supernatant was extracted, dried, concentrated, and purified by column chromatography (DCM to DCM / MeOH 40 / 1) to obtain the target aromatic amine product 5, a white solid, 40 mg, 91%.

[0025] The NMR data for the target aromatic amine product 5 are as follows: NMR (400 MHz, Chloroform-d) δ 7.89 (d, J = 9.0 Hz, 2H), 6.84 (d, J = 8.9 Hz, 2H), 3.85 (s, 3H), 3.31 (m, 4H), 1.74 –1.54 (m, 6H). NMR (101 MHz, Chloroform-d) δ 167.3, 154.6, 131.3, 118.8,113.7, 51.6, 48.9, 25.5, 24.4. Example 7 Preparation method of aromatic amine product 6 with the following structural formula: Add 0.20 mmol of 4-bromobenzonitrile and 0.60 mmol of piperidine to a 25 mL Schlenk reaction tube. o -CBCP (0.20 mg), (including 4-bromobenzonitrile, The molar ratio of 1:0.05 was used to disperse the product with DMAc (1.0 mL). After ultrasonic dispersion for 30 s, the mixture was evacuated and purged with nitrogen three times. The mixture was then irradiated with a 3 W blue LED (λ=425 nm) at 25 °C and magnetically stirred for 12 h. After the reaction, o-CBCP was recovered by centrifugation and washed. The supernatant was extracted, dried, concentrated, and purified by column chromatography (DCM to DCM / MeOH 40 / 1) to obtain the target aromatic amine product 6, a white solid, 30 mg, 81%.

[0026] The NMR data for the target aromatic amine product 6 are as follows: NMR (400 MHz, Chloroform-d) δ 7.45 (d, J = 9.0 Hz, 2H), 6.83 (d, J = 9.0 Hz, 2H), 3.32 (m, 4H), 1.66 (m, 6H). NMR (101 MHz, Chloroform-d) δ 153.6, 133.5, 120.4, 114.1, 98.9, 48.4, 25.3, 24.3. Example 8 Preparation method of aromatic amine product 7 with the following structural formula: Add 0.20 mmol of 4-bromotrifluorotoluene and 0.60 mmol of piperidine to a 25 mL Schlenk reaction tube. o -CBCP (0.20 mg), (including 4-bromotrifluorotoluene, The molar ratio of the reagents was 1:0.05, and DMAc (1.0 mL) was added. After ultrasonic dispersion for 30 s, the mixture was evacuated and nitrogen-purged three times. The mixture was then irradiated with a 3 W blue LED (λ=425 nm) at 25 °C and magnetically stirred for 12 h. After the reaction was complete, the product was recovered by centrifugation. o -CBCP and washing; the supernatant was extracted, dried, concentrated and purified by column chromatography (Pe / DCM 3 / 1→DCM) to obtain the target aromatic amine product 7, white solid, 37 mg, 81%.

[0027] The NMR data for the target aromatic amine product 7 are as follows: NMR (400 MHz, Chloroform-d) δ 7.37 (d, J = 8.5 Hz, 2H), 6.83 (d, J = 8.5 Hz, 2H), 3.18 (m, 4H), 1.58 (m, 6H). NMR(101 MHz, Chloroform-d) δ 153.9, 126.4 (q, J = 4.0 Hz), 125.0 (q, J = 271.7Hz), 119.6 (q, J = 32.3 Hz), 114.7, 119.5, 114.7, 49.4, 25.6, 24.4. Example 9 Preparation method of aromatic amine product 8 with the following structural formula: Add 4-bromobenzyl sulfone (0.20 mmol), piperidine (0.60 mmol), and [other ingredients] to a 25 mL Schlenk reaction tube. o -CBCP (0.20 mg), (including 4-bromophenyl sulfone, The molar ratio of 1:0.05 was used to disperse the product with DMAc (1.0 mL). After ultrasonic dispersion for 30 s, the mixture was evacuated and purged with nitrogen three times. The mixture was then irradiated with a 3 W blue LED (λ=425 nm) at 25 °C and magnetically stirred for 12 h. After the reaction, o-CBCP was recovered by centrifugation and washed. The supernatant was extracted, dried, concentrated, and purified by column chromatography (DCM to DCM / MeOH 40 / 1) to obtain the target aromatic amine product 8, a white solid, 43 mg, 90%.

[0028] The NMR data for the target aromatic amine product 8 are as follows: NMR (400 MHz, Chloroform-d) δ 7.70 (d, J = 9.1 Hz, 2H), 6.88 (d, J = 9.0 Hz, 2H), 3.34 (m, 4H), 2.98 (s, 3H), 1.64 (m, 6H). NMR (101 MHz, Chloroform-d) δ 154.5, 129.1, 127.4, 113.7, 48.6, 45.1,25.3, 24.3. Example 10 Preparation method of aromatic amine product 9 with the following structural formula: Add 0.20 mmol of 4-bromobenzamide and 0.60 mmol of piperidine to a 25 mL Schlenk reaction tube. o-CBCP (0.20 mg), (including 4-bromobenzamide, The molar ratio of 1:0.05 was used to disperse the product with DMAc (1.0 mL). After ultrasonic dispersion for 30 s, the mixture was evacuated and purged with nitrogen three times. The mixture was then irradiated with a 3 W blue LED (λ=425 nm) at 25 °C and magnetically stirred for 12 h. After the reaction, o-CBCP was recovered by centrifugation and washed. The supernatant was extracted, dried, concentrated, and purified by column chromatography (DCM / MeOH 30 / 1→10 / 1) to obtain the target aromatic amine product 9, a white solid, 31 mg, 76%.

[0029] The NMR data for the target aromatic amine product 9 are as follows: NMR (400 MHz, Chloroform-d) δ 7.72 (d, J = 8.0 Hz, 3H), 7.66 (s, 1H), 6.97 (s, 1H), 6.90 (d, J = 8.0 Hz, 3H), 3.26 (m, 6H), 1.57 (m, 6H). NMR (101 MHz, Chloroform-d) δ 167.7, 153.0, 128.9,122.8, 113.5, 48.3, 24.9, 23.9. Example 11 Preparation method of aromatic amine product 10 with the following structural formula: Add 0.20 mmol of 4-bromochlorobenzene and 0.60 mmol of piperidine to a 25 mL Schlenk reaction tube. o -CBCP (0.20 mg), (including 4-bromochlorobenzene, The molar ratio of o-CBCP was 1:0.05, and DMAc (1.0 mL) was added. After ultrasonic dispersion for 30 s, the mixture was evacuated and purged with nitrogen three times. The mixture was then irradiated with a 3 W blue LED (λ=425 nm) at 25 °C and magnetically stirred for 12 h. After the reaction, o-CBCP was recovered by centrifugation and washed. The supernatant was extracted, dried, concentrated, and purified by column chromatography (Pe / DCM 5 / 1→2 / 1) to obtain the target aromatic amine product 10, a white solid, 27 mg, 69%.

[0030] The NMR data for the target aromatic amine product 10 are as follows: NMR (400 MHz, Chloroform-d) δ 7.22 (d, J= 8.4 Hz, 2H), 6.85 (d, J = 8.4 Hz, 2H), 3.13 (m, 4H), 1.71 (m, 4H), 1.58(m, 2H). NMR (101 MHz, Chloroform-d) δ 150.9, 128.9, 123.9, 117.7, 50.7,25.8, 24.3. Example 12 Preparation method of aromatic amine product 11 with the following structural formula: Add p-dibromobenzene (0.20 mmol), piperidine (0.60 mmol), and [other ingredients] to a 25 mL Schlenk reaction tube. o -CBCP (0.20 mg), (including p-dibromobenzene, The molar ratio of o-CBCP was 1:0.05, and DMAc (1.0 mL) was added. After ultrasonic dispersion for 30 s, the mixture was evacuated and purged with nitrogen three times. The mixture was then irradiated with a 3 W blue LED (λ=425 nm) at 25 °C and magnetically stirred for 12 h. After the reaction, o-CBCP was recovered by centrifugation and washed. The supernatant was extracted, dried, concentrated, and purified by column chromatography (Pe / DCM 5 / 1→2 / 1) to obtain the target aromatic amine product 11, a white solid, 31 mg, 65%.

[0031] The NMR data for the target aromatic amine product 11 are as follows: NMR (400 MHz, Chloroform-d) δ 7.31 (d, J = 9.0 Hz, 2H), 6.79 (d, J = 9.0 Hz, 2H), 3.12 (m, 4H), 1.69 (m, 4H), 1.59(m, 2H). NMR (101 MHz, Chloroform-d) δ 151.3, 131.9, 118.1, 111.2, 50.6,25.8, 24.3. Example 13 Preparation method of aromatic amine product 12 with the following structural formula: Add 0.20 mmol of 4-fluorobromobenzene and 0.60 mmol of piperidine to a 25 mL Schlenk reaction tube. o -CBCP (0.20 mg), (including 4-fluorobromobenzene, The molar ratio of o-CBCP was 1:0.05, and DMAc (1.0 mL) was added. After ultrasonic dispersion for 30 s, the mixture was evacuated and purged with nitrogen three times. The mixture was then irradiated with a 3 W blue LED (λ=425 nm) at 25 °C and magnetically stirred for 12 h. After the reaction, o-CBCP was recovered by centrifugation and washed. The supernatant was extracted, dried, concentrated, and purified by column chromatography (Pe / DCM 5 / 1→2 / 1) to obtain the target aromatic amine product 12, a white solid, 10 mg, 28%.

[0032] The NMR data for the target aromatic amine product 12 are as follows: NMR (400 MHz, Chloroform-d) δ 6.90 (m,4H), 3.06 (m, 4H), 1.72 (m, 4H), 1.55 (m, 2H). NMR (101 MHz, Chloroform-d)δ 157.1 (d, J = 239.4 Hz), 149.2, 118.5 (d, J = 8.1 Hz), 118.4, 115.5 (d, J =22.2 Hz), 51.9, 26.1, 24.3. Example 14 Preparation method of aromatic amine product 13 with the following structural formula: Add 0.20 mmol of 3-bromopyridine and 0.60 mmol of piperidine to a 25 mL Schlenk reaction tube. o -CBCP (0.20 mg), (including 3-bromopyridine, The molar ratio of 1:0.05 was used to disperse the product with DMAc (1.0 mL). After ultrasonic dispersion for 30 s, the mixture was evacuated and purged with nitrogen three times. The mixture was then irradiated with a 3 W blue LED (λ=425 nm) at 25 °C and magnetically stirred for 12 h. After the reaction, o-CBCP was recovered by centrifugation and washed. The supernatant was extracted, dried, concentrated, and purified by column chromatography (DCM / MeOH 60 / 1→30 / 1) to obtain the target aromatic amine product 13, a white solid, 19 mg, 59%.

[0033] The NMR data for the target aromatic amine product 13 are as follows: NMR (400 MHz, Chloroform-d) δ 8.30 (d, J= 2.9 Hz, 1H), 8.04 (m, 1H), 7.15 (m, 2H), 3.17 (m, 4H), 1.70 (m, 4H), 1.59(m, 2H). NMR (101 MHz, Chloroform-d) δ 147.8, 140.1, 139.1, 123.5, 122.7,49.9, 25.7, 24.2. Example 15 Preparation method of aromatic amine product 14 with the following structural formula: Add 0.20 mmol of 4-bromoacetylbenzene and 0.60 mmol of pyrrolidine to a 25 mL Schlenk reaction tube. o -CBCP (0.20 mg), (including 4-bromoacetylbenzene, The molar ratio of 1:0.05 was used to disperse the product with DMAc (1.0 mL). After ultrasonic dispersion for 30 s, the mixture was evacuated and purged with nitrogen three times. The mixture was then irradiated with a 3 W blue LED (λ=425 nm) at 25 °C and magnetically stirred for 12 h. After the reaction, o-CBCP was recovered by centrifugation and washed. The supernatant was extracted, dried, concentrated, and purified by column chromatography (DCM to DCM / MeOH 40 / 1) to obtain the target aromatic amine product 14, a white solid, 35 mg, 92%.

[0034] The NMR data for the target aromatic amine product 14 are as follows: NMR (400 MHz, Chloroform-d) δ 7.86 (d, J = 9.0 Hz, 2H), 6.52 (d, J = 8.9 Hz, 2H), 3.36 (m, 4H), 2.50 (s, 3H), 2.04(m, 4H). NMR (101 MHz, Chloroform-d) δ 196.4, 151.1, 130.8, 125.1, 110.8, 47.7, 26.1, 25.6. Example 16 Preparation method of aromatic amine product 15 with the following structural formula: Add 0.20 mmol of 4-bromoacetylbenzene and 0.60 mmol of morpholine to a 25 mL Schlenk reaction tube. o-CBCP (0.20 mg), (including 4-bromoacetylbenzene, The molar ratio of 1:0.05 was used to disperse the product with DMAc (1.0 mL). After ultrasonic dispersion for 30 s, the mixture was evacuated and purged with nitrogen three times. The mixture was then irradiated with a 3 W blue LED (λ=425 nm) at 25 °C and magnetically stirred for 12 h. After the reaction, o-CBCP was recovered by centrifugation and washed. The supernatant was extracted, dried, concentrated, and purified by column chromatography (DCM to DCM / MeOH 40 / 1) to obtain the target aromatic amine product 15, a white solid, 29 mg, 71%.

[0035] The NMR data for the target aromatic amine product 15 are as follows: NMR (400 MHz, Chloroform-d) δ 7.89 (d, J = 9.0 Hz, 2H), 6.86 (d, J = 9.0 Hz, 2H), 3.85 (m, 4H), 3.30 (m, 4H), 2.52(s, 3H). NMR (101 MHz, Chloroform-d) δ 196.5, 154.2, 130.4, 128.2, 113.3, 66.6, 47.6, 26.2. Example 17 Preparation method of aromatic amine product 16 with the following structural formula: Add 0.20 mmol of 4-bromoacetylbenzyl and 0.60 mmol of N-methylbenzylamine to a 25 mL Schlenk reaction tube. o -CBCP (0.20 mg), (including 4-bromoacetylbenzene, The molar ratio of 1:0.05 was used to disperse the product with DMAc (1.0 mL). After ultrasonic dispersion for 30 s, the mixture was evacuated and purged with nitrogen three times. The mixture was then irradiated with a 3 W blue LED (λ=425 nm) at 25 °C and magnetically stirred for 12 h. After the reaction, o-CBCP was recovered by centrifugation and washed. The supernatant was extracted, dried, concentrated, and purified by column chromatography (DCM→DCM / MeOH 20 / 1) to obtain the target aromatic amine product 16, a white solid, 38 mg, 79%.

[0036] The NMR data for the target aromatic amine product 16 are as follows: NMR (400 MHz, Chloroform-d) δ 7.88 (d, J= 8.0 Hz, 2H), 7.36 (m, 2H), 7.29 (m, 1H), 7.21 (m, 2H), 6.73 (m, 2H), 4.66(s, 2H), 3.16 (s, 3H), 2.52 (s, 3H). NMR (101 MHz, Chloroform-d) δ 196.3, 152.9, 137.6, 130.7, 128.8, 127.3, 126.5, 125.8, 110.9, 55.9, 38.8, 26.1. Example 18 Preparation method of aromatic amine product 17 with the following structural formula: Add 0.20 mmol of 4-bromoacetylbenzene and 0.60 mmol of cyclohexylamine to a 25 mL Schlenk reaction tube. o -CBCP (0.20 mg), (including 4-bromoacetylbenzene, The molar ratio of 1:0.05 was used to disperse the product with DMAc (1.0 mL). After ultrasonic dispersion for 30 s, the mixture was evacuated and purged with nitrogen three times. The mixture was then irradiated with a 3 W blue LED (λ=425 nm) at 25 °C and magnetically stirred for 12 h. After the reaction, o-CBCP was recovered by centrifugation and washed. The supernatant was extracted, dried, concentrated, and purified by column chromatography (DCM / MeOH 40 / 1→15 / 1) to obtain the target aromatic amine product 17, a white solid, 23 mg, 53%.

[0037] The NMR data for the target aromatic amine product 17 are as follows: NMR (400 MHz, Chloroform-d) δ 7.79 (d, J = 8.8 Hz, 2H), 6.52 (d, J = 8.8 Hz, 2H), 4.17 (s, 1H), 3.36 (m, 1H), 2.48(s, 3H), 2.04 (m, 2H), 1.77 (m, 2H), 1.66 (m, 1H), 1.39 (m, 2H), 1.21 (m,3H). NMR (101 MHz, Chloroform-d) δ 196.3, 151.5, 131.0, 126.3, 111.7, 51.4,33.2, 26.1, 25.8, 24.9. Example 19 Preparation method of aromatic amine product 18 with the following structural formula: Add 0.20 mmol of 4-bromoacetylbenzene and 0.60 mmol of n-hexylamine to a 25 mL Schlenk reaction tube. o -CBCP (0.20 mg), (including 4-bromoacetylbenzene, The molar ratio of 1:0.05 was used to disperse the product with DMAc (1.0 mL). After ultrasonic dispersion for 30 s, the mixture was evacuated and purged with nitrogen three times. The mixture was then irradiated with a 3 W blue LED (λ=425 nm) at 25 °C and magnetically stirred for 12 h. After the reaction, o-CBCP was recovered by centrifugation and washed. The supernatant was extracted, dried, concentrated, and purified by column chromatography (DCM / MeOH 40 / 1→15 / 1) to obtain the target aromatic amine product 18, a white solid, 34 mg, 77%.

[0038] The NMR data for the target aromatic amine product 18 are as follows: NMR (400 MHz, Chloroform-d) δ 7.82 (d, J = 8.8 Hz, 2H), 6.54 (d, J = 8.8 Hz, 2H), 4.17 (s, 1H), 3.17 (m, 2H), 2.50(s, 3H), 1.65 (m, 2H), 1.57 (s, 1H), 1.35 (m, 6H), 0.90 (m, 3H). NMR (101MHz, Chloroform-d) δ 196.3, 152.3, 130.8, 126.5, 111.2, 43.3, 31.6, 29.3,26.7, 25.9, 22.6, 14.0. Visible light / nickel dual-catalyzed C–N cross-coupling method of aryl iodides and aromatic amines (Examples 20-31) Example 20 Preparation method of aromatic amine product 19 with the following structural formula: Add iodobenzene (0.20 mmol) and aniline (0.40 mmol) to a 25 mL Schlenk flask. o -CBCP (0.10mg), (including iodobenzene, The molar ratio of the compounds was 1:0.05, triethylamine (2 equiv.) and DMAc (1.0 mL). After ultrasonic dispersion for 30 s, the mixture was evacuated and purged with nitrogen three times, then irradiated with a 3 W blue LED (λ=425 nm) at 25 °C and magnetically stirred for 12 h. After the reaction, o-CBCP was recovered by centrifugation and washed; the supernatant was extracted, dried, concentrated and purified by column chromatography (Pe / DCM 3 / 1 to 1 / 1) to obtain the target aromatic amine product 19, a white solid, 30 mg, 89%.

[0039] The NMR data for the target aromatic amine product 19 are as follows: NMR (400 MHz, Chloroform-d) δ 7.31 (m,4H), 7.11 (m, 4H), 6.97 (m, 2H), 5.71 (s, 1H). NMR (101 MHz, Chloroform-d)δ 143.2, 129.5, 121.1, 117.9. Example 21 Preparation method of aromatic amine product 20 with the following structural formula: Add 0.20 mmol of 4-methoxyiodobenzene and 0.40 mmol of aniline to a 25 mL Schlenk flask. o -CBCP (0.10 mg), (including 4-methoxyiodobenzene, The molar ratio of o-CBCP was 1:0.05, triethylamine (2 equiv.) and DMAc (1.0 mL). After ultrasonic dispersion for 30 s, the mixture was evacuated and purged with nitrogen three times, then irradiated with a 3 W blue LED (λ=425 nm) at 25 °C and magnetically stirred for 12 h. After the reaction, o-CBCP was recovered by centrifugation and washed; the supernatant was extracted, dried, concentrated and purified by column chromatography (Pe / DCM 3 / 1 to 1 / 1) to obtain the target aromatic amine product 20, a white solid, 26 mg, 65%.

[0040] The NMR data for the target aromatic amine product 20 are as follows: NMR (400 MHz, Chloroform-d) δ 7.22 (m,2H), 7.09 (m, 2H), 6.88 (m, 5H), 5.50 (s, 1 H), 3.81 (s, 3H). NMR (101 MHz, Chloroform-d) δ 155.4, 145.3, 135.8, 129.4, 122.3, 119.7, 115., 114.8, 55.7. Example 22 Preparation method of aromatic amine product 21 with the following structural formula: Add 0.20 mmol of 4-tert-butyliodobenzene and 0.40 mmol of aniline to a 25 mL Schlenk flask. o -CBCP (0.10 mg), (including 4-tert-butyliodobenzene, The molar ratio of the compounds was 1:0.05, triethylamine (2 equiv.) and DMAc (1.0 mL). After ultrasonic dispersion for 30 s, the mixture was evacuated and purged with nitrogen three times. The mixture was then irradiated with a 3 W blue LED (λ=425 nm) at 25 °C and magnetically stirred for 12 h. After the reaction, o-CBCP was recovered by centrifugation and washed. The supernatant was extracted, dried, concentrated, and purified by column chromatography (Pe / DCM 3 / 1 to 1 / 1) to obtain the target aromatic amine product 21, a white solid, 31 mg, 69%.

[0041] The NMR data for the target aromatic amine product 21 are as follows: NMR (400 MHz, Chloroform-d) δ 7.18 (m,4H), 6.95 (m, 4H), 6.80 (m, 1H), 5.53 (s, 1H), 1.23 (s, 9H). NMR (101 MHz, Chloroform-d) δ 144.3, 143.9, 140.5, 129.4, 126.3, 120.5, 118.3, 117.3, 34.3,31.6. Example 23 Preparation method of aromatic amine product 22 with the following structural formula: Add p-methyliodobenzene (0.20 mmol), aniline (0.40 mmol), and other ingredients to a 25 mL Schlenk flask. o -CBCP (0.10 mg), (including p-methyliodobenzene, The molar ratio of the compounds was 1:0.05, triethylamine (2 equiv.) and DMAc (1.0 mL). After ultrasonic dispersion for 30 s, the mixture was evacuated and purged with nitrogen three times, then irradiated with a 3 W blue LED (λ=425 nm) at 25 °C and magnetically stirred for 12 h. After the reaction, o-CBCP was recovered by centrifugation and washed; the supernatant was extracted, dried, concentrated and purified by column chromatography (Pe / DCM 3 / 1 to 1 / 1) to obtain the target aromatic amine product 22, a white solid, 24 mg, 65%.

[0042] The NMR data for the target aromatic amine product 22 are as follows: NMR (400 MHz, Chloroform-d) δ 7.16 (m,2H), 7.01 (m, 2H), 6.91 (m, 4H), 6.79 (m, 1H), 5.50 (s, 1H), 2.22 (s, 3H). NMR (101 MHz, Chloroform-d) δ 144.0, 140.3, 130.9, 129.9, 129.3, 120.3,118.9, 116.9, 20.7. Example 24 Preparation method of aromatic amine product 23 with the following structural formula: Add p-chloroiodobenzene (0.20 mmol), aniline (0.40 mmol), and other ingredients to a 25 mL Schlenk flask. o -CBCP (0.10 mg), (including chloriodobenzene, The molar ratio of the compounds was 1:0.05, triethylamine (2 equiv.) and DMAc (1.0 mL). After ultrasonic dispersion for 30 s, the mixture was evacuated and purged with nitrogen three times, then irradiated with a 3 W blue LED (λ=425 nm) at 25 °C and magnetically stirred for 12 h. After the reaction, o-CBCP was recovered by centrifugation and washed; the supernatant was extracted, dried, concentrated and purified by column chromatography (Pe / DCM 3 / 1 to 1 / 1) to obtain the target aromatic amine product 23, a white solid, 37 mg, 91%.

[0043] The NMR data for the target aromatic amine product 23 are as follows: NMR (400 MHz, Chloroform-d) δ 7.25 (m,2H), 7.17 (m, 2H), 7.01 (m, 2H), 6.91 (m, 3H), 5.61 (s, 1H). NMR (101 MHz, Chloroform-d) δ 142.7, 141.9, 129.6, 129.4, 125.6, 121.6, 118.9, 118.2. Example 25 Preparation method of aromatic amine product 24 with the following structural formula: Add p-trifluoromethyliodobenzene (0.20 mmol), aniline (0.40 mmol), and other ingredients to a 25 mL Schlenk flask. o -CBCP (0.10 mg), (including trifluoromethyliodobenzene, The molar ratio of the compounds was 1:0.05, triethylamine (2 equiv.) and DMAc (1.0 mL). After ultrasonic dispersion for 30 s, the mixture was evacuated and purged with nitrogen three times, then irradiated with a 3 W blue LED (λ=425 nm) at 25 °C and magnetically stirred for 12 h. After the reaction, o-CBCP was recovered by centrifugation and washed; the supernatant was extracted, dried, concentrated and purified by column chromatography (Pe / DCM 3 / 1 to 1 / 1) to obtain the target aromatic amine product 24, a white solid, 39 mg, 82%.

[0044] The NMR data for the target aromatic amine product 24 are as follows: NMR (400 MHz, Chloroform-d) δ 7.38 (d, J = 8.5 Hz, 2H), 7.24 (m, 2H), 7.06 (m, 2H), 6.93 (m, 3H), 5.81 (s, 1H). NMR (101 MHz, Chloroform-d) δ 146.8, 141.2, 129.6, 126.71 (q, J = 4.0 Hz), 124.6 (q, J = 271.7 Hz), 122.9, 121.67 (q, J = 32.3 Hz), 120.1, 115.4. Example 26 Preparation method of aromatic amine product 25 with the following structural formula Add iodobenzene (0.20 mmol) and p-methylaniline (0.40 mmol) to a 25 mL Schlenk flask. o -CBCP (0.10 mg), (including iodobenzene, The molar ratio of the compounds was 1:0.05, triethylamine (2 equiv.) and DMAc (1.0 mL). After ultrasonic dispersion for 30 s, the mixture was evacuated and purged with nitrogen three times, then irradiated with a 3 W blue LED (λ=425 nm) at 25 °C and magnetically stirred for 12 h. After the reaction, o-CBCP was recovered by centrifugation and washed; the supernatant was extracted, dried, concentrated and purified by column chromatography (Pe / DCM 3 / 1 to 1 / 1) to obtain the target aromatic amine product 25, a white solid, 32 mg, 87%.

[0045] The NMR data for the target aromatic amine product 25 are as follows: NMR (400 MHz, Chloroform-d) δ 7.13 (m,2H), 6.98 (m, 2H), 6.90 (m, 4H), 6.78 (m, 1H), 5.46 (s, 1H), 2.20 (s, 3H). NMR (101 MHz, Chloroform-d) δ 144.0, 140.4, 130.9, 129.9, 129.4, 120.4,118.9, 116.9, 20.8. Example 27 The preparation method of the aromatic amine product 26 with the following structural formula: Add iodobenzene (0.20 mmol) and m-methylaniline (0.40 mmol) to a 25 mL Schlenk flask. o -CBCP (0.10 mg), (including iodobenzene, The molar ratio of the compounds was 1:0.05, triethylamine (2 equiv.) and DMAc (1.0 mL). After ultrasonic dispersion for 30 s, the mixture was evacuated and purged with nitrogen three times, then irradiated with a 3 W blue LED (λ=425 nm) at 25 °C and magnetically stirred for 12 h. After the reaction, o-CBCP was recovered by centrifugation and washed; the supernatant was extracted, dried, concentrated and purified by column chromatography (Pe / DCM 3 / 1 to 1 / 1) to obtain the target aromatic amine product 26, a white solid, 28 mg, 76%.

[0046] The NMR data for the target aromatic amine product 26 are as follows: NMR (400 MHz, Chloroform-d) δ 7.32 (m,2H), 7.21 (m, 1H), 7.13 (m, 2H), 6.98 (m, 3H), 6.82 (d, J= 7.5 Hz, 1H), 5.68(s, 1H), 2.37 (s, 3H). NMR (101 MHz, Chloroform-d) δ 143.4, 143.2, 139.3,129.4, 129.3, 121.9, 120.9, 118.6, 117.9, 115.0, 21.6. Example 28 Preparation method of aromatic amine product 27 with the following structural formula: Add iodobenzene (0.20 mmol) and o-methylaniline (0.40 mmol) to a 25 mL Schlenk flask. o -CBCP (0.10 mg), (including iodobenzene, The molar ratio of the compounds was 1:0.05, triethylamine (2 equiv.) and DMAc (1.0 mL). After ultrasonic dispersion for 30 s, the mixture was evacuated and purged with nitrogen three times, then irradiated with a 3 W blue LED (λ=425 nm) at 25 °C and magnetically stirred for 12 h. After the reaction, o-CBCP was recovered by centrifugation and washed; the supernatant was extracted, dried, concentrated and purified by column chromatography (Pe / DCM 3 / 1 to 1 / 1) to obtain the target aromatic amine product 27, a white solid, 15 mg, 41%.

[0047] The NMR data for the target aromatic amine product 27 are as follows: NMR (400 MHz, Chloroform-d) δ 7.23 (m,4H), 7.11 (m, 1H), 6.87 (m, 4H), 5.36 (s, 1H), 2.25 (s, 3H). NMR (101 MHz, Chloroform-d) δ 144.1, 141.3, 131.1, 129.4, 128.4, 126.9, 122.1, 120.6,118.9, 117.6, 18.0. Example 29 Preparation method of aromatic amine product 28 with the following structural formula: Add iodobenzene (0.20 mmol) and 4-fluoroaniline (0.40 mmol) to a 25 mL Schlenk flask. o -CBCP (0.10 mg), (including iodobenzene, The molar ratio of the compounds was 1:0.05, triethylamine (2 equiv.) and DMAc (1.0 mL). After ultrasonic dispersion for 30 s, the mixture was evacuated and purged with nitrogen three times, then irradiated with a 3 W blue LED (λ=425 nm) at 25 °C and magnetically stirred for 12 h. After the reaction, o-CBCP was recovered by centrifugation and washed; the supernatant was extracted, dried, concentrated and purified by column chromatography (Pe / DCM 3 / 1 to 1 / 1) to obtain the target aromatic amine product 28, a white solid, 20 mg, 53%.

[0048] The NMR data for the target aromatic amine product 28 are as follows: NMR (400 MHz, Chloroform-d) δ 7.24 (m,2H), 7.04 (m, 2H), 6.94 – 6.84 (m, 4H), 6.90 (m, 1H), 5.55 (s, 1H). NMR (101 MHz, Chloroform-d) δ 158.2 (d, J = 241.4 Hz), 144.1, 139.1 (d, J = 3.0Hz), 129.5, 120.7, 120.6, 116.9, 116.1 (d, J = 22.2 Hz). Example 30 The preparation method of the aromatic amine product 29 with the following structural formula: Add iodobenzene (0.20 mmol) and 4-chloroaniline (0.40 mmol) to a 25 mL Schlenk flask. o -CBCP (0.10 mg), (including iodobenzene, The molar ratio of the compounds was 1:0.05, triethylamine (2 equiv.) and DMAc (1.0 mL). After ultrasonic dispersion for 30 s, the mixture was evacuated and purged with nitrogen three times. The mixture was then irradiated with a 3 W blue LED (λ=425 nm) at 25 °C and magnetically stirred for 12 h. After the reaction, o-CBCP was recovered by centrifugation and washed. The supernatant was extracted, dried, concentrated, and purified by column chromatography (Pe / DCM 3 / 1 to 1 / 1) to obtain the target aromatic amine product 29, a white solid, 28 mg, 69%.

[0049] The NMR data for the target aromatic amine product 29 are as follows: NMR (400 MHz, Chloroform-d) δ 7.28 (m,2H), 7.23 (m, 2H), 7.06 (m, 2H), 6.98 (m, 3H), 5.67 (s, 1H). NMR (101 MHz, Chloroform-d) δ 142.8, 141.9, 129.6, 129.4, 125.6, 121.6, 118.9, 118.2. Example 31 Preparation method of aromatic amine product 30 with the following structural formula: Add iodobenzene (0.20 mmol) and 3,4-dichloroaniline (0.40 mmol) to a 25 mL Schlenk flask. o -CBCP (0.10 mg), (including iodobenzene, The molar ratio of the compounds was 1:0.05, triethylamine (2 equiv.) and DMAc (1.0 mL). After ultrasonic dispersion for 30 s, the mixture was evacuated and purged with nitrogen three times, then irradiated with a 3 W blue LED (λ=425 nm) at 25 °C and magnetically stirred for 12 h. After the reaction, o-CBCP was recovered by centrifugation and washed; the supernatant was extracted, dried, concentrated and purified by column chromatography (Pe / DCM 3 / 1 to 1 / 1) to obtain the target aromatic amine product 30, a white solid, 28 mg, 59%.

[0050] The NMR data for the target aromatic amine product 30 are as follows: NMR (400 MHz, Chloroform-d) δ 7.20 (m,3H), 7.05 (d, J = 2.7 Hz, 1H), 6.97 (m, 3H), 6.78 (m, 1H), 5.61 (s, 1H). NMR(101 MHz, Chloroform-d) δ 143.4, 141.7, 133.1, 130.9, 129.7, 123.2, 122.6,119.3, 118.2, 116.5. Recovery and recycling of polymer catalysts Example 32 Taking Examples 2-19 above as an example, the product is recovered by centrifugation after the reaction is completed. o-CBCP solid was directly added to the next reaction after being centrifuged and washed twice with the polar aprotic solvent N,N-dimethylacetamide (DMAc). In multiple cycles, the product yield showed only a slight decrease, indicating that the π-conjugated porous organic polymer photocatalyst framework is stable and suitable for repeated use.

Claims

1. A carbazole-biphenyl-substituted octafluoro-9H-carbazole derivative, characterized in that, The carbazolylbiphenyl-substituted octafluoro-9H-carbazole derivative comprises a biphenyl, a perfluorocarbazole structural unit, and Ar, and has the structure shown in formula (I): Formula (I) Wherein, Ar is 9H-carbazole group; Ar is attached to the ortho, meta, or para position of the benzene ring on the side away from the perfluorocarbazole structural unit in the biphenyl group through its nitrogen atom; the perfluorocarbazole structural unit is 1,2,3,4,5,6,7,8-octafluoro-9H-carbazole structural unit.

2. A π-conjugated porous organic polymer photocatalyst, characterized in that, The photocatalyst comprises a first structural unit and a second structural unit, wherein the first structural unit is derived from the carbazolyl biphenyl-substituted octafluoro-9H-carbazolyl derivative as described in claim 1, and the second structural unit is derived from 1,2,3,5-tetra(carbazo-9-yl)-4,6-dicyanophenyl (4CzIPN) as shown in formula (V); and the first structural unit and the second structural unit are connected by carbon-carbon single bonds on the 9H-carbazolyl group to form a conjugated network. Formula (V).

3. The π-conjugated porous organic polymer photocatalyst as described in claim 2, characterized in that, The photocatalyst has o -CBCP m -CBCP or p -CBCP has three structures, as shown in equations (VI), (VII), and (VIII) respectively: Formula (VI) Equation (VII) Formula (VIII).

4. The π-conjugated porous organic polymer photocatalyst as described in claim 3, characterized in that, The photocatalyst is a solid powder.

5. A method for preparing the π-conjugated porous organic polymer photocatalyst as described in claims 2-4, characterized in that, The process includes the following steps: Under an inert gas atmosphere, a carbazole-biphenyl-substituted octafluoro-9H-carbazole derivative and 1,2,3,5-tetra(carbazole-9-yl)-4,6-dicyanobenzene are dissolved in an organic solvent to obtain a monomer solution. The obtained monomer solution is added to a ferric chloride dispersion for oxidative polymerization. After the reaction is completed, the reaction system is quenched, acid-washed, washed, and dried to obtain the π-conjugated porous organic polymer photocatalyst.

6. The preparation method according to claim 5, characterized in that, The inert gas is nitrogen; the organic solvent is dichloromethane or chloroform; the reaction temperature of the oxidative polymerization is 20-40 °C, and the reaction time is 48-96 h; the quenching is performed using methanol; the acid washing is performed using hydrochloric acid; and the washing solvent includes water and tetrahydrofuran.

7. A visible light-driven nickel-catalyzed C–N cross-coupling reaction method for aryl halides and amines, characterized in that, Using the π-conjugated porous organic polymer photocatalyst described in any one of claims 2-4 as a photocatalyst, under visible light irradiation, with nickel salt as a metal catalyst, aryl halides and amines undergo a coupling reaction in a polar aprotic solvent to generate aromatic amine products.

8. The method as described in claim 7, characterized in that, The aryl halide is an aryl bromide or an aryl iodide; the amine is an aliphatic amine or an aromatic amine; the nickel salt is... , , , The reaction mixture contains one or more of the following: its hydrates or complexes; the polar aprotic solvent is one or more of N,N-dimethylacetamide, N,N-dimethylformamide, and dimethyl sulfoxide; the visible light source is a blue LED light source; the reaction temperature is 25-40℃; and the molar ratio of aryl halide: amine: π-conjugated porous organic polymer photocatalyst: nickel salt is 1:2-3:0.00024-0.00049:0.01-0.

1.

9. The method according to any one of claims 7-8, characterized in that, When the aryl halide is an aryl iodide and the amine is an aromatic amine, the reaction system includes an organic base, and the molar ratio of the aryl iodide: aromatic amine: organic base is 1:2:

2.

10. The method as described in claim 9, characterized in that, The organic base is triethylamine.

Images