Preparation method of biaryl and biheterocyclic derivatives

Abstract

The invention discloses a preparation method of biaryl and biheterocyclic derivatives. Specifically disclosed is a preparation method of a compound as shown in a formula II, which comprises the following step: in an organic solvent, in the presence of a bivalent nickel salt, TEOA, a bidentate nitrogen ligand and an organic photocatalyst, under the irradiation of visible light, carrying out a coupling reaction as shown in the specification on a compound as shown in a formula I to obtain the compound as shown in the formula II. The preparation method disclosed by the invention is mild in reaction condition and wide in substrate application range, and efficient synthesis of biaryl and biheterocyclic derivatives can be realized.

Description

[0001] This application claims priority to Chinese patent application CN2025110171461, filed on July 23, 2025, the entire contents of which are incorporated herein by reference. Technical Field

[0002] This invention relates to the field of organic chemical synthesis technology, and in particular to a method for preparing biaryl and biheterocyclic derivatives. Background Technology

[0003] Compounds with a biphenyl skeleton are important organic compounds with wide-ranging and significant applications in industrial production, pharmaceutical research, and scientific studies. For example, SDIPBI, an electronic material with conductive properties, is used in the manufacture of solar cells. Many natural products and clinical drug molecules contain biphenyl structures, such as Daclatasvir for treating hepatitis C virus infection, Mastigophorene A for stimulating nerve growth, Versiperol A for significantly inhibiting the growth of Staphylococcus aureus, α-DDB for treating liver damage, and Hemicholinium-3, a biphenyl derivative that acts as a choline transporter inhibitor. Representative biphenyl derivatives are shown below:

[0004]

[0005] Compounds with bicyclic heterocyclic skeletons are indispensable organic compounds, especially bipyridines, which have important applications in coordination chemistry, optoelectronic materials, catalysis, supramolecular chemistry, biomedicine, ionic liquids, and materials science. Their multifunctionality makes them a key research object in chemistry and materials science. For example, bipyridine and its derivatives (such as 2,2'-bipyridine and 4,4'-bipyridine) are common bidentate ligands that can form stable complexes with various metal ions and are widely used in catalysis, optoelectronic materials, and other fields. The chiral 2,2'-bipyridine ligand first reported by Bolm has been successfully used as a multidentate ligand in catalytic reactions. Katsuki independently developed chiral 2,2'-bipyridine in 1992. In 2022, Li Pengfei's research group realized the asymmetric carbon-carbon coupling reaction of aryl aldehydes and aryl halides by using SBpy ligands, demonstrating the strong practical value of bipyridine ligands. Bipyridine compounds can also recognize specific molecules and self-assemble into supramolecular structures through hydrogen bonding, π-π stacking, and other interactions, making them applicable to molecular sensors and nanomaterials. Derivatives with structures similar to bipyridine compounds also possess certain medicinal value; for example, monosaccharide derivatives of orellanine may exhibit similar anticancer activity, particularly selective toxicity against certain cancer cells. Representative bipyridine derivatives are shown below:

[0006]

[0007] Due to the unique advantages and important roles of biaryl and bipyridine derivatives, the synthesis of functionalized biaryl and biheterocyclic compounds has attracted widespread attention from organic chemists. Transition metal-catalyzed reductive coupling reactions of aryl halides are one of the important methods for synthesizing biphenyl compounds. Traditional synthetic methods mainly use Ni as a catalyst, requiring Zn, Mg, Mn, etc., as reducing agents to promote the formation of low-valent nickel complexes, resulting in the generation of large amounts of metal salts after the reaction, causing environmental pollution. With the development of photochemistry, metal / photoco-catalyzed methods have provided new pathways for the synthesis of these compounds. Photoreactions are usually mild, requiring no high temperatures to induce the reaction under light. However, the reported self-coupling reactions of aryl halides are very limited, with only a few cases reported using expensive noble metals Pd and Au as catalysts. These reactions also suffer from problems such as the need for pre-prepared catalysts and poor substrate universality. Previous reports on the synthesis of bicyclic compounds, particularly the self-coupling reactions of pyridine halides via nickel-catalyzed thermal reactions, typically suffer from drawbacks such as the need for large amounts of nickel catalysts, the use of Zn or Mn as reducing agents, the use of highly hazardous N₂H₄ reducing agents, and poor substrate universality. Metal / photosynthetic self-coupling reactions of heteroaryl halides also present some limitations, such as the need for pre-prepared catalysts or the use of noble metal catalysts like palladium and gold. Therefore, developing mild and efficient synthetic methods for biaryl and bipyridine derivatives is of great significance for biomedicine, advanced materials, and other related fields.

[0008] Transition metal-catalyzed self-coupling reactions are a powerful means of constructing biaryl and biheterocyclic derivatives. Traditional synthetic methods require the use of stoichiometric or excess catalysts and excess metal reducing agents, which does not conform to the development concept of green chemistry.

[0009] In the literature, the synthesis of biaryl and biheterocyclic derivatives often requires the use of transition metal catalysis. However, the existing synthetic methods for biaryl and biheterocyclic derivatives have certain limitations, such as the need for equivalent amounts of metal reagents, pre-prepared reagents, hazardous reducing agents or expensive metal catalysts, and the need for high temperatures and long reaction times. We need to further enrich the synthetic methods for biaryl and biheterocyclic derivatives. Summary of the Invention

[0010] To address the shortcomings of existing methods for preparing biaryl and biheterocyclic derivatives, such as demanding reaction conditions and the need for expensive metal catalysts, this invention provides a method for preparing biaryl and bipyridine derivatives. Based on existing research, we have found that TEOA can effectively replace metal reducing agents, reducing their use. Furthermore, organic photocatalysts exhibit better solubility in organic solvents, thus improving reaction yield. Through research on the self-coupling reaction of aryl and heteroaryl halides, we have achieved the synthesis of biaryl and biheterocyclic derivatives under mild conditions in a simple and efficient manner using a nickel / photocatalytic synergistic method. The preparation method of this invention uses an organic photocatalyst as the reaction catalyst, achieving the self-coupling reaction of aryl / heteroaryl halides under light irradiation. The reaction conditions are mild, the substrate range is wide, and it enables the efficient synthesis of biaryl and biheterocyclic derivatives.

[0011] The present invention provides a method for preparing the compound shown in Formula II, which includes the following steps: in an organic solvent, in the presence of a divalent nickel salt, TEOA, a bidentate nitrogen ligand and an organic photocatalyst, and under visible light irradiation, the compound shown in Formula I is subjected to the following coupling reaction to obtain the compound shown in Formula II.

[0012]

[0013] Ring Ar is

[0014] A is CH or N;

[0015] B is either CH or N;

[0016] Ring Ar 1 For C6-C 10 Aryl;

[0017] X is a halogen;

[0018] R is independently a hydrogen atom, a C1-C6 alkyl group substituted with one or more halogens, or -COOR. 1 Halogen, -CN, C1-C6 alkyl, -(C=O)-R 2 -(C=O)-NR 3 R 4 , C1-C6 alkoxy groups, C6-C 10 Aryl, -NR 5 R 6 C2-C 12 unsaturated hydrocarbon groups, C3-C 12 Cycloalkyl, 3-12-membered heterocycloalkyl, or 5-12-membered heteroaryl;

[0019] The C3-C 12Cycloalkyl, 3-12 membered heterocycloalkyl, C6-C 10 The aryl and 5-12 heteroaryl groups are each independently bounded by one or more R groups. a replace;

[0020] R 1 and R a1 Each is independently a C1-C6 alkyl group, a C1-C6 alkyl group substituted with one or more halogens, or a C2-C... 12 unsaturated hydrocarbon groups, C3-C 12 cycloalkyl or with one or more R a Replacement C3-C 12 cycloalkyl;

[0021] R 2 It is a C1-C6 alkyl group, a C1-C6 alkyl group substituted with one or more halogens, a 3-12 membered heterocyclic alkyl group, or a group substituted with one or more R... a Substituted 3-12 membered heterocyclic alkyl groups;

[0022] R 3 R 4 R 5 and R 6 Each of the following is independently H, a C1-C6 alkyl group, a C1-C6 alkyl group substituted with one or more halogens, or a C6-C... 10 aryl or aryl with one or more R a Replacement C6-C 10 Aryl;

[0023] R a Independently, it is a C1-C6 alkoxy group, a C1-C6 alkyl group, a C1-C6 alkyl group substituted with one or more halogens, a halogen, or -COOR. a1 ;

[0024] n is 0, 1, 2, 3, 4 or 5;

[0025] The heteroatoms in the 3-12 membered heterocyclic alkyl group are selected from one, two, or three of N, O, and S, and the number of heteroatoms is one, two, or three; the atoms in the 5-12 membered heteroaryl group are selected from one, two, or three of N, O, and S, and the number of heteroatoms is one, two, or three.

[0026] In certain preferred embodiments of the present invention, certain groups in the compound represented by Formula I are defined as follows, and groups not mentioned are as described in any embodiment of the present invention (hereinafter referred to as "in a certain embodiment").

[0027] In one embodiment, the halogen is fluorine, chlorine, bromine, or iodine; for example, chlorine, bromine, or iodine.

[0028] In one embodiment, the C1-C6 alkyl group is a C1-C4 alkyl group; for example, methyl, ethyl, isopropyl, or tert-butyl.

[0029] In one embodiment, the C1-C6 alkoxy group is a C1-C4 alkoxy group; for example, methoxy, isopropoxy, or tert-butoxy.

[0030] In one embodiment, the C6-C 10 The aryl group is either phenyl or naphthyl.

[0031] In one scheme, the C2-C 12 The unsaturated hydrocarbon group is C2-C 12 The alkenyl group; the C2-C 12 The alkenyl group preferably contains one, two, or three double bonds; the C2-C 12 The alkenyl group is, for example, C4-C 10 alkenyl groups; for example, alkenyl groups.

[0032] In one embodiment, the C3-C 12 The cycloalkyl group is C5-C 10 cycloalkyl; for example

[0033] In one embodiment, the 3-12 membered heterocyclic alkyl group is a 5-6 membered heterocyclic alkyl group; the heteroatom in the 3-12 membered heterocyclic alkyl group is preferably selected from one or two of N and O; the number of heteroatoms is preferably one or two; for example

[0034] In one embodiment, the 5-12-membered heteroaryl group is a 5-6-membered heteroaryl group; the heteroatoms in the 5-12-membered heteroaryl group are preferably selected from one or two types of N and O; the number of heteroatoms is preferably one or two; for example

[0035] In one scheme, ring Ar is

[0036] In one embodiment, R is independently a hydrogen atom, a C1-C6 alkyl group substituted with one or more halogens, or -COOR. 1 Halogen, -CN, C1-C6 alkyl, -(C=O)-R 2 -(C=O)-NR 3 R 4 , C1-C6 alkoxy groups, C6-C 10 Aryl, -NR 5 R 63-12-membered heterocyclic alkyl or 5-12-membered heteroaryl; the heteroatoms in the 3-12-membered heterocyclic alkyl are selected from 1, 2 or 3 of N, O and S, and the number of heteroatoms is 1, 2 or 3; the atoms in the 5-12-membered heteroaryl are selected from 1, 2 or 3 of N, O and S, and the number of heteroatoms is 1, 2 or 3; the C6-C 10 aryl groups are oxidized by one or more R groups. a replace.

[0037] In one particular scheme, R 1 and R a1 Each is independently a C1-C6 alkyl group, C2-C 12 Unsaturated hydrocarbon groups or C3-C 12 Cycloalkyl.

[0038] In one particular scheme, R 2 It is a C1-C6 alkyl or a 3-12 membered heterocyclic alkyl; the heteroatoms in the 3-12 membered heterocyclic alkyl are selected from 1, 2 or 3 of N, O and S, and the number of heteroatoms is 1, 2 or 3.

[0039] In one particular scheme, R 3 R 4 R 5 and R 6 Each is independently a C1-C6 alkyl or C6-C 10 Aryl.

[0040] In one particular scheme, R a Independently C1-C6 alkoxy or -COOR a1 .

[0041] In one scheme, ring Ar is

[0042] In one particular scheme, X is Cl, Br, or I.

[0043] In a given scheme, R is independently H, -CF3, -COOEt, F, -CN, Cl, -CH3, -COO t Bu, -(CO)CH3, -(CO)N(CH3)2, -OMe、 Benzene ring, -O t Bu、-O i Pr, -N(CH3)2 or

[0044] In a given scheme, n is 0, 1, or 2.

[0045] In one embodiment, the compound represented by Formula I is the compound represented by Formula I-1;

[0046]

[0047] The definitions of A and X are as described above;

[0048] R b1 It can be H, halogen, or -CN;

[0049] R b2 H, C1-C6 alkyl group substituted with one or more halogens, C1-C6 alkyl group, -COOR 1 -(C=O)-NR 3 R 4 -(C=O)-R 2 , C1-C6 alkoxy or halogen;

[0050] R b3 H, a C1-C6 alkyl group substituted with one or more halogens, or -COOR 1 Halogen, -CN, C1-C6 alkyl, -(C=O)-R 2 or -(C=O)-NR 3 R 4 ;

[0051] R b4 H, C1-C6 alkyl, C1-C6 alkoxy, C6-C 10 aryl, C1-C6 alkoxy, and substituted with one or more R a Replacement C6-C 10 aryl, 5-12-membered heteroaryl, 3-12-membered heterocycloalkyl or -NR 5 R 6 .

[0052] In one embodiment, the compound represented by Formula I is the compound represented by Formula I-2;

[0053]

[0054] The definition of X is as described above;

[0055] R c1 H, a C1-C6 alkyl group substituted with one or more halogens, or a halogen. In one embodiment, the compound represented by Formula I is a compound represented by Formula I-3;

[0056]

[0057] The definition of X is as described above;

[0058] R c2It is a C1-C6 alkyl group that has been substituted with one or more halogens.

[0059] In one embodiment, the compound represented by Formula I is any of the following compounds:

[0060]

[0061]

[0062] In one embodiment, the compound represented by Formula II is any of the following compounds:

[0063]

[0064]

[0065] In one embodiment, the reaction can also be carried out in the presence of a base; the base is an organic base or an inorganic base, and the organic base is triethylamine. t One or more of BuOK, DMAP (4-dimethylaminopyridine) and MTBD (7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene); the inorganic base is t BuONa, LiO t One or more of Bu, NaOMe, K3PO4, Na2CO3, NaHCO3, KOMe, K2CO3, and KHCO3.

[0066] In one embodiment, the coupling reaction may also be carried out under an inert protective gas, which is one or more of nitrogen, helium, argon, and neon; for example, nitrogen.

[0067] In one embodiment, the organic solvent is one or more of aromatic solvents, ether solvents, nitrile solvents, and amide solvents; the aromatic solvent is preferably one or more of benzene, toluene, and xylene; the ether solvent is preferably one or more of diethyl ether, 1,4-dioxane, and tetrahydrofuran; the nitrile solvent is preferably acetonitrile; and the amide solvent is preferably N,N-dimethylformamide or N,N-dimethylacetamide.

[0068] In one embodiment, the organic solvent is preferably one or both of acetonitrile and 1,4-dioxane.

[0069] In one embodiment, the wavelength of the visible light is 440–490 nm; for example, 450–470 nm; for example, 456 nm.

[0070] In one embodiment, the power of the visible light source is 30–100 W; for example, 2 x 40 W.

[0071] In one embodiment, the divalent nickel salt is NiBr2·DME.

[0072] In one embodiment, the bidentate nitrogen ligand is a bipyridine ligand, a phenanthroline ligand, or a diazafluorenone ligand; the bipyridine ligand is preferably 2,2'-bipyridine; the phenanthroline ligand is preferably 4,7-dimethyl-1,10-phenanthroline; and the diazafluorenone ligand is preferably 4,5-diafluoren-9-one, for example, 4,5-diafluoren-9-one or 4,7-dimethyl-1,10-phenanthroline.

[0073] In one embodiment, the organic photocatalyst is an aromatic photocatalyst, such as 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN).

[0074] In one embodiment, the molar volume ratio of the compound represented by Formula I to the organic solvent is (0.01–1.0) mol / L; preferably (0.1–0.3) mol / L; for example, 0.2 mol / L.

[0075] In one embodiment, the molar ratio of the compound represented by Formula I to the divalent nickel salt is (50–200):1; preferably (80–150):1; for example, 100:1.

[0076] In one embodiment, the molar ratio of the compound represented by Formula I to the bidentate nitrogen ligand is (5–30):1; preferably (10–20):1; for example, 16.7:1.

[0077] In one embodiment, the molar ratio of the compound represented by Formula I to the organic photocatalyst is (50–200):1; preferably (80–150):1; for example, 100:1.

[0078] In one embodiment, the molar ratio of the compound represented by Formula I to the TEOA is (0.1–1.2):1; preferably (0.4–0.8):1; for example, 0.5:1.

[0079] In one scheme, in an organic solvent, in the presence of NiBr2·DME, TEOA, bidentate nitrogen ligand and 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile, under visible light irradiation, the compound shown in Formula I is coupled to obtain the compound shown in Formula II.

[0080] The organic solvent is one or both of acetonitrile and 1,4-dioxane;

[0081] The bidentate nitrogen ligand is 4,5-diazylfluorene-9-one or 4,7-dimethyl-1,10-phenanthroline.

[0082] In one embodiment, when X is I, the bidentate nitrogen ligand is 4,5-diazylfluorene-9-one; and the organic solvent is 1,4-dioxane.

[0083] In one embodiment, when X is Cl or Br, the bidentate nitrogen ligand is 4,7-dimethyl-1,10-phenanthroline; and the organic solvent is acetonitrile.

[0084] In one embodiment, the reaction temperature of the coupling reaction is 0℃-100℃, preferably 20℃-50℃; for example, 25℃.

[0085] The progress of the coupling reaction is monitored using conventional detection methods in the art (e.g., HPLC), with the disappearance or cessation of reaction of the compound represented by Formula I as the reaction endpoint. In one embodiment, the reaction time of the coupling reaction is 0.1-200 h, preferably 12-48 h; for example, 12 h or 24 h.

[0086] Unless otherwise specified, the terms used in this invention may be defined as follows:

[0087] Those skilled in the art will understand that, according to conventions used in the art, the structural formulas of the groups described in this invention are... This refers to the fact that the corresponding group is connected to other fragments or groups in the compound through this site.

[0088] In the term "one or more", when any variable is "multiple", the meaning of each variable is independent and does not affect each other; for example, "C1-C6 alkyl group substituted by one or more halogens" can be -CF3.

[0089] The term "multiple" refers to 2, 3, 4, 5, or 6.

[0090] The term "halogen" refers to F, Cl, Br, or I.

[0091] The term "alkyl" refers to a straight-chain or branched alkyl group having a specified number of carbon atoms (e.g., C1-C6). Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl.

[0092] The term "alkoxy" refers to a straight-chain or branched alkoxy group having a specified number of carbon atoms (e.g., C1-C6). Examples of alkoxy groups include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, or tert-butoxy.

[0093] The term "aryl" refers to an aryl group having a specified number of carbon atoms (e.g., C6-C). 10 Aryl groups are aromatic cyclic groups, which can be monocyclic or polycyclic. Aryl groups include, but are not limited to, benzene rings and naphthalene rings.

[0094] The term "alkenyl" refers to a group having a specific number of carbon atoms (e.g., C2-C). 12 A straight-chain or branched hydrocarbon group with one or more double bonds. The one or more carbon-carbon double bonds can be internal or terminal.

[0095] The term "cycloalkyl" refers to a ring with a specified number of carbon atoms (e.g., C3-C). 12 ), saturated cyclic groups whose ring atoms consist only of carbon atoms; for example

[0096] The term "heterocyclic alkyl" refers to a saturated cyclic group having a specified number of ring atoms (e.g., 3-12), a specified number of heteroatoms or heterogroups (e.g., 1, 2, or 3), and a specified type of heteroatomole or heterogroup (one or more of N, O, and S). Examples of heterocyclic alkyl groups include, but are not limited to:

[0097] The term "heteroaryl" refers to an aromatic cyclic group having a specified number of ring atoms (e.g., 5-12), a specified number of heteroatoms (e.g., 1, 2, or 3), and a specified type of heteroatom (one or more of N, O, and S), and can be monocyclic or polycyclic. The heteroaryl group is attached to the rest of the molecule via a carbon atom or heteroatom. Heteroaryl groups include, but are not limited to:

[0098] Without violating common sense in the field, the above-mentioned preferred conditions can be combined arbitrarily to obtain various preferred embodiments of the present invention.

[0099] The reagents and raw materials used in this invention are all commercially available.

[0100] The positive and progressive effects of this invention are as follows: the raw materials used in this invention are inexpensive and readily available, easy to synthesize, have a wide substrate range, and can obtain biaryl or biheterocyclic derivatives in good yields under mild conditions. Detailed Implementation

[0101] The following embodiments are provided to better understand the present invention and are not limited to the preferred embodiments described herein. They do not constitute a limitation on the content and scope of protection of the present invention. Any product that is the same as or similar to the present invention, derived under the guidance of the present invention or by combining the features of the present invention with other prior art, falls within the scope of protection of the present invention.

[0102] Abbreviation Full Chinese name <![CDATA[NiBr2·DME]]> Ethylene glycol dimethyl ether nickel bromide 4CzIPN 2,4,5,6-Tetra(9-carbazolyl)-isophthalonitrile TEOA Triethanolamine DCM dichloromethane

[0103] Synthesis of aryl iodides:

[0104]

[0105] Under an Ar atmosphere, m-iodobenzoyl chloride (1.5 equiv), 30 mL DCM, and Et3N (1.1 equiv) were added sequentially to a Schlenk tube. A disubstituted amine (1.0 equiv) was then slowly added at 0 °C, followed by a slow increase to room temperature. The reaction was monitored by TLC. The precipitate was removed by diatomaceous earth filtration. After evaporation of DCM, the mixture was extracted with ethyl acetate, washed with water and saturated brine, dried over anhydrous sodium sulfate, and purified by filtration and concentration.

[0106]

[0107] On a 10 mmol scale, silica gel column chromatography was performed with petroleum ether / ethyl acetate as eluent at a ratio of 10:1 to give 1.46 g of a white solid, in 48% yield. Mp: 35-40 °C. 1 H NMR (400MHz, CDCl3) δ7.83-7.82(m,1H),7.73-7.70(m,1H),7.45-7.43(m,1H),7.11(t,J=7. 6Hz,1H),3.60(t,J=7.2Hz,2H),3.37(t,J=6.8Hz,2H),1.95-1.90(m,2H),1.89-1.84(m,2H). 13 C NMR (100MHz, CDCl3) δ167.4,138.9,138.4,135.6,129.7,125.9,93.8,49.3,46.0,26.1,24.1.IR( neat):3056,2975,2943,2920,2878,1599,1556,1478,1424,1397,1203,801,761,736,700,676cm -1 HRMS (ESI) calculated value (calcd for) C 11 H 12 NOI[M+H] + 302.0036, Measured value (found) 302.0037.

[0108] Synthesis of heteroaryl bromides:

[0109]

[0110] In a glove box, 3 mol% Pd(PPh3)4 was added to a Schlenk tube. Then, under an Ar atmosphere, 2,6-dibromopyridine (1.0 equiv), boric acid (1.0 equiv), K2CO3 (2.5 equiv), 20 mL of 1,4-dioxane, and 5 mL of water were added sequentially to dissolve the precipitate. The mixture was heated to 80 °C and refluxed. The reaction was monitored by TLC. After returning to room temperature, the precipitate was removed by diatomaceous earth filtration. The reaction was quenched with saturated brine, extracted with ethyl acetate, washed with water and saturated brine, dried over anhydrous sodium sulfate, and purified by filtration and concentration.

[0111]

[0112] On a 5 mmol scale, silica gel column chromatography was performed with petroleum ether / ethyl acetate as eluent in a 1:1 ratio to give 425.3 mg of a pale yellow solid, in 36% yield. 1 H NMR (400MHz, CDCl3) δ9.15 (d, J = 2Hz, 1H), 8.64 (dd, J = 4.8, 1.2Hz, 1H), 8.30 (dt, J = 8.0, 2Hz, 1H), 7.69(d,J=7.6Hz,1H),7.62(t,J=7.6Hz,1H),7.45(d,J=8.0Hz,1H),7.38(dd,J=8.4,4.8Hz,1H). 13 C NMR (100MHz, CDCl3) δ 155.8, 150.4, 148.0, 142.5, 139.2, 134.4, 133.2, 127.1, 123.6, 119.0. IR (neat): 3038, 2962, 1716, 1576, 1547, 1426, 1386, 1179, 1132, 1122, 1065, 1017, 983, 777, 727, 697, 684. HRMS (ESI) calculated values ​​(calcd for) C 10 H7N2Br[M+H] + 234.9865, 234.9867 (found)

[0113]

[0114] On a 5 mmol scale, silica gel column chromatography was performed with petroleum ether / ethyl acetate as eluent at a ratio of 10:1 to give 796.0 mg of a colorless liquid, with a yield of 60%. 1H NMR (400MHz, CDCl3) δ7.86 (dt, J=8.0, 2.0Hz, 2H), 7.53 (t, J=8.0, 1.2Hz, 1H), 7.40-7.36(m,2H),7.08(t,J=7.2Hz,1H),6.98(d,J=8.4Hz,1H),3.86(s,3H). 13 C NMR (100MHz, CDCl3) δ156.9,156.8,141.3,137.9,131.2,130.5,127.1,125.8,123.8,121.0,111.3,55.5.I R(neat):2959,2838,1576,1541,1495,1430,1391,1263,1241,1166,1120,1032,1022,798,755,747,665cm -1 HRMS (ESI) calculated value (calcd for) C 12 H 10 NOBr[M+H] + 264.0019, Measured value (found) 264.0013.

[0115]

[0116] 5 mmol scale, silica gel column chromatography, eluent: petroleum ether / ethyl acetate = 10:1, yielded 355.3 mg of white solid, 32% yield. Mp 40-45℃. 1 H NMR (400MHz, CDCl3) δ8.02(t,J=0.8Hz,1H),7.50-7.46(m,2H),7.34(d,J=7.6Hz,1H),7.29(d,J=8.0Hz,1H),6.84(t,J=0.8Hz,1H). 13 C NMR (100MHz, CDCl3) δ152.8,143.9,141.9,138.7,125.7,125.7,118.5,108.4.IR(neat):314 2,1592,1571,1541,1507,1434,1412,1159,1126,1106,1065,1007,982,872,780,737,657cm -1 HRMS (ESI) calculated value (calcd for) C9H6NOBr[M+H] + 223.9706, Measured value (found): 223.9703.

[0117]

[0118] Chromatography at a scale of 5 mmol, using silica gel column chromatography with petroleum ether / ethyl acetate as eluent (5:1), yielded 851.3 mg of a white solid, 56% yield. Mp 58-63℃. 1 H NMR (400MHz, CDCl3) δ8.13(d,J=8.4Hz,1H),8.05(d,J=8.4Hz,1H),7.73(d,J=7.6Hz,1H), 7.62(t,J=7.6Hz,1H),7.45(d,J=8.0Hz,1H),4.40(q,J=7.2Hz,2H),1.42(t,J=7.2Hz,3H). 13 C NMR (100MHz, CDCl3) δ166.2,157.3,142.3,141.5,139.1,131.3,130.0,127.1,126.8,119.5,61.1,14.3.IR(neat) :3072,2979,2934,2898,1708,1548,1431,1367,1268,1161,1124,1106,1046,1016,984,848,796,761,696,670cm - 1 HRMS (ESI) calculated value (calcd for) C 14 H 12 NO2Br[M+H] + 306.0124, Measured value (found): 306.0125.

[0119]

[0120] On a 5 mmol scale, silica gel column chromatography was performed with petroleum ether / ethyl acetate as eluent at a ratio of 10:1 to give 538.8 mg of a pale yellow liquid, with a yield of 38%. 1 H NMR (400MHz, CDCl3) δ8.07-8.04(m,1H),7.91-7.87(m,2H),7.65-7.57(m,2H),7.54-7.46(m,5H). 13C NMR (100MHz, CDCl3) δ160.2,141.7,138.6,136.7,133.8,130.8,129.4,128.4,127.7,126.7,126.3,126.0,12 5.2,125.123.8.IR(neat):3044,1573,1545,1432,1393,1158,1132,1114,984,844,787,774,745,730,665cm -1 HRMS (ESI) calculated value (calcd for) C 15 H 10 NBr[M+H] + 284.0069, 284.0075 (found)

[0121] Example 1:

[0122]

[0123] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,5-diazafluoren-9-one (5.5 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), 1,4-dioxane (2.5 mL), triethanolamine (TEOA) (149.2 mg, 1.0 mmol), and 1a (136.0 mg, 0.5 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 12 h. After the reaction was completed, the reaction system was removed from the blue light and filtered through a short silica gel column (20 cm in length, 2 cm in diameter, 200-300 mesh). The solution was washed with DCM (10 mL x 3), concentrated, and subjected to silica gel plate chromatography. The eluent (or eluting agent) was pure petroleum ether, yielding 56.8 mg of white solid, with a yield of 78%. 1 H NMR (400MHz, CDCl3) δ7.75-7.69 (m, 8H). 13 C NMR (100MHz, CDCl3) δ143.2, 130.3 (q, J = 31.8Hz), 127.6, 125.9 (q, J = 3.8Hz), 124.1 (q, J = 270.3Hz). 19 F NMR(376MHz, CDCl3)δ-62.6(s).

[0124] Example 2:

[0125]

[0126] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,5-diazafluoren-9-one (5.5 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), 1,4-dioxane (2.5 mL), triethanolamine (TEOA) (149.2 mg, 1.0 mmol), and 1b (138.0 mg, 0.5 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 12 h. After the reaction was completed, the reaction system was removed from the blue light, and the reaction solution was filtered through a short silica gel column. The solution was washed with DCM, concentrated, and subjected to silica gel plate chromatography with petroleum ether / ethyl acetate in a ratio of 10:1 to obtain 52.7 mg of white solid, with a yield of 71%. 1 H NMR (400MHz, CDCl3) δ8.13 (d, J = 8.4Hz, 4H), 7.68 (d, J = 8.0Hz, 4H), 4.40 (q, J = 7.2Hz, 4H), 1.40 (t, J = 7.2Hz, 6H). 13 C NMR (100MHz, CDCl3) δ166.3,144.2,130.1,130.0,127.1,61.1,14.3.

[0127] Example 3:

[0128]

[0129] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,5-diazafluoren-9-one (5.5 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), 1,4-dioxane (2.5 mL), triethanolamine (TEOA) (149.2 mg, 1.0 mmol), and 1c (136.0 mg, 0.5 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 24 h. After the reaction was completed, the reaction system was removed from the blue light, and the reaction solution was filtered through a short silica gel column, washed with DCM, concentrated, and subjected to silica gel plate chromatography with pure petroleum ether as the eluent, yielding 39.8 mg of white solid, with a yield of 55%. 1 H NMR (400MHz, CDCl3) δ7.84 (s, 2H), 7.78 (d, J = 8.0Hz 2H), 7.67 (d, J = 8.0Hz 2H), 7.60 (d, J = 8.0Hz 2H). 13 C NMR (100MHz, CDCl3) δ140.6, 131.5 (q, J = 28.9Hz), 130.5, 129.5, 124.7 (q, J = 3.8Hz), 124.0 (q, J = 3.8Hz), 124.0 (q, J = 269.0Hz). 19 F NMR(376MHz, CDCl3)δ-62.703(m).

[0130] Example 4:

[0131]

[0132] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,5-diazafluoren-9-one (5.5 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), 1,4-dioxane (2.5 mL), triethanolamine (TEOA) (149.2 mg, 1.0 mmol), and 1d (111.0 mg, 0.5 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 12 h. After the reaction was completed, the reaction system was removed from the blue light, and the reaction solution was filtered through a short silica gel column, washed with DCM, concentrated, and subjected to silica gel plate chromatography with pure petroleum ether as the eluent, yielding 28.6 mg of white solid, with a yield of 60%. 1 H NMR (400MHz, CDCl3) δ7.52-7.48 (m, 4H), 7.13 (t, J = 8.8Hz, 4H). 13 C NMR (100MHz, CDCl3) δ162.4 (d, J = 245.2Hz), 136.4 (d, J = 3.0Hz), 128.5 (d, J = 7.6Hz), 115.7 (d, J = 21.3Hz). 19 F NMR (376MHz, CDCl3) δ-115.7 (m, J=-115.7).

[0133] Example 5:

[0134]

[0135] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,5-diazafluoren-9-one (5.5 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), 1,4-dioxane (2.5 mL), triethanolamine (TEOA) (149.2 mg, 1.0 mmol), and 1e (111.0 mg, 0.5 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 12 h. After the reaction was completed, the reaction system was removed from the blue light, and the reaction solution was filtered through a short silica gel column, washed with DCM, concentrated, and subjected to silica gel plate chromatography with pure petroleum ether as the eluent, yielding 27.8 mg of white solid, with a yield of 58%. 1 H NMR (400MHz, CDCl3) δ7.40-7.33(m,4H),7.22-7.13(m,4H). 13 C NMR (100MHz, CDCl3) δ159.8 (dd, J=248.6, 1.5Hz), 131.6 (t, J=2.3Hz), 129.7 (t, J=3.8Hz ),124.0(t,J=1.6Hz),124.0(t,J=1.6Hz),123.5(dd,J=10.6,4.6Hz),116.0-115.5(m). 19 F NMR(376MHz, CDCl3)δ-114.8(m).

[0136] Example 6:

[0137]

[0138] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,5-diazafluoren-9-one (5.5 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), 1f (114.5 mg, 0.5 mmol), 1,4-dioxane (2.5 mL), and triethanolamine (TEOA) (149.2 mg, 1.0 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 24 h. After the reaction was completed, the reaction system was removed from the blue light, and the reaction solution was filtered through a short silica gel column, washed with DCM, concentrated, and subjected to silica gel plate chromatography with petroleum ether / ethyl acetate in a 1:1 ratio to obtain 39.0 mg of white solid, with a yield of 76%. 1 H NMR (500MHz, CDCl3) δ7.83 (d, J = 8Hz, 2H), 7.74-7.701 (m, 2H), 7.59-7.55 (m, 4H). 13 C NMR (100MHz, CDCl3) δ141.5,133.5,132.8,130.5,129.2,117.5,112.3.

[0139] Example 7:

[0140]

[0141] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,5-diazafluoren-9-one (5.5 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), 1 g (114.5 mg, 0.5 mmol), 1,4-dioxane (2.5 mL), and triethanolamine (TEOA) (149.2 mg, 1.0 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 24 h. After the reaction was completed, the reaction system was removed from the blue light, and the reaction solution was filtered through a short silica gel column, washed with DCM, concentrated, and subjected to silica gel plate chromatography with petroleum ether / ethyl acetate in a ratio of 2:1 to obtain 38.2 mg of a pale yellow solid, with a yield of 75%. 1H NMR (400MHz, CDCl3) δ7.78 (d, J = 8.4 Hz, 4H), 7.69 (d, J = 8.4 Hz, 4H). 13 C NMR (100MHz, CDCl3) δ143.4,132.8,127.9,118.4,112.3.

[0142] Example 8:

[0143]

[0144] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,5-diazafluoren-9-one (5.5 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), 1,4-dioxane (2.5 mL), triethanolamine (TEOA) (149.2 mg, 1.0 mmol), and 1 h (119.2 mg, 0.5 mmol) were added sequentially. After capping, the sample was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 24 h. After the reaction was completed, the reaction system was removed from the blue light, and the reaction solution was filtered through a short silica gel column. The solution was washed with DCM, concentrated, and subjected to silica gel column chromatography with pure petroleum ether as the eluent, yielding 30.2 mg of white solid, with a yield of 54%. 1 H NMR (400MHz, CDCl3) δ7.49-7.46(m,4H),7.43-7.39(m,4H). 13 C NMR (100MHz, CDCl3) δ138.4,133.7,129.0,128.2.

[0145] Example 9:

[0146]

[0147] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,5-diazafluoren-9-one (5.5 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), 1,4-dioxane (2.5 mL), triethanolamine (TEOA) (149.2 mg, 1.0 mmol), and 1i (109.0 mg, 0.5 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 24 h. After the reaction was completed, the reaction system was removed from the blue light, and the reaction solution was filtered through a short silica gel column, washed with DCM, concentrated, and subjected to silica gel plate chromatography with pure petroleum ether as the eluent, yielding 27.1 mg of colorless liquid, with a yield of 59%. 1 H NMR (400MHz, CDCl3) δ7.43-7.40 (m, 4H), 7.34 (t, J = 7.8Hz 2H), 7.18 (d, J = 7.6 2H) 2.44 (s, 6H). 13 C NMR (100MHz, CDCl3) δ141.3,138.2,128.6,128.0,127.9,124.3,21.5.

[0148] Example 10:

[0149]

[0150] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,5-diazafluoren-9-one (5.5 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), 1j (109.0 mg, 0.5 mmol), 1,4-dioxane (2.5 mL), and triethanolamine (TEOA) (149.2 mg, 1.0 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 24 h. After the reaction was completed, the reaction system was removed from the blue light, and the reaction solution was filtered through a short silica gel column, washed with DCM, concentrated, and subjected to silica gel plate chromatography with pure petroleum ether as the eluent, yielding 13.2 mg of white solid, with a yield of 29%. 1H NMR (400MHz, CDCl3) δ7.48 (d, J = 8.0 Hz 4H), 7.23 (d, J = 8.4 4H) 2.39 (s, 6H). 13 C NMR (100MHz, CDCl3) δ138.3,136.7,129.4,126.8,21.1.

[0151] Example 11:

[0152]

[0153] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,5-diazafluoren-9-one (5.5 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), 1,4-dioxane (2.5 mL), triethanolamine (TEOA) (149.2 mg, 1.0 mmol), and 1kJ (116.0 mg, 0.5 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 24 h. After the reaction was completed, the reaction system was removed from the blue light, and the reaction solution was filtered through a short silica gel column, washed with DCM, concentrated, and subjected to silica gel plate chromatography with pure petroleum ether as the eluent, yielding 20.3 mg of colorless liquid, with a yield of 39%. 1 H NMR (400MHz, CDCl3) δ7.21 (s, 4H), 7.00 (s, 2H), 2.39 (s, 12H). 13 C NMR (100MHz, CDCl3) δ141.4,138.1,128.7,125.1,21.4.

[0154] Example 12:

[0155]

[0156] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,5-diazafluoren-9-one (5.5 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), 1,4-dioxane (2.5 mL), triethanolamine (TEOA) (149.2 mg, 1.0 mmol), and 1 L (127.0 mg, 0.5 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 12 h. After the reaction was complete, the reaction system was removed from the blue light, and the reaction solution was filtered through a short silica gel column, washed with DCM, concentrated, and subjected to silica gel plate chromatography with pure petroleum ether as the eluent, yielding 39.8 mg of a white solid (63%). 1 H NMR (400MHz, CDCl3) δ7.99-7.97(m,4H),7.62(t,J=6.8Hz,2H),7.54-7.43(m,6H),7.31(t,J=8.0Hz,2H). 13 C NMR (100MHz, CDCl3) δ138.4,133.5,132.8,128.1,127.9,127.8,126.5,125.9,125.8,125.3.

[0157] Example 13:

[0158]

[0159] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,5-diazafluoren-9-one (5.5 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), 1m (127.0 mg, 0.5 mmol), 1,4-dioxane (2.5 mL), and triethanolamine (TEOA) (149.2 mg, 1.0 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 24 h. After the reaction was completed, the reaction system was removed from the blue light, and the reaction solution was filtered through a short silica gel column, washed with DCM, concentrated, and subjected to silica gel plate chromatography with pure petroleum ether as the eluent, yielding 41.7 mg of a pale yellow solid, with a yield of 66%.1 H NMR (400MHz, CDCl3) δ8.18(s,2H),7.97-7.88(m,8H),7.55-7.48(m,4H). 13 C NMR (100MHz, CDCl3) δ138.4,133.7,132.7,128.5,128.2,127.7,126.3,126.1,126.0,125.7.

[0160] Example 14:

[0161]

[0162] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,5-diazafluoren-9-one (5.5 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), 1,4-dioxane (2.5 mL), triethanolamine (TEOA) (149.2 mg, 1.0 mmol), and 1N (152.1 mg, 0.5 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 12 h. After the reaction was complete, the reaction system was removed from the blue light, filtered through a short silica gel column, washed with DCM, concentrated, and subjected to silica gel plate chromatography with petroleum ether / ethyl acetate in a 10:1 eluent, yielding 40.2 mg of a white solid, a yield of 45%. Mp 80-85℃. 1 H NMR (400MHz, CDCl3) δ8.07 (d, J = 8.4Hz, 4H), 7.65 (d, J = 8.4Hz, 4H) 1.62 (s, 18H). 13 C NMR(100MHz, CDCl3)δ165.5,144.0,131.4,130.0,127.0,81.1,28.2.IR(neat):3007, 2973,2931,1702,1605,1368,1304,1291,1255,1156,1117,1100,1007,847,762,706cm -1 HRMS (ESI) calculated value (calcdfor) C 22 H 26 O4[M+Na] + 377.1723, Measured value (found) 377.1730.

[0163] Example 15:

[0164]

[0165] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,5-diazafluoren-9-one (5.5 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), 1,4-dioxane (2.5 mL), triethanolamine (TEOA) (149.2 mg, 1.0 mmol), and 1O (152.1 mg, 0.5 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 12 h. After the reaction was complete, the reaction system was removed from the blue light, filtered through a short silica gel column, washed with DCM, concentrated, and subjected to silica gel plate chromatography with petroleum ether / ethyl acetate in a 10:1 eluent, yielding 16.3 mg, a yield of 18%. Mp 71-79℃. 1 H NMR (400MHz, CDCl3) δ8.24 (s, 2H), 8.00 (d, J = 8.0Hz, 2H), 7.78-7.76 (m, 2H), 7.51 (t, J = 7.6Hz, 2H) 1.62 (s, 18H). 13 C NMR (100MHz, CDCl3) δ165.6,140.4,132.6,131.1,128.7,128.5,128.0,81.2,28.2.IR(neat):2 971,2928,2869,1707,1367,1314,1295,1281,1244,1158,1110,1088,908,850,743,690,682cm -1 HRMS (ESI) calculated value (calcd for) C 22 H 26 O4[M+Na] + 377.1723, Measured value (found) 377.1724.

[0166] Example 16:

[0167]

[0168] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,5-diazafluoren-9-one (5.5 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), 1p (123.0 mg, 0.5 mmol), 1,4-dioxane (2.5 mL), and triethanolamine (TEOA) (149.2 mg, 1.0 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 24 h. After the reaction was completed, the reaction system was removed from the blue light, and the reaction solution was filtered through a short silica gel column. After washing with DCM, the solution was concentrated and subjected to silica gel plate chromatography with petroleum ether / ethyl acetate in a ratio of 3:1 to obtain 36.3 mg of a pale yellow solid, with a yield of 61%. 1 H NMR (400MHz, CDCl3) δ8.05 (d, J = 8.4Hz 4H), 7.71 (d, J = 8.4Hz 4H), 2.64 (s, 6H). 13 C NMR (100MHz, CDCl3) δ197.6,144.3,136.6,129.0,127.4,26.6.

[0169] Example 17:

[0170]

[0171] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,5-diazafluoren-9-one (5.5 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), 1q (137.6 mg, 0.5 mmol), 1,4-dioxane (2.5 mL), and triethanolamine (TEOA) (149.2 mg, 1.0 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 24 h. After the reaction was complete, the reaction system was removed from the blue light, filtered through a short silica gel column, washed with DCM, concentrated, and subjected to silica gel plate chromatography with pure ethyl acetate as the eluent, yielding 28.8 mg of a pale yellow solid, with a yield of 39%. Mp: 170-177℃. 1H NMR (400MHz, CDCl3) δ7.62 (d, J = 7.6Hz 4H), 7.51 (d, J = 8.0Hz 4H), 3.13-3.04 (m, 12H). 13 C NMR(100MHz, CDCl3)δ171.2,141.4,135.5,127.6,126.7,39.5,35.3.IR(neat):3055,3021,2917,28 53,1725,1621,1608,1510,1488,1547,1393,1264,1218,1086,1021,1006,919,843,751,730,705cm -1 HRMS (ESI) calculated value (calcd for) C 18 H 20 N₂O₂[M+H] + 297.1598, 297.1596 (found)

[0172] Example 18:

[0173]

[0174] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,5-diazafluoren-9-one (5.5 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), 1,4-dioxane (2.5 mL), triethanolamine (TEOA) (149.2 mg, 1.0 mmol), and 1r (137.5 mg, 0.5 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 24 h. After the reaction was complete, the reaction system was removed from the blue light, filtered through a short silica gel column, washed with DCM, concentrated, and subjected to silica gel plate chromatography with pure ethyl acetate as the eluent, yielding 44.3 mg of a pale yellow solid, with a yield of 60%. Mp 110-118℃. 1 H NMR (400MHz, CDCl3) δ7.60-7.58(m,4H),7.44(t,J=7.6Hz 2H),7.37-7.35(m,2H),3.10(s,6H),2.98(s,6H). 13C NMR (100MHz, CDCl3) δ171.3,140.4,136.9,128.8,128.1,126.0,125.6,39.5,35.2.IR(ne at):2920,2852,1620,1576,1498,1445,1384,1259,1088,1050,811,798,751,705,696.cm - 1 HRMS (ESI) calculated value (calcd for) C 18 H 20 N₂O₂[M+H] + 297.1598, Measured value (found) 297.1597.

[0175] Example 19:

[0176]

[0177] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,5-diazafluoren-9-one (5.5 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), 1,4-dioxane (2.5 mL), triethanolamine (TEOA) (149.2 mg, 1.0 mmol), and 1s (150.6 mg, 0.5 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 24 h. After the reaction was complete, the reaction system was removed from the blue light, filtered through a short silica gel column, washed with DCM, concentrated, and subjected to silica gel plate chromatography. The eluent was pure ethyl acetate, yielding 27.8 mg of a pale yellow liquid, with a yield of 32%. MPa: 34-36℃. 1 H NMR (400MHz, CDCl3) δ7.72 (s, 2H), 7.62 (d, J = 6.8Hz 2H), 7.49-7.43 (m, 4H), 3.65 (t, J = 6.8Hz 4H),3.44(t,J=6.8Hz4H),2.00-1.93(m,4H),1.90-1.84(m,4H). 13C NMR (100MHz, CDCl3) δ169.4,140.5,137.9,128.8,128.3,126.1,125.8,49.6,46.1,26.3,24 .4.IR(neat):2975,2949,2868,1616,1575,1421,1340,1228,1201,917,797,726,705,664cm -1 HRMS (ESI) calculated value (calcd for) C 22 H 24 N₂O₂[M+H] + 349.1911, Measured value (found) 394.1906.

[0178] Example 20:

[0179]

[0180] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,5-diazafluoren-9-one (5.5 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), 1t (150.6 mg, 0.5 mmol), 1,4-dioxane (2.5 mL), and triethanolamine (TEOA) (149.2 mg, 1.0 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 24 h. After the reaction was complete, the reaction system was removed from the blue light, filtered through a short silica gel column, washed with DCM, concentrated, and subjected to silica gel plate chromatography with pure ethyl acetate as the eluent, yielding 21.6 mg of a yellow solid, with a yield of 25%. Mp: 140-147℃. 1 H NMR (400MHz, CDCl3) δ7.61 (br, 8H), 3.66 (t, J = 6.8Hz 4H), 3.48 (t, J = 6.4Hz 4H), 1.99-1.94 (m, 4H), 1.92-1.87 (m, 4H). 13C NMR (100MHz, CDCl3) δ169.3,141.7,136.4,127.7,126.9,126.1,125.8,49.6,46.2,26.4,24.4 .IR(neat):2920,2883,1720,1613,1547,1419,1334,1230,1005,916,900,846,754,725,661cm -1 HRMS (ESI) calculated value (calcd for) C 22 H 24 N₂O₂[M+H] + :349.1905, f measured value (found) 394.1906.

[0181] Example 21:

[0182]

[0183] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,5-diazafluoren-9-one (5.5 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), 1,4-dioxane (2.5 mL), triethanolamine (TEOA) (149.2 mg, 1.0 mmol), and 1u (147.0 mg, 0.5 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 24 h. After the reaction was complete, the reaction system was removed from the blue light, filtered through a short silica gel column, washed with DCM, concentrated, and subjected to silica gel plate chromatography with petroleum ether / ethyl acetate in a 10:1 eluent, yielding 34.1 mg of a white solid, with a yield of 41%. Mp 66-70℃. 1 H NMR (400MHz, CDCl3) δ7.93-7.91(m,2H),7.85-7.83(m,2H),7.49-7.46(m,2H),4.41(q,J=6.8Hz 4H),1.41(t,J=6.8Hz 6H). 13C NMR (100MHz, CDCl3) δ165.1, 159.4 (dd, J = 251.2, 1.6Hz), 132.8 (m), 131.4 (t, J = 2.3Hz), 127.1 (dd, J = 4.4, 4.4Hz), 125.2, 117.2-116.8 (m), 61.5, 14.2. 19 FNMR(376MHz, CDCl3)δ-113.5(m)IR(neat):2990,2965,2909,2853,1716,1422,1409,1396,1276,1250,1199,1088,1025,936,758,717cm -1 HRMS (EI) calculated value (calcd for) C 22 H 26 O4[M] + 334.1011, Measured value (found): 334.1018.

[0184] Example 22:

[0185]

[0186] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,5-diazafluoren-9-one (5.5 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), 1v (145.1 mg, 0.5 mmol), 1,4-dioxane (2.5 mL), and triethanolamine (TEOA) (149.2 mg, 1.0 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 24 h. After the reaction was complete, the reaction system was removed from the blue light, filtered through a short silica gel column, washed with DCM, concentrated, and subjected to silica gel plate chromatography with petroleum ether / ethyl acetate in a 5:1 eluent, yielding 36.8 mg of a white solid, with a yield of 45%. Mp 58-60℃. 1 H NMR (400MHz, CDCl3) δ8.13 (d, J = 1.6Hz 2H), 7.62 (dd, J = 7.8Hz, 1.6Hz 2H), 7.32 (d, J = 8.0Hz 2H), 4.40 (q, J = 7.2Hz 4H), 2.63 (s, 6H), 1.42 (t, J = 6.8Hz 6H). 13C NMR (100MHz, CDCl3) δ167.6,139.0,137.6,132.2,130.4,130.0,128.8,60.9,21.4,14.3.IR(ne at):2985,2972,2920,1717,1480,1388,1360,1287,1233,1160,1089,1023,818,777,716,685cm -1 HRMS (ESI) calculated value (calcd for) C 20 H 22 O4[M+Na] + 349.1410, Measured value (found) 349.1414.

[0187] Example 23:

[0188]

[0189] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,5-diazafluoren-9-one (5.5 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), 1 w (146.0 mg, 0.5 mmol), 1,4-dioxane (2.5 mL), and triethanolamine (TEOA) (149.2 mg, 1.0 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 24 h. After the reaction was complete, the reaction system was removed from the blue light, filtered through a short silica gel column, washed with DCM, concentrated, and subjected to silica gel plate chromatography with petroleum ether / ethyl acetate / dichloromethane in a ratio of 3:2:1, yielding 50.1 mg of a white solid, with a yield of 61%. Mp: 138-142℃. 1 H NMR (400MHz, CDCl3) δ7.89-7.87 (m, 2H), 7.18 (d, J = 8.0Hz, 2H), 7.13 (s, 2H), 3.97 (d, J = 1.2Hz 6H), 3.90 (d, J = 1.2Hz 6H). 13C NMR (100MHz, CDCl3) δ166.2,159.5,145.5,132.2,119.4,119.1,110.9,56.1,52.0.IR(neat):2 995,2949,2842,1698,1602,1434,1389,1285,1237,1186,1148,1107,1026,865,831,770,709cm -1 HRMS (ESI) calculated value (calcd for) C 18 H 18 O6[M+H] + 331.1176, Measured value (found) 331.1170.

[0190] Example 24:

[0191]

[0192] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,5-diazafluoren-9-one (5.5 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), 1,4-dioxane (2.5 mL), triethanolamine (TEOA) (149.2 mg, 1.0 mmol), and 1x (158.0 mg, 0.5 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 24 h. After the reaction was complete, the reaction system was removed from the blue light, and the reaction solution was filtered through a short silica gel column. The solution was washed with DCM, concentrated, and subjected to silica gel plate chromatography with petroleum ether / ethyl acetate in a 5:1 eluent, yielding 50.1 mg of a pale yellow liquid (53% yield). Mp 33-38℃. 1 H NMR (400MHz, CDCl3) δ8.13 (d, J = 8.4Hz 4H), 7.68 (d, J = 8.4Hz 4H), 5.91-5.81 (m, 2H), 5.11-5.01 (m, 4H), 4.36 (t, J = 6.4Hz 4H), 2.24 (q, J = 7.2Hz 4H),1.93-1.86(m,4H). 13C NMR (100MHz, CDCl3) δ166.2,144.3,137.4,130.1,129.9,127.2,115.4,64.4,30.1,27.9.IR(ne at):3075,2954,2920,2847,1713,1607,1396,1264,1176,1101,1024,1006,912,847,756,698cm -1 HRMS (ESI) calculated value (calcd for) C 24 H 26 O4[M+H] + 379.1904, Measured value (found) 379.1909.

[0193] Example 25:

[0194]

[0195] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,5-diazafluoren-9-one (5.5 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), 1,4-dioxane (2.5 mL), triethanolamine (TEOA) (149.2 mg, 1.0 mmol), and 1y (192.2 mg, 0.5 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 24 h. After the reaction was complete, the reaction system was removed from the blue light, filtered through a short silica gel column, washed with DCM, concentrated, and subjected to silica gel plate chromatography with petroleum ether / ethyl acetate at a ratio of 10:1, yielding 29.2 mg of a white solid, a yield of 23%. Mp 46-50℃. 1 H NMR (400MHz, CDCl3) δ8.13(d,J=8.4Hz 4H),7.68(d,J=8.4Hz 4H),5.51-5.47(m,2H),5.10-5.09(m,2H),4.87(d,J=6.8Hz 2H),2.14-2.09(m,8H),1.78(s,6H),1.68(s,6H),1.61(s,6H). 13C NMR (100MHz, CDCl3) δ166.3,144.3,142.5,131.8,130.2,130.0,127.2,123.7,118.3,62.0,39.5,26.3,25.6,17.7 ,16.6.IR(neat):2968,2917,2855,1702,1665,1606,1442,1382,1275,1261,1181,1098,1006,919,847,756,697cm -1 HRMS (ESI) calculated value (calcd for) C 34 H 42 O4[M+Na] + 537.2975, Measured value (found): 537.2978.

[0196] Example 26:

[0197]

[0198] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,5-diazafluoren-9-one (5.5 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), 1z (191.1 mg, 0.5 mmol), 1,4-dioxane (2.5 mL), and triethanolamine (TEOA) (149.2 mg, 1.0 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 24 h. After the reaction was complete, the reaction system was removed from the blue light, filtered through a short silica gel column, washed with DCM, concentrated, and subjected to silica gel plate chromatography with petroleum ether / ethyl acetate / dichloromethane in a ratio of 4:2:1, yielding 95.2 mg of a white solid, with a yield of 75%. Mp 205-208℃. 1 H NMR (400MHz, CDCl3) δ8.18(d,J=8.0Hz 4H),7.70(d,J=8.4Hz4H),5.22(s,2H),2.20-2.17(m,8H),1.93-1.84(m,12H),1.79(s,4H),1.66(d,J=12Hz 4H). 13C NMR (100MHz, CDCl3) δ165.5,144.3,130.6,130.1,127.2,77.6,37.3,36.3,32.02,32.01,27.3,27.0.IR( neat):2920,2912,2901,2858,1716,1704,1343,1278,1267,1176,1109,1099,1080,1041,979,969,755cm -1 HRMS (ESI) calculated value (calcd for) C 34 H 38 O4[M+H] + 511.2843, Measured value (found): 511.2846.

[0199] Example 27:

[0200]

[0201] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,7-dimethyl-1,10-phenanthroline (6.25 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), acetonitrile (CH3CN) (2.5 mL), triethanolamine (TEOA) (149.2 mg, 1.0 mmol), and 3a (94.0 mg, 0.5 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 24 h. After the reaction was completed, the reaction system was removed from the blue light, and the reaction solution was filtered through a short silica gel column. The solution was washed with DCM, concentrated, and subjected to silica gel plate chromatography with petroleum ether / ethyl acetate in a ratio of 10:1 to obtain 47.2 mg of white solid, with a yield of 87%. 1 H NMR (400MHz, CDCl3) δ8.01 (d, J = 7.2Hz, 2H), 7.67 (t, J = 8.0Hz, 2H), 6.75 (d, J = 8.4Hz, 2H), 4.04 (s, 6H). 13 C NMR (100MHz, CDCl3) δ163.4,153.4,139.1,113.6,110.8,53.1.

[0202] Example 28:

[0203]

[0204] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,7-dimethyl-1,10-phenanthroline (6.25 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), acetonitrile (CH3CN) (2.5 mL), triethanolamine (TEOA) (149.2 mg, 1.0 mmol), and 3a' (71.9 mg, 0.5 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 24 h. After the reaction was completed, the reaction system was removed from the blue light, and the reaction solution was filtered through a short silica gel column. The solution was washed with DCM, concentrated, and subjected to silica gel plate chromatography with petroleum ether / ethyl acetate in a ratio of 10:1 to obtain 25.9 mg of white solid, with a yield of 48%. 1 H NMR (400MHz, CDCl3) δ8.01 (d, J = 7.2Hz, 2H), 7.68 (t, J = 8.0Hz, 2H), 6.75 (d, J = 8.0Hz, 2H), 4.04 (s, 6H). 13 C NMR (100MHz, CDCl3) δ163.4,153.4,139.2,113.6,110.8,53.1.

[0205] Example 29:

[0206]

[0207] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,7-dimethyl-1,10-phenanthroline (6.25 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), acetonitrile (CH3CN) (2.5 mL), triethanolamine (TEOA) (149.2 mg, 1.0 mmol), and 4b (86.0 mg, 0.5 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 24 h. After the reaction was completed, the reaction system was removed from the blue light, and the reaction solution was filtered through a short silica gel column, washed with DCM, concentrated, and subjected to silica gel plate chromatography with pure petroleum ether as the eluent, yielding 34.6 mg of white solid, with a yield of 75%. 1 H NMR (400MHz, CDCl3) δ8.17(d,J=8.0Hz,2H),7.67(t,J=8.0Hz,2H),7.14(d,J=7.6Hz,2H),2.62(s,6H). 13 C NMR (100MHz, CDCl3) δ157.8,155.9,136.9,123.0,118.1,24.6.

[0208] Example 30:

[0209]

[0210] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,7-dimethyl-1,10-phenanthroline (6.25 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), 3c (117.0 mg, 0.5 mmol), acetonitrile (CH3CN) (2.5 mL), and triethanolamine (TEOA) (149.2 mg, 1.0 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 24 h. After the reaction was completed, the reaction system was removed from the blue light, and the reaction solution was filtered through a short silica gel column, washed with DCM, concentrated, and subjected to silica gel plate chromatography with pure petroleum ether as the eluent, yielding 68.4 mg of white solid, with a yield of 89%. 1H NMR (400MHz, CDCl3) δ8.64(d,J=7.6Hz,2H),8.21(d,J=7.2Hz,4H),7.91(t,J =7.6Hz,2H),7.79(d,J=8.0Hz,2H),7.56(t,J=8.0Hz,4H),7.51-7.46(m,2H). 13 C NMR (100MHz, CDCl3) δ156.2,155.8,139.3,137.5,128.9,128.6,126.9,120.2,119.5.

[0211] Example 31:

[0212]

[0213] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,7-dimethyl-1,10-phenanthroline (6.25 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), acetonitrile (CH3CN) (2.5 mL), triethanolamine (TEOA) (149.2 mg, 1.0 mmol), and 3d (79.0 mg, 0.5 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 24 h. After the reaction was completed, the reaction system was removed from the blue light, and the reaction solution was filtered through a short silica gel column. The solution was washed with DCM, concentrated, and subjected to silica gel plate chromatography with petroleum ether / ethyl acetate as eluent in a 1:1 ratio to obtain 14.1 mg of white solid, with a yield of 36%. 1 H NMR (400MHz, CDCl3) δ8.76-8.75(m,4H),7.56-7.54(m,4H). 13 C NMR (100MHz, CDCl3) δ150.7, 145.5, 121.4.

[0214] Example 32:

[0215]

[0216] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,7-dimethyl-1,10-phenanthroline (6.25 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), 3e (113.0 mg, 0.5 mmol), acetonitrile (CH3CN) (2.5 mL), and triethanolamine (TEOA) (149.2 mg, 1.0 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 24 h. After the reaction was completed, the reaction system was removed from the blue light, and the reaction solution was filtered through a short silica gel column. The solution was washed with DCM, concentrated, and subjected to silica gel plate chromatography with petroleum ether / ethyl acetate in a ratio of 10:1 to obtain 39.5 mg of white solid, with a yield of 54%. 1 H NMR (400MHz, CDCl3) δ8.95 (s, 2H), 8.61 (d, J = 8.4Hz, 2H), 8.08 (d, J = 7.6Hz, 2H). 13 C NMR (100MHz, CDCl3) δ 157.7, 146.3 (q, J = 3.8Hz), 134.3 (q, J = 3.7Hz), 127.2 (q, J = 33.4Hz), 123.5 (q, J = 271.0Hz), 121.3. 19 F NMR(376MHz, CDCl3)δ-62.6(s).

[0217] Example 33:

[0218]

[0219] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,7-dimethyl-1,10-phenanthroline (6.25 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), 3f (113.0 mg, 0.5 mmol), acetonitrile (CH3CN) (2.5 mL), and triethanolamine (TEOA) (149.2 mg, 1.0 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 24 h. After the reaction was completed, the reaction system was removed from the blue light, and the reaction solution was filtered through a short silica gel column. The solution was washed with DCM, concentrated, and subjected to silica gel plate chromatography with petroleum ether / ethyl acetate in a ratio of 5:1 to obtain 55.0 mg of white solid, with a yield of 75%. 1 H NMR (400MHz, CDCl3) δ8.97 (s, 2H), 8.11 (dd, J = 8.0Hz, 1.6Hz, 2H), 7.86 (d, J = 8.4Hz, 2H). 13 C NMR (100MHz, CDCl3) δ148.6 (q, J = 34.9Hz), 148.5, 136.1, 135.0.121.3 (q, J = 272.5Hz), 120.8 (q, J = 2.3Hz). 19 F NMR(376MHz, CDCl3)δ-68.0(s).

[0220] Example 34:

[0221]

[0222] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,7-dimethyl-1,10-phenanthroline (6.25 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), 3 g (113.0 mg, 0.5 mmol), acetonitrile (CH3CN) (2.5 mL), and triethanolamine (TEOA) (149.2 mg, 1.0 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 24 h. After the reaction was complete, the reaction system was removed from the blue light, filtered through a short silica gel column, washed with DCM, concentrated, and subjected to silica gel plate chromatography with petroleum ether / ethyl acetate in a 5:1 eluent, yielding 60.1 mg of a pale yellow solid, with a yield of 82%. Mp 66-72℃. 1 HNMR (500MHz, CDCl3) δ8.90 (d, J = 4.5Hz, 2H), 7.93 (s, 2H), 7.77-7.76 (m 2H). 13 C NMR (125MHz, CDCl3) δ151.2, 149.6 (q, J = 35.6Hz), 146.2, 121.2 (q, J = 272.4Hz), 118.3 (q, J = 2.8Hz). 19 F NMR(376MHz, CDCl3)δ-68.1.IR(neat):2917,2844,1605,1550,1400,1326,1188,1142,1121,1085,1062,992,897,842,690cm -1 HRMS (EI) calculated value (calcd for) C 18 H 18 O6[M] + 292.0430, 292.0427 (found)

[0223] Example 35:

[0224]

[0225] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,7-dimethyl-1,10-phenanthroline (6.25 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), acetonitrile (CH3CN) (2.5 mL), and triethanolamine (TEOA) (149.2 mg, 1.0 mmol) were added sequentially to a 4 mL sample vial for 3 h (115.1 mg, 0.5 mmol). After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 24 h. After the reaction was complete, the reaction system was removed from the blue light, filtered through a short silica gel column, washed with DCM, concentrated, and subjected to silica gel plate chromatography with petroleum ether / ethyl acetate in a 4:1 eluent, yielding 56.4 mg of a white solid (75% yield). Mp: 127-130℃. 1 HNMR (400MHz, CDCl3) δ7.87(d,J=7.6Hz,2H),7.64(t,J=7.6Hz,2H),6.66(d,J=8.0Hz,2H),1.69(s,18H). 13 C NMR(100MHz, CDCl3)δ163.1,153.4,138.9,113.1,112.9,79.2,28.7.IR(neat):3452,3358,32 38,3037,2977,2925,1621,1568,1456,1430,1410,1362,1304,1169,1148,929,909,818,796cm -1 HRMS (ESI) calculated value (calcd for) C 18 H 24 N₂O₂[M+H] + 301.1911, Measured value (found) 301.1914.

[0226] Example 36:

[0227]

[0228] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,7-dimethyl-1,10-phenanthroline (6.25 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), acetonitrile (CH3CN) (2.5 mL), triethanolamine (TEOA) (149.2 mg, 1.0 mmol), and 3i (108.0 mg, 0.5 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 24 h. After the reaction was complete, the reaction system was removed from the blue light, filtered through a short silica gel column, washed with DCM, concentrated, and subjected to silica gel plate chromatography with petroleum ether / ethyl acetate in a 4:1 eluent, yielding 50.3 mg of a white solid (74% yield). Mp: 70-80℃. 1 H NMR (400MHz, CDCl3) δ7.92 (d, J = 7.2Hz, 2H), 7.65 (t, J = 8.4Hz, 2H), 6.68 (d, J = 8.4Hz, 2H), 5.51-5.44 (m, 2H), 1.42 (d, J = 6.4Hz, 12H). 13 C NMR(100MHz, CDCl3)δ162.7,153.5,139.1,113.0,111.4,67.8,22.0.IR(neat):3079,3056, 2977,2938,2870,1569,1429,1367,1293,1264,1140,1121,1097,1067,950,809,787,734cm -1 HRMS (ESI) calculated value (calcd for) C 16 H 20 N₂O₂[M+H] + 273.1598, 273.1604 (found)

[0229] Example 37:

[0230]

[0231] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,7-dimethyl-1,10-phenanthroline (6.25 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), acetonitrile (CH3CN) (2.5 mL), triethanolamine (TEOA) (149.2 mg, 1.0 mmol), and 3j (88.0 mg, 0.5 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 24 h. After the reaction was complete, the reaction system was removed from the blue light, filtered through a short silica gel column, washed with DCM, concentrated, and subjected to silica gel plate chromatography with petroleum ether / ethyl acetate in a 10:1 eluent, yielding 20.5 mg of a white solid, with a yield of 43%. Mp 90-98℃. 1 HNMR (400MHz, CDCl3) δ8.64-8.60 (m, 2H), 8.15 (dd, J = 10.0Hz, 2.4Hz 2H), 7.08-7.04 (m, 2H). 13 C NMR (100MHz, CDCl3) δ170.9, 168.3, 151.5 (d, J = 7.6Hz), 112.0 (d, J = 17.5Hz), 109.1 (d, J = 19.0Hz). 19 F NMR(376MHz, CDCl3)δ-101.6(m).IR(neat):3097,3061,3029,3006,2920,2855,1593,1569,1455,1383,1285,1263,1225,1095,992,877,840cm -1 . HRMS (ESI) calculated value (calcd for) C 10 H6N2F2[M+H] + :193.0572, Measured value (found) 193.0566.

[0232] Example 38:

[0233]

[0234] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,7-dimethyl-1,10-phenanthroline (6.25 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), acetonitrile (CH3CN) (2.5 mL), triethanolamine (TEOA) (149.2 mg, 1.0 mmol), and 3k (88.0 mg, 0.5 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 24 h. After the reaction was completed, the reaction system was removed from the blue light, and the reaction solution was filtered through a short silica gel column, washed with DCM, concentrated, and subjected to silica gel plate chromatography with petroleum ether / dichloromethane = 1:1 as the eluent, yielding 23.2 mg of white solid, with a yield of 48%. 1 H NMR (400MHz, DMSO-d6) δ8.41 (d, J = 5.6Hz, 2H), 7.87-7.85 (m, 2H), 7.74 (s, 2H). 13 C NMR (100MHz, DMSO-d6) δ164.0 (d, J = 234.5Hz), 149.1 (dd, J = 8.8Hz, 3.8Hz), 148.7 (d, J = 15.2Hz), 120.0 (d, J = 4.6Hz), 107.6 (d, J = 39.5Hz). 19 F NMR(376MHz,DMSO-d6)δ-63.2(s).

[0235] Example 39:

[0236]

[0237] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,7-dimethyl-1,10-phenanthroline (6.25 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), 3L (132.1 mg, 0.5 mmol), acetonitrile (CH3CN) (2.5 mL), and triethanolamine (TEOA) (149.2 mg, 1.0 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 24 h. After the reaction was complete, the reaction system was removed from the blue light, filtered through a short silica gel column, washed with DCM, concentrated, and subjected to silica gel plate chromatography with petroleum ether / ethyl acetate in a 10:1 eluent, yielding 47.3 mg of a white solid, with a yield of 51%. Mp: 148-152℃. 1 HNMR (400MHz, CDCl3) δ8.52(d,J=7.6Hz,2H),8.06(d,J=7.6Hz,2H),7.93(d,J=8.0Hz,2H),7.84 (t,J=8.0Hz,2H),7.43-7.39(m,2H),7.16(t,J=7.6Hz,2H),7.05(d,J=8.4Hz,2H),3.90(s,6H). 13 C NMR (100MHz, CDCl3) δ157.3,156.0,154.8,136.3,131.5,129.8,129.2,124.9,121.0,119.0,111.5,55.6 .IR(neat):2956,2912,2857,2826,1605,1564,1491,1461,1434,1383,1260,1236,1021,815,803,748cm -1 HRMS (ESI) calculated value (calcd for) C 24 H 21 N₂O₂[M+H] + 369.1597, Measured value (found) 369.1592.

[0238] Example 40:

[0239]

[0240] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,7-dimethyl-1,10-phenanthroline (6.25 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), 3m (132.1 mg, 0.5 mmol), acetonitrile (CH3CN) (2.5 mL), and triethanolamine (TEOA) (149.2 mg, 1.0 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 24 h. After the reaction was complete, the reaction system was removed from the blue light source, and the reaction solution was filtered through a short silica gel column. The solution was washed with DCM, concentrated, and subjected to silica gel plate chromatography with pure dichloromethane as the eluent, yielding 44.8 mg of a white solid (49% yield). Mp: 153-158℃. 1 H NMR(400MHz, CDCl3)δ8.60(d,J=7.6Hz,2H),7.91(t,J=8.0Hz,2H),7.79-7.77(m, 4H),7.72(d,J=8.0Hz,2H),7.44(t,J=8.0Hz,2H),7.01-7.00(m,2H),3.94(s,6H). 13 C NMR (100MHz, CDCl3) δ160.1,156.0,155.8,140.9,137.6,129.7,120.4,119.7,119.4,114.5,112.6,55. 4.IR(neat):2962,2923,2852,1592,1566,1490,1435,1297,1267,1218,1180,1032,879,780,724,687cm -1 HRMS (ESI) calculated value (calcd for) C 24 H 20 N₂O₂[M+H] + 369.1598, Measured value (found): 365.1591.

[0241] Example 41:

[0242]

[0243] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,7-dimethyl-1,10-phenanthroline (6.25 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), 3n (153.1 mg, 0.5 mmol), acetonitrile (CH3CN) (2.5 mL), and triethanolamine (TEOA) (149.2 mg, 1.0 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 24 h. After the reaction was complete, the reaction system was removed from the blue light, and the reaction solution was filtered through a short silica gel column. The solution was washed with DCM, concentrated, and subjected to silica gel plate chromatography with petroleum ether / ethyl acetate in a 4:1 eluent, yielding 32.8 mg of a white solid (29% yield). Mp: 180-187℃. 1 HNMR(400MHz, CDCl3)δ8.63(d,J=8.0Hz,2H),8.24(d,J=8.4Hz,4H),8.18(d,J=8.4Hz,4H), 7.95(t,J=7.6Hz,2H),7.84(d,J=8.0Hz,2H),4.43(q,J=7.2Hz,4H),1.44(t,J=7.2Hz,6H). 13 C NMR(100MHz, CDCl3)δ166.4,155.9,155.1,143.3,137.8,130.7,130.0,126.8,120.8,120.2,61.0,14.3.IR(neat): 2998,2983,2956,2936,2925,2891,2855,1706,1561,1435,1363,1270,1127,1110,1022,1013,868,814,743,698cm -1 HRMS (ESI) calculated value (calcd for) C 28 H 25 N₂O₄[M+H] + 453.1809, Measured value (found) 453.1816.

[0244] Example 42:

[0245]

[0246] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,7-dimethyl-1,10-phenanthroline (6.25 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), 3O (112.1 mg, 0.5 mmol), acetonitrile (CH3CN) (2.5 mL), and triethanolamine (TEOA) (149.2 mg, 1.0 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 24 h. After the reaction was complete, the reaction system was removed from the blue light, filtered through a short silica gel column, washed with DCM, concentrated, and subjected to silica gel plate chromatography with petroleum ether / ethyl acetate at a ratio of 10:1, yielding 50.3 mg of a pale yellow solid (70% yield). Mp 166-170℃. 1 H NMR (400MHz, CDCl3) δ8.43(d,J=8.0Hz,2H),8.13(s,2H),7.82(t,J=7.6Hz,2H),7.53(s,2H),7.48(d,J=7.6Hz,2H),7.01(s,2H). 13 C NMR (100MHz, CDCl3) δ155.7,150.9,143.8,141.3,137.4,127.3,119.9,119.0,108.8.I R(neat):3136,1593,1567,1500,1440,1153,1081,1057,1003,932,871,776,723,705cm -1 HRMS (ESI) calculated value (calcd for) C 18 H 13 N₂O₂[M+H] + 289.0971, Measured value (found) 289.0978.

[0247] Example 43:

[0248]

[0249] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,7-dimethyl-1,10-phenanthroline (6.25 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), 3p (144.6 mg, 0.5 mmol), acetonitrile (CH3CN) (2.5 mL), and triethanolamine (TEOA) (149.2 mg, 1.0 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 24 h. After the reaction was complete, the reaction system was removed from the blue light, and the reaction solution was filtered through a short silica gel column. The solution was washed with DCM, concentrated, and subjected to silica gel plate chromatography with petroleum ether / ethyl acetate in a 3:1 eluent, yielding 58.3 mg of a white solid (57% yield). Mp: 180-186℃. 1 HNMR (400MHz, CDCl3) δ8.61(d,J=8.4Hz,2H),8.36-8.33(m,2H),7.99-7.91(m,6H),7.75(d,J=7.2Hz,2H),7.65-7.61(m,4H),7.58-7.55(m,4H). 13 C NMR (100MHz, CDCl3) δ158.5,155.8,138.6,137.4,134.0,131.3,128.9,128.4,127.6,126.4,125.9,125.8,125.3,12 5.0,119.5.IR(neat):3045,2959,2925,2844,1567,1442,1393,1260,1251,1085,991,970,797,774,751,737,715cm -1 HRMS (ESI) calculated value (calcd for) C 30 H 20 N2[M+H] + 409.1699, Measured value (found) 409.1705.

[0250] Example 44:

[0251]

[0252] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,7-dimethyl-1,10-phenanthroline (6.25 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), 3q (117.6 mg, 0.5 mmol), acetonitrile (CH3CN) (2.5 mL), and triethanolamine (TEOA) (149.2 mg, 1.0 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 24 h. After the reaction was complete, the reaction system was removed from the blue light, filtered through a short silica gel column, washed with DCM, concentrated, and subjected to silica gel plate chromatography with petroleum ether / ethyl acetate / dichloromethane in a ratio of 2:1:1 as the eluent, yielding 61.8 mg of a white solid, with a yield of 80%. Mp: 184-190℃. 1 H NMR (400MHz, CDCl3) δ9.33 (s, 2H), 8.65 (d, J = 4.0Hz, 2H), 8.56 (d, J = 8.0Hz, 2H), 8.4 0(d,J=8.0Hz,2H),7.89(t,J=8.0Hz,2H),7.74(d,J=7.6Hz,2H),7.41-7.39(m,2H). 13 C NMR(100MHz, CDCl3)δ155.7,153.6,149.8,148.3,137.8,134.5,134.1,123.4,120.3,120.1.IR(neat):30 48,2998,2956,2915,2847,1725,1591,1579,1561,1446,1373,1161,1115,1086,1016,990,784,709,657cm -1 HRMS (ESI) calculated value (calcd for) C 20 H 15 N4[M+H] + 311.1291, Measured value (found): 311.1288.

[0253] Example 45:

[0254]

[0255] In a nitrogen-filled glove box, ethylene glycol dimethyl ether nickel bromide (NiBr2) was added sequentially to a 4 mL sample vial. ·The reaction mixture consisted of DME (7.7 mg, 0.005 mmol), 4,7-dimethyl-1,10-phenanthroline (6.25 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), 3r (113.6 mg, 0.5 mmol), acetonitrile (CH3CN) (2.5 mL), and triethanolamine (TEOA) (149.2 mg, 1.0 mmol). After capping, the mixture was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 24 h. After the reaction was complete, the reaction system was removed from the Blue light, filtered through a short silica gel column, washed with DCM, concentrated, and subjected to silica gel plate chromatography with petroleum ether / ethyl acetate as eluent (10:1) to give 39.5 mg of a pale yellow solid (54% yield). MP219-224℃. 1 H NMR (400MHz, CDCl3) δ7.70 (d, J = 7.2Hz, 2H), 7.53 (t, J = 7.6Hz, 2H), 6.35 (d, J = 8.4Hz, 2H), 3.55 (t, J = 6.8Hz, 8H), 2.05-2.00 (m, 8H). 13 C NMR(100MHz, CDCl3)δ156.8,155.1,137.4,108.3,106.1,46.59,25.5.IR(neat): 2962,2925,2852,2834,1575,1446,1372,1346,1277,1248,1156,993,780,729cm -1 HRMS (ESI) calculated value (calcd for) C 18 H 23 N4[M+H] + 295.1917, Measured value (found) 295.1917.

[0256] Example 46:

[0257]

[0258] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,7-dimethyl-1,10-phenanthroline (6.25 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), 3s (120.6 mg, 0.5 mmol), acetonitrile (CH3CN) (2.5 mL), and triethanolamine (TEOA) (149.2 mg, 1.0 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 24 h. After the reaction was complete, the reaction system was removed from the blue light, filtered through a short silica gel column, washed with DCM, concentrated, and subjected to silica gel plate chromatography with petroleum ether / ethyl acetate / dichloromethane in a ratio of 10:2:1, yielding 59.6 mg of a pale yellow solid, with a yield of 74%. Mp: 170-178℃. 1 H NMR (400MHz, CDCl3) δ7.72 (d, J = 7.2Hz, 2H), 7.56 (t, J = 8.0Hz, 2H), 6.65 (d, J = 8.4Hz, 2H), 3.62 (s, 8H), 1.67 (s, 12H). 13 C NMR(100MHz, CDCl3)δ159.0,154.8,137.9,109.7,106.9,46.4,25.5,24.8.IR(neat):2988, 2935,2844,1568,1456,1438,1377,1361,1277,1244,1227,1129,1103,976,933,777,728cm -1 HRMS (ESI) calculated value (calcd for) C 20 H 27 N4[M+H] + 323.2230, Measured value (found): 323.2225.

[0259] Example 47:

[0260]

[0261] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,7-dimethyl-1,10-phenanthroline (6.25 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), 3t (121.6 mg, 0.5 mmol), acetonitrile (CH3CN) (2.5 mL), and triethanolamine (TEOA) (149.2 mg, 1.0 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 24 h. After the reaction was complete, the reaction system was removed from the blue light, and the reaction solution was filtered through a short silica gel column. The solution was washed with DCM, concentrated, and subjected to silica gel plate chromatography with petroleum ether / ethyl acetate in a 5:1 eluent, yielding 58.3 mg of a pale yellow solid (71% yield). Mp: 190-196℃. 1 HNMR (400MHz, CDCl3) δ7.78(d,J=7.6Hz,2H),7.61(t,J=8.0Hz,2H),6.64(d,J=7.4Hz,2H),3.86(t,J=4.4Hz,8H),3.57(t,J=4.8Hz,8H). 13 C NMR(100MHz, CDCl3)δ158.8,154.5,138.1,110.9,106.7,66.8,45.6.IR(neat):2 977,2956,2930,2865,2818,1439,1263,1240,1112,981,942,929,858,731,652cm -1 HRMS (ESI) calculated value (calcd for) C 18 H 23 N4O2[M+H] + 327.1816, Measured value (found) 327.1810.

[0262] Example 48:

[0263]

[0264] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,7-dimethyl-1,10-phenanthroline (6.25 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), 3u (100.6 mg, 0.5 mmol), acetonitrile (CH3CN) (2.5 mL), and triethanolamine (TEOA) (149.2 mg, 1.0 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 24 h. After the reaction was complete, the reaction system was removed from the blue light, filtered through a short silica gel column, washed with DCM, concentrated, and subjected to silica gel plate chromatography with petroleum ether / ethyl acetate in a 5:1 eluent, yielding 30.3 mg of a white solid (50% yield). Mp: 168-173℃. 1 HNMR (400MHz, CDCl3) δ7.74(d,J=7.6Hz,2H),7.57(t,J=7.6Hz,2H),6.53(d,J=8.4Hz,2H),3.16(s,12H). 13 C NMR(100MHz, CDCl3)δ158.7,154.7,137.7,108.6,105.6,37.9.IR(neat):2923,28 47,2808,1575,1562,1494,1421,1399,1367,1247,1184,1161,977,960,772,725cm -1 HRMS (ESI) calculated value (calcd for) C 14 H 18 N4[M+H] + 243.1604, 243.1598 (found)

[0265] Example 49:

[0266]

[0267] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,7-dimethyl-1,10-phenanthroline (6.25 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), 3V (118.1 mg, 0.5 mmol), acetonitrile (CH3CN) (2.5 mL), and triethanolamine (TEOA) (149.2 mg, 1.0 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 24 h. After the reaction was complete, the reaction system was removed from the blue light, and the reaction solution was filtered through a short silica gel column. The solution was washed with DCM, concentrated, and subjected to silica gel plate chromatography with petroleum ether / ethyl acetate at a ratio of 10:1, yielding 61.5 mg of a pale yellow solid (67% yield). Mp: 153-158℃. 1 H NMR (400MHz, CDCl3) δ7.85 (d, J = 7.2Hz, 2H), 7.49-7.40 (m, 6H), 7.34 (d, J = 8.0Hz, 4H), 7.22 (t, J = 7.2Hz, 2H), 6.61 (d, J = 8.0Hz, 2H), 3.63 (s, 6H). 13 C NMR (100MHz, CDCl3) δ 158.0, 154.5, 147.0, 137.3, 129.5, 126.0, 125.0, 110.3, 109.1, 38.2. IR (neat): 3061, 3035, 2928, 1561, 1494, 1455, 1444, 1400, 1347, 1282, 1135, 1085, 976, 786. HRMS (ESI) calculated values ​​(calcd for) C 24 H 23 N4[M+H] + 367.1917, Measured value (found) 267.1917.

[0268] Example 50:

[0269]

[0270] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,7-dimethyl-1,10-phenanthroline (6.25 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), acetonitrile (CH3CN) (2.5 mL), triethanolamine (TEOA) (149.2 mg, 1.0 mmol), and 3 w (104.0 mg, 0.5 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 24 h. After the reaction was completed, the reaction system was removed from the blue light, and the reaction solution was filtered through a short silica gel column. The solution was washed with DCM, concentrated, and subjected to silica gel plate chromatography with petroleum ether / ethyl acetate in a ratio of 10:1 to obtain 45.8 mg of a pale yellow solid, with a yield of 71%. 1 H NMR (400MHz, CDCl3) δ8.85(d,J=8.8Hz,2H),8.31(d,J=8.4Hz,2H),8.25(d,J=8.4Hz,2H),7.86(d,J=8.0Hz,2H),7.78-7.74(m,2H),7.59-7.55(m,2H). 13 C NMR (100MHz, CDCl3) δ156.2,147.9,136.7,129.9,129.5,528.4,127.6,126.9,119.4.

[0271] Example 51:

[0272]

[0273] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,7-dimethyl-1,10-phenanthroline (6.25 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), acetonitrile (CH3CN) (2.5 mL), triethanolamine (TEOA) (149.2 mg, 1.0 mmol), and 3x (104.0 mg, 0.5 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 24 h. After the reaction was completed, the reaction system was removed from the blue light, and the reaction solution was filtered through a short silica gel column, washed with DCM, concentrated, and subjected to silica gel plate chromatography with petroleum ether / ethyl acetate in a ratio of 5:1 to obtain 28.7 mg of a pale yellow solid, with a yield of 45%. 1 H NMR (400MHz, CDCl3) δ9.30 (s, 2H), 8.47 (s, 2H), 8.19 (d, J = 8.4Hz, 2H), 7.96 (d, J = 7.6Hz, 2H), 7.79 (t, J = 7.2Hz, 2H), 7.64 (t, J = 7.2Hz, 2H). 13 C NMR (100MHz, CDCl3) δ149.5,147.7,133.8,130.7,130.0,129.4,128.1,127.9,127.4.

[0274] Example 52:

[0275]

[0276] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,7-dimethyl-1,10-phenanthroline (6.25 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), 3y (104.0 mg, 0.5 mmol), acetonitrile (CH3CN) (2.5 mL), and triethanolamine (TEOA) (149.2 mg, 1.0 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 24 h. After the reaction was complete, the reaction system was removed from the blue light, filtered through a short silica gel column, washed with DCM, concentrated, and subjected to silica gel plate chromatography with petroleum ether / ethyl acetate in a 3:1 eluent, yielding 40.2 mg of a pale yellow solid, with a yield of 63%. Mp 146-149℃. 1 H NMR (400MHz, CDCl3) δ9.03 (d, J = 4.0Hz, 2H), 8.22 (d, J = 8.4Hz, 2H), 7.74-7.70 (m, 2H), 7.40-7.34 (m, 6H). 13 C NMR(100MHz, CDCl3)δ149.8,148.3,144.2,129.9,129.8,127.1,126.8,125.7,121.7.IR(neat):30 63,3027,2993,2992,2844,1579,1564,1508,1500,1460,1415,1381,1296,881,873,857,756,686cm -1 HRMS (ESI) calculated value (calcd for) C 18 H 12 N2[M+H] + 257.1073, 257.1076 (found)

[0277] Example 53:

[0278]

[0279] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,7-dimethyl-1,10-phenanthroline (6.25 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), 3z (104.0 mg, 0.5 mmol), acetonitrile (CH3CN) (2.5 mL), and triethanolamine (TEOA) (149.2 mg, 1.0 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 24 h. After the reaction was complete, the reaction system was removed from the blue light, and the reaction solution was filtered through a short silica gel column. The solution was washed with DCM, concentrated, and subjected to silica gel plate chromatography with petroleum ether / ethyl acetate in a 5:1 eluent, yielding 31.2 mg of a pale yellow solid (49% yield). Mp 33-36℃. 1 HNMR (500MHz, CDCl3) δ9.38 (s, 2H), 8.56 (s, 2H), 8.09 (d, J = 8.5Hz, 2H), 7.63 (t, J = 7.0Hz, 2H), 7.55 (t, J = 8.0Hz, 2H), 7.39 (d, J = 8.5Hz, 2H). 13 C NMR(125MHz, CDCl3)δ153.0,143.9,135.3,130.8,128.2,128.0,127.9,127.5,124.8.IR(neat):3 043,2928,2847,1620,1569,1504,1495,1380,1257,1233,1152,948,899,782,800,750,730,684cm -1 HRMS (ESI) calculated value (calcd for) C 18 H 12 N2[M+H] + 257.1073, 257.1074 (found)

[0280] Example 54:

[0281]

[0282] In a nitrogen-filled glove box, nickel glycol dimethyl ether bromide (NiBr2·DME) (7.7 mg, 0.005 mmol), 4,7-dimethyl-1,10-phenanthroline (6.25 mg, 0.03 mmol), 2,4,5,6-tetra(9-carbazolyl)-isophthalonitrile (4CzIPN) (3.9 mg, 0.005 mmol), 3aa (79.5 mg, 0.5 mmol), acetonitrile (CH3CN) (2.5 mL), and triethanolamine (TEOA) (149.2 mg, 1.0 mmol) were added sequentially to a 4 mL sample vial. After capping, the vial was removed from the glove box and then placed under 2x40 W 456 nm Blue light at room temperature for 24 h. After the reaction was completed, the reaction system was removed from the blue light, and the reaction solution was filtered through a short silica gel column, washed with DCM, concentrated, and subjected to silica gel plate chromatography with pure ethyl acetate as the eluent, yielding 22.3 mg of a pale yellow solid, with a yield of 56%. 1 H NMR (400MHz, CDCl3) δ9.32 (s, 2H), 8.99 (s, 4H). 13 C NMR (100MHz, CDCl3) δ158.9, 154.8, 128.4.

[0283] Finally, it should be noted that the above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing a compound of formula II, characterized in that, It includes the following steps: In an organic solvent, in the presence of a divalent nickel salt, TEOA, a bidentate nitrogen ligand, and an organic photocatalyst, and under visible light irradiation, the compound shown in Formula I was subjected to the coupling reaction shown below to obtain the compound shown in Formula II. Ring Ar is A is CH or N; B is either CH or N; Ring Ar 1 For C6-C 10 Aryl; X is a halogen; R is independently a hydrogen atom, a C1-C6 alkyl group substituted with one or more halogens, or -COOR. 1 Halogen, -CN, C1-C6 alkyl, -(C=O)-R 2 -(C=O)-NR 3 R 4 , C1-C6 alkoxy groups, C6-C 10 Aryl, -NR 5 R 6 C2-C 12 unsaturated hydrocarbon groups, C3-C 12 Cycloalkyl, 3-12-membered heterocycloalkyl, or 5-12-membered heteroaryl; The C3-C 12 Cycloalkyl, 3-12 membered heterocycloalkyl, C6-C 10 The aryl and 5-12 heteroaryl groups are each independently bounded by one or more R groups. a replace; R 1 and R a1 Each is independently a C1-C6 alkyl group, a C1-C6 alkyl group substituted with one or more halogens, or a C2-C... 12 unsaturated hydrocarbon groups, C3-C 12 cycloalkyl or with one or more R a Replacement C3-C 12 cycloalkyl; R 2 It is a C1-C6 alkyl group, a C1-C6 alkyl group substituted with one or more halogens, a 3-12 membered heterocyclic alkyl group, or a group substituted with one or more R... a Substituted 3-12 membered heterocyclic alkyl groups; R 3 R 4 R 5 and R 6 Each of the following is independently H, a C1-C6 alkyl group, a C1-C6 alkyl group substituted with one or more halogens, or a C6-C... 10 aryl or aryl with one or more R a Replacement C6-C 10 Aryl; R a Independently, it is a C1-C6 alkoxy group, a C1-C6 alkyl group, a C1-C6 alkyl group substituted with one or more halogens, a halogen, or -COOR. a1 ; n is 0, 1, 2, 3, 4 or 5; The heteroatoms in the 3-12 membered heterocyclic alkyl group are selected from one, two, or three of N, O, and S, and the number of heteroatoms is one, two, or three; the atoms in the 5-12 membered heteroaryl group are selected from one, two, or three of N, O, and S, and the number of heteroatoms is one, two, or three.

2. The method for preparing the compound of formula II as described in claim 1, characterized in that, It satisfies one or more of the following conditions: (1) The halogen is fluorine, chlorine, bromine or iodine; (2) The C1-C6 alkyl group is a C1-C4 alkyl group; (3) The alkoxy groups of C1-C6 are alkoxy groups of C1-C4; (4) The C6-C 10 The aryl group is phenyl or naphthyl; (5) The C2-C 12 The unsaturated hydrocarbon group is C2-C 12 alkenyl groups; (6) The C3-C 12 The cycloalkyl group is C5-C 10 cycloalkyl; (7) The 3-12 membered heterocyclic alkyl group is a 5-6 membered heterocyclic alkyl group; (8) The heteroatom in the 3-12 membered heterocyclic alkyl group is selected from one or two of N and O; (9) The number of heteroatoms in the 3-12 membered heterocyclic alkyl group is 1 or 2; (10) The 5-12-membered heteroaryl group is a 5-6-membered heteroaryl group; (11) The heteroatoms in the 5-12 membered heteroaryl group are selected from one or two of N and O; (12) The number of heteroatoms in the 5-12 membered heteroaryl group is 1 or 2; (13) The reaction is carried out in the presence of a base; (14) The coupling reaction is carried out under an inert protective gas; (15) The organic solvent is one or more of aromatic solvents, ether solvents, nitrile solvents and amide solvents; (16) The wavelength of the visible light is 440–490 nm; (17) The power of the visible light source is 30 to 100 W; (18) The divalent nickel salt is NiBr2·DME; (19) The bidentate nitrogen ligand is a bipyridine ligand, a phenanthroline ligand, or a diazafluorenone ligand; (20) The organic photocatalyst is an aromatic photocatalyst; (21) The molar volume ratio of the compound represented by Formula I to the organic solvent is (0.01 to 1.0) mol / L; (22) The molar ratio of the compound represented by Formula I to the divalent nickel salt is (50-200):1; (23) The molar ratio of the compound represented by Formula I to the bidentate nitrogen ligand is (5-30):1; (24) The molar ratio of the compound represented by Formula I to the organic photocatalyst is (50-200):1; (25) The molar ratio of the compound represented by Formula I to the TEOA is (0.1–1.2):1; (26) The reaction temperature of the coupling reaction is 0℃-100℃.

3. The method for preparing the compound represented by Formula II as described in claim 2, characterized in that, It satisfies one or more of the following conditions: (1) The halogen is chlorine, bromine or iodine; (2) The alkyl group of C1-C6 is methyl, ethyl, isopropyl or tert-butyl; (3) The alkoxy group of the C1-C6 is methoxy, isopropoxy or tert-butoxy; (4) The C2-C 12 The alkenyl group contains one, two, or three double bonds; (5) The C2-C 12 The alkenyl group is C4-C 10 alkenyl groups; (6) The C3-C 12 cycloalkyl is (7) The 3-12 membered heterocyclic alkyl group is (8) The 5-12 member heteroaryl group is (9) The base is an organic base or an inorganic base; (10) The inert protective gas is one or more of nitrogen, helium, argon and neon; (11) The aromatic solvent is one or more of benzene, toluene and xylene; (12) The ether solvent is one or more of diethyl ether, 1,4-dioxane and tetrahydrofuran; (13) The nitrile solvent is acetonitrile; (14) The amide solvent is N,N-dimethylformamide or N,N-dimethylacetamide; (15) The wavelength of the visible light is 450–470 nm; (16) The power of the visible light source is 2x40W; (17) The bipyridine ligand is 2,2'-bipyridine; (18) The phenanthroline ligand is 4,7-dimethyl-1,10-phenanthroline; (19) The diazafluorenone ligand is 4,5-diazafluoren-9-one; (20) The organic photocatalyst is 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile; (21) The molar volume ratio of the compound represented by Formula I to the organic solvent is (0.1–0.3) mol / L; (22) The molar ratio of the compound represented by Formula I to the divalent nickel salt is (80-150):1; (23) The molar ratio of the compound represented by Formula I to the bidentate nitrogen ligand is (10-20):1; (24) The molar ratio of the compound represented by Formula I to the organic photocatalyst is (80-150):1; (25) The molar ratio of the compound represented by Formula I to the TEOA is (0.4–0.8):1; (26) The reaction temperature of the coupling reaction is 20℃-50℃.

4. The method for preparing the compound represented by Formula II as described in claim 3, characterized in that, It satisfies one or more of the following conditions: (1) The C2-C 12 The alkenyl group is (2) The organic base is triethylamine, t One or more of BUOK, DMAP, and MTBD; (3) The inorganic base is t BuONa, LiO t One or more of Bu, NaOMe, K3PO4, Na2CO3, NaHCO3, KOMe, K2CO3 and KHCO3; (4) The organic solvent is one or both of acetonitrile and 1,4-dioxane; (5) The wavelength of the visible light is 456 nm; (6) The bidentate nitrogen ligand is 4,5-diazylfluorene-9-one or 4,7-dimethyl-1,10-phenanthroline; (7) The molar volume ratio of the compound represented by Formula I to the organic solvent is 0.2 mol / L; (8) The molar ratio of the compound represented by Formula I to the divalent nickel salt is 100:1; (9) The molar ratio of the compound represented by Formula I to the bidentate nitrogen ligand is 16.7:1; (10) The molar ratio of the compound represented by Formula I to the organic photocatalyst is 100:1; (11) The molar ratio of the compound represented by Formula I to the TEOA is 0.5:1; (12) The reaction temperature of the coupling reaction is 25℃.

5. The method for preparing the compound of formula II as described in claim 1, characterized in that, It satisfies one or more of the following conditions: (1) Ring Ar is (2) R is independently a hydrogen atom, a C1-C6 alkyl group substituted with one or more halogens, or -COOR 1 Halogen, -CN, C1-C6 alkyl, -(C=O)-R 2 -(C=O)-NR 3 R 4 , C1-C6 alkoxy groups, C6-C 10 Aryl, -NR 5 R 6 3-12-membered heterocyclic alkyl or 5-12-membered heteroaryl; the heteroatoms in the 3-12-membered heterocyclic alkyl are selected from 1, 2 or 3 of N, O and S, and the number of heteroatoms is 1, 2 or 3; the atoms in the 5-12-membered heteroaryl are selected from 1, 2 or 3 of N, O and S, and the number of heteroatoms is 1, 2 or 3; the C6-C 10 aryl groups are oxidized by one or more R groups. a replace; (3)R 1 and R a1 Each is independently a C1-C6 alkyl group, C2-C 12 Unsaturated hydrocarbon groups or C3-C 12 cycloalkyl; (4)R 2 It is a C1-C6 alkyl or a 3-12 membered heterocyclic alkyl; the heteroatoms in the 3-12 membered heterocyclic alkyl are selected from one, two or three of N, O and S, and the number of heteroatoms is one, two or three; (5)R 3 R 4 R 5 and R 6 Each is independently a C1-C6 alkyl or C6-C 10 Aryl; (6)R a Independently C1-C6 alkoxy or -COOR a1 .

6. The method for preparing the compound of formula II as described in claim 1, characterized in that, It satisfies one or more of the following conditions: (1) Ring Ar is (2) X is Cl, Br, or I; (3) R is independently H, -CF3, -COOEt, F, -CN, Cl, -CH3, -COO t Bu, -(CO)CH3, -(CO)N(CH3)2, -OMe、 Benzene ring, -O t Bu、-O i Pr、 -N(CH3)2 or (4) n is 0, 1 or 2.

7. The method for preparing the compound of formula II as described in claim 1, characterized in that, It satisfies one or more of the following conditions: (1) The compound shown in Formula I is the compound shown in Formula I-1; R b1 It can be H, halogen, or -CN; R b2 H, C1-C6 alkyl group substituted with one or more halogens, C1-C6 alkyl group, -COOR 1 -(C=O)-NR 3 R 4 -(C=O)-R 2 , C1-C6 alkoxy or halogen; R b3 H, a C1-C6 alkyl group substituted with one or more halogens, or -COOR 1 Halogen, -CN, C1-C6 alkyl, -(C=O)-R 2 or -(C=O)-NR 3 R 4 ; R b4 H, C1-C6 alkyl, C1-C6 alkoxy, C6-C 10 aryl, C1-C6 alkoxy, and substituted with one or more R a Replacement C6-C 10 aryl, 5-12-membered heteroaryl, 3-12-membered heterocycloalkyl or -NR 5 R 6 ; (2) The compound shown in Formula I is the same as the compound shown in Formula I-2; R c1 H, a C1-C6 alkyl group or halogen substituted with one or more halogens; (3) The compound shown in Formula I is the same as the compound shown in Formula I-3; R c2 It is a C1-C6 alkyl group that has been substituted with one or more halogens.

8. The method for preparing the compound of formula II as described in claim 1, characterized in that, It satisfies one or two of the following conditions: (1) The compound represented by Formula I is any of the following compounds: (2) The compound represented by Formula II is any of the following compounds:

9. A method for preparing the compound of formula II as described in any one of claims 1 to 8, characterized in that, In an organic solvent, in the presence of NiBr2·DME, TEOA, bidentate nitrogen ligand and 2,4,5,6-tetrakis(9-carbazolyl)-isophthalonitrile, under visible light irradiation, the compound shown in Formula I was coupled to give the compound shown in Formula II. The organic solvent is one or both of acetonitrile and 1,4-dioxane; The bidentate nitrogen ligand is 4,5-diazylfluorene-9-one or 4,7-dimethyl-1,10-phenanthroline.

10. The method for preparing the compound of formula II as described in claim 9, characterized in that, It satisfies one or two of the following conditions: (1) When X is I, the bidentate nitrogen ligand is 4,5-diazylfluorene-9-one; the organic solvent is 1,4-dioxane; (2) When X is Cl or Br, the bidentate nitrogen ligand is 4,7-dimethyl-1,10-phenanthroline; the organic solvent is acetonitrile.

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