Aza-aromatic fused ring compound and light-emitting device

Abstract

The invention relates to an aza-aromatic fused ring compound and a light-emitting device, and belongs to the technical field of organic light-emitting materials. The technical problem that in the prior art, the half-peak width of a thermally activated delayed fluorescent material is large is solved. The aza-aromatic fused ring unit is used as a luminescent material, on one hand, the relaxation degree of an excited state structure can be reduced by using a rigid skeleton structure of the aza-aromatic fused ring compound, so that a relatively narrow half-peak width is realized; on the other hand, separation of HOMO and LUMO is achieved through the resonance effect between electron-deficient groups and nitrogen atoms, and therefore small delta EST and TADF effects are achieved, and then high luminous efficiency is achieved. Meanwhile, by changing the types of aromatic rings and heteroaromatic rings contained in the fused ring compound or introducing different substituent groups, the delayed fluorescence lifetime and the half-peak width can be further adjusted.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic light-emitting materials, and particularly relates to a nitrogen-containing heteroaromatic condensed ring compound and a light-emitting device. Background Art

[0002] Organic light-emitting devices (OLEDs) have the characteristics of rich colors, thin thickness, wide viewing angles, fast response, and the ability to fabricate flexible devices, and are considered to be the most promising next-generation flat panel display and solid-state lighting technologies. OLEDs usually consist of an ITO anode, a hole injection layer (HIL), a hole transport layer (HTL), a light-emitting layer (EL), a hole blocking layer (HBL), an electron transport layer (ETL), an electron injection layer (EIL), and a cathode. One or two organic layers can be omitted as needed. By combining holes (Hole) and electrons (Electron) injected from the positive electrode and the negative electrode on the organic thin film to form excitons (Exciton), when the excitons return from the excited state to the stable ground state, they release energy in the form of light and thus emit light.

[0003] Due to the limitation of the spin quantum statistics law, traditional fluorescent materials can only utilize singlet excitons accounting for 25% of all excitons during the electroluminescence process, and the remaining 75% of triplet excitons are deactivated through non-radiative transitions. Therefore, the maximum value of the internal quantum efficiency (IQE) of its device is 25%. Phosphorescent metal complexes can convert triplet excitons into photons by utilizing the spin-orbit coupling effect of heavy metal atoms, realizing the utilization of triplet excitons and achieving an internal quantum efficiency of 100%. However, this approach faces the problem of the high cost of phosphorescent metal complexes.

[0004] Thermally activated delayed fluorescence (TADF) materials are the third generation of organic light-emitting materials after traditional fluorescence and phosphorescent materials. Such materials generally have a small singlet-triplet energy level difference (ΔE ST ), and utilize the thermally activated reverse intersystem crossing (RISC) process to transfer triplet excitons to singlet excitons to emit fluorescence, thereby realizing the full utilization of singlet and triplet excitons and achieving an internal quantum efficiency of 100%. At the same time, such materials should also have a high fluorescence quantum efficiency (PLQY) to promote the decay of singlet excitons in the form of light and improve the device efficiency. Currently, the main implementation approach of TADF molecules is to introduce electron donor (D) and electron acceptor (A) units, so that the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) are separated, thereby realizing a small ΔE STHowever, due to the obvious vibrational relaxation of its excited state, this D-A structure exhibits a large Stokes shift, and its emission spectrum is relatively wide, with a full width at half maximum (FWHM) generally in the range of 70 - 100 nm. In practical applications, it is usually necessary to use a filter or construct an optical microcavity to improve the color purity, but this will lead to a decrease in the external quantum efficiency of the device or make the device structure complex.

[0005] Therefore, how to develop a luminescent material that not only has the TADF effect but also has the characteristic of a narrow full width at half maximum spectrum through reasonable chemical structure design to solve the defect of the wide full width at half maximum faced by the above materials has become one of the problems that many forward-looking researchers in the field urgently need to solve. Summary of the Invention

[0006] The present invention aims to solve the technical problem of the wide full width at half maximum of thermally activated delayed fluorescence materials in the prior art, and provides a nitrogen-containing heteroaromatic condensed ring compound and a light-emitting device. The nitrogen-containing heteroaromatic condensed ring compound of the present invention not only has the TADF effect but also has the characteristic of a narrow full width at half maximum spectrum.

[0007] To solve the above technical problems, the technical solution of the present invention is specifically as follows:

[0008] A nitrogen-containing heteroaromatic condensed ring compound has any one of the structures shown in Formula (Ⅰ) - Formula (Ⅲ):

[0009]

[0010] Wherein, in Formula (Ⅰ), a and d are independently integers from 0 to 3, and b and c are independently integers from 0 to 4; in Formula (Ⅱ), a and b are independently integers from 0 to 3, and c and d are independently integers from 0 to 4; in Formula (Ⅲ), a and b are independently integers from 0 to 3, and c and d are independently integers from 0 to 4;

[0011] X 1 and X 2 are independently selected from a single bond (i.e., Ar 1 is directly connected to Ar 3 , Ar 2 is directly connected to Ar 4 by a single bond), O, S, Se, Te, N(R 1 ), B(R 1 ), C(R 1 R 2 ), Si(R 1 R 2 ), O=S=O or (R 1 )P=O;

[0012] Y 1 and Y 2 are independently selected from S, N(R 1) or one of the following structures:

[0013]

[0014] wherein, R a ~R d are independently selected from H, D, C1-C30 linear alkyl, C3-C30 branched alkyl, C1-C30 ether chain, C1-C30 thioether chain, C1-C30 ester group chain or C3-C30 cycloalkyl;

[0015] Ar 1 ~Ar 4 are independently selected from C6-C60 aryl or C5-C60 heteroaryl, and the heteroatoms in the heteroaryl are selected from one or more of Si, Ge, N, P, O, S and Se;

[0016] R 1 、R 2 、R 3 and R 4 are independently selected from H, D, F, Cl, Br, I, -CN, -NO 2 、

[0017] C3-C30 cycloalkyl, C3-C30 cycloalkenyl, C2-C30 heterocycloalkyl, C2-C30 heterocycloalkenyl, C6-C60 aryl or C5-C60 heteroaryl, and the heteroatoms in the heterocycloalkyl, heterocycloalkenyl and heteroaryl are selected from one or more of Si, Ge, N, P, O, S and Se;

[0018] The R 1 、R 2 and R 3 are independently selected from H, D, F, Cl, Br, I, CN, OH, SH, NH 2 、C1-C30 linear alkyl, C3-C30 branched alkyl, C1-C30 ether chain, C1-C30 thioether chain, C1-C30 ester group chain, C3-C30 cycloalkyl, C3-C30 cycloalkenyl, C2-C30 heterocycloalkyl, C2-C30 heterocycloalkenyl, C6-C60 aryl, C4-C60 aryl or C4-C60 heteroaryl; the heteroatoms in the heterocycloalkyl, heterocycloalkenyl and heteroaryl are selected from one or more of Si, Ge, N, P, O, S and Se; or wherein R 1 and R 2 are bridged by a single bond or a heteroatom, and the bridging heteroatom is selected from one or more of Si, Ge, N, P, O, S and Se.

[0019] In the above technical solution, preferably, the Ar 1 ~Ar 4 Independently selected from one of the groups represented by A1 to A20:

[0020]

[0021] Among them, L 1 , L 2 and L 3 independently selected from H, D, F, Cl, Br, I, CN, OH, SH, NH 2 , C1~C30 straight-chain alkyl, C3~C30 branched alkyl, C1~C30 ether chain, C1~C30 thioether chain, C1~C30 ester chain, C3~C30 cycloalkyl, C3~C30 cycloalkenyl, C2~C30 heterocycloalkyl, C2~C30 heterocycloalkenyl, C6~C60 aromatic, C4~C60 aromatic or C4~C60 heteroaromatic; the heteroatoms in the heterocycloalkyl, heterocycloalkenyl and heteroaromatic groups are selected from one or more of Si, Ge, N, P, O, S and Se.

[0022] In the above technical solution, preferably, X 1 and X 2 independently selected from single bonds (i.e., Ar 1 with Ar 3 ,Ar 2 with Ar 4 directly connected by a single bond), O, S, Se, N (R 1 )、C(R 1 R 2 ) or Si(R 1 R 2 ).

[0023] In the above technical solution, preferably, the Y 1 and Y 2 Independently selected from one of the following structures:

[0024]

[0025] In the above technical solution, preferably, the nitrogen heteroaromatic fused ring compound has any one of the structures shown in formula (A) to formula (C):

[0026]

[0027]

[0028]

[0029] The preparation method of the nitrogen-containing heteroaromatic fused-ring compound of the present invention can be prepared by the methods commonly used in the art for preparing such compounds, without any special limitations. Preferably, the nitrogen-containing heteroaromatic fused-ring compound of the present invention is prepared by the method shown in the following synthetic route.

[0030] The preparation method of the nitrogen-containing heteroaromatic fused-ring compound shown in formula (I) has the following synthetic route:

[0031]

[0032] The preparation method of the nitrogen-containing heteroaromatic fused-ring compound shown in formula (II) has the following synthetic route:

[0033]

[0034] The preparation method of the nitrogen-containing heteroaromatic fused-ring compound shown in formula (III) has the following synthetic route:

[0035]

[0036] The present invention also provides an application of the nitrogen-containing heteroaromatic fused-ring compound as a luminescent material, especially in an organic electroluminescent device.

[0037] The present invention does not particularly limit the structure of the organic electroluminescent device. A conventional organic electroluminescent device well-known to those skilled in the art can be used. Those skilled in the art can select and adjust according to the application situation, quality requirements and product requirements. Preferably, the organic electroluminescent device includes an anode, a cathode, and an organic thin film layer located between the anode and the cathode. The organic thin film layer includes the nitrogen-containing heteroaromatic fused-ring compound of the present invention. Further, the organic thin film layer includes a light-emitting layer, and the light-emitting layer includes the nitrogen-containing heteroaromatic fused-ring compound of the present invention. Specifically, the structure of the organic electroluminescent device of the present invention preferably includes: a substrate; an anode disposed on the substrate; an organic thin film layer disposed on the anode; and a cathode disposed on the organic thin film layer.

[0038] The thickness of the substrate is preferably 0.3 - 0.7 mm, more preferably 0.4 - 0.6 mm; the present invention does not particularly limit the selection of the substrate. A substrate of a conventional organic electroluminescent device well-known to those skilled in the art can be used. Those skilled in the art can select and adjust according to the application situation, quality requirements and product requirements. In the present invention, the substrate is preferably glass or plastic.

[0039] According to the present invention, the anode is preferably a material easy for hole injection, more preferably a conductive metal or a conductive metal oxide, and still more preferably indium tin oxide.

[0040] The organic thin film layer can be one layer or multiple layers, and at least one layer is a light-emitting layer; in the present invention, the organic thin film layer preferably includes a light-emitting layer; the light-emitting layer includes the azapolycyclic aromatic compounds represented by the above formulas (I) to (III); the azapolycyclic aromatic compounds represented by the formulas (I) to (III) provided by the present invention directly form an organic electroluminescent layer as a light-emitting material.

[0041] The cathode is preferably a metal, including but not limited to calcium, magnesium, barium, aluminum, and silver, and preferably aluminum.

[0042] In order to improve the performance and efficiency of the device, the organic thin film layer between the anode and the light-emitting layer preferably further includes one or more of a hole injection layer, a hole transport layer, and an electron blocking layer. The organic thin film layer between the light-emitting layer and the cathode preferably further includes one or more of a hole blocking layer, an electron injection layer, and an electron transport layer. The present invention has no particular limitation on the materials and thicknesses of the hole injection layer, the hole transport layer, the electron blocking layer, the organic electroluminescent layer, the hole blocking layer, the electron injection layer, and the electron transport layer, and they can be selected and adjusted according to the materials and thicknesses well-known to those skilled in the art. The present invention has no particular limitation on the preparation processes of the electrodes, the hole injection layer, the hole transport layer, the electron blocking layer, the organic electroluminescent layer, the hole blocking layer, the electron injection layer, and the electron transport layer, and preferably vacuum evaporation, solution spin coating, solution blade coating, inkjet printing, offset printing, and stereolithography processes are used for preparation.

[0043] The present invention has no special limitation on the preparation method of the organic electroluminescent device, and it can be carried out according to the following method: forming an anode on the substrate; forming one or more organic thin film layers on the anode, including a light-emitting layer; forming a cathode on the organic thin film layer. The light-emitting layer includes the azapolycyclic aromatic compounds represented by the formulas (I) to (III).

[0044] The present invention has no special limitation on the structure and materials of the organic electroluminescent device in the above preparation method, as well as the corresponding preferred principles, and they can correspond to the materials and structures, and the corresponding preferred principles in the aforementioned organic electroluminescent device, and will not be elaborated one by one here.

[0045] The present invention first forms an anode on the substrate. The present invention has no special limitation on the formation method of the anode, and it can be carried out according to the methods well-known to those skilled in the art. The present invention has no special limitation on the formation methods of the light-emitting layer and the organic thin film layers below and above the light-emitting layer, and they can be formed on the anode by vacuum evaporation, solution spin coating, solution blade coating, inkjet printing, offset printing, or stereolithography. After the organic layer is formed, a cathode is prepared on its surface. The present invention has no special limitation on the formation method of the cathode, and it is preferably the methods well-known to those skilled in the art, including but not limited to vacuum deposition.

[0046] The beneficial effects of the present invention are as follows:

[0047] The present invention provides a nitrogen-containing heteroaromatic fused-ring compound as shown in Formula (I) - Formula (III). Compared with the prior art, the present invention uses a nitrogen-containing heteroaromatic fused-ring unit as a luminescent material. On the one hand, the rigid backbone structure of the nitrogen-containing heteroaromatic fused-ring compound can be used to reduce the degree of excited-state structural relaxation, thereby achieving a narrower full width at half maximum (FWHM); on the other hand, the resonance effect between the electron-deficient group and the nitrogen atom is used to achieve the separation of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), thereby achieving a smaller ΔE ST and thermally activated delayed fluorescence (TADF) effect, and further achieving high luminescence efficiency. At the same time, by changing the types of aromatic rings and heteroaromatic rings contained in the fused-ring compound, or introducing different substituents, the delayed fluorescence lifetime and the full width at half maximum can be further adjusted.

[0048] Experimental results show that when the nitrogen-containing heteroaromatic fused-ring compound of the present invention is used as the light-emitting layer of an electroluminescent device, a narrow electroluminescent full width at half maximum can be achieved without a filter and a microcavity structure, and a high external quantum efficiency of the device can also be achieved. Detailed implementation manners

[0049] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts fall within the protection scope of the present invention.

[0050] The reagents used in the following examples are all commercially available.

[0051] Example 1

[0052]

[0053] Under an argon atmosphere, 1-1 (5.00 g, 29.93 mmol), 1-2 (5.43 g, 14.37 mmol), anhydrous potassium carbonate (7.86 g, 56.87 mmol), copper(I) iodide (1.08 g, 5.69 mmol), 18-crown-6-ether (1.50 g, 5.69 mmol) and 34 mL of o-dichlorobenzene were added to a 100 mL two-necked flask. After stirring at 180 °C for 24 hours and cooling to room temperature, the reaction solution was poured into 100 mL of ice water and extracted with dichloromethane (100 mL × 3). The organic phase was dried with anhydrous sodium sulfate, and then the filtrate was concentrated under reduced pressure. The obtained crude product was purified by a chromatography column to obtain product 1-3 (4.96 g, yield: 60%).

[0054] Elemental analysis of its structure (C 36 H 28 N2 O 4 ):Theoretical values: C, 78.24; H, 5.11; N, 5.07; O, 11.58; Measured values: C, 78.25; H, 5.10; N, 5.08; O, 11.57.

[0055] MALDI-TOF-MS: Theoretical value 552.2; Experimental value 552.1.

[0056] Add 1-3 (4.00 g, 7.24 mmol), 140 mL of tetrahydrofuran, 70 mL of methanol, 70 mL of water, and sodium hydroxide (1.74 g, 43.44 mmol) to a 500 mL single-necked flask. Stir at 80 °C for 16 hours. The reaction system changes from a suspension to a clear liquid. Cool the reaction solution to room temperature, rotary evaporate the solvent, then add 50 mL of water to suspend the solid in water, and adjust the pH to 1 with concentrated hydrochloric acid. Filter the suspension, wash with 100 mL of deionized water, and dry the filter cake in a vacuum oven to obtain the yellow solid product 1-4 (3.59 g, yield: 100%), which is directly used for the next step without purification.

[0057] Under an argon atmosphere, add 1-4 (3.59 g, 7.24 mmol) and 210 mL of dichloromethane to a 500 mL two-necked flask. Then, dropwise add oxalyl chloride (28.05 mL, 331.48 mmol) and N,N-dimethylformamide (7.02 mL, 90.67 mmol) successively. After the addition is complete, stir at 45 °C for 3 hours. Cool the reaction to room temperature, and dropwise add tin(IV) chloride (16.95 mL, 144.80 mmol). After the addition is complete, stir at 45 °C for 21 hours. Cool the reaction to room temperature, under an ice-water bath condition, adjust the pH to 10 with 2 M sodium hydroxide solution, then add 100 mL of dichloromethane for dilution, and wash with deionized water three times (100 mL × 3). Then dry with anhydrous sodium sulfate. The concentrated solution obtained after removing the solvent from the organic phase is purified by a chromatography column to obtain the product 1-5 (4.09 g, yield: 75%).

[0058] Elemental analysis of its structure (C 32 H 16 N 2 O 2 ):Theoretical values: C, 83.47; H, 3.50; N, 6.08; O, 6.95; Measured values: C, 83.46; H, 3.49; N, 6.07; O, 6.98.

[0059] MALDI-TOF-MS: Theoretical value 460.1; Experimental value 460.1.

[0060] Add 1-5 (4.09 g, 8.89 mmol) and Lawson's reagent (5.75 g, 14.22 mmol) into a 250 mL two-necked flask, add 160 mL of toluene and stir to dissolve. Bubble argon into the reaction flask for 30 minutes, then heat the reaction solution to 110 °C and react for 1 hour. After the reaction is completed, cool to room temperature, rotary evaporate under reduced pressure to remove the reaction solvent, and purify the obtained crude product by a chromatography column to obtain product 1-6 (2.84 g, yield: 65%) (i.e., compound A1-1).

[0061] Elemental analysis of its structure (C 32 H 16 N 2 S 2 ): Theoretical values: C, 78.02; H, 3.27; N, 5.69; S, 13.02; Measured values: C, 78.03; H, 3.26; N, 5.70; S, 13.01.

[0062] MALDI-TOF-MS: Theoretical value 492.2; Experimental value 492.1.

[0063] Example 2

[0064]

[0065] Under an argon atmosphere, add 2-1 (5.00 g, 17.91 mmol), 1-2 (3.25 g, 8.60 mmol), anhydrous potassium carbonate (4.70 g, 34.03 mmol), cuprous iodide (0.65 g, 3.40 mmol), 18-crown-6-ether (0.90 g, 3.40 mmol) and 20 mL of o-dichlorobenzene into a 100 mL two-necked flask. After stirring at 180 °C for 24 hours, cool to room temperature. Pour the reaction solution into 100 mL of ice water, extract with dichloromethane (100 mL × 3), dry the organic phase with anhydrous sodium sulfate, then concentrate the filtrate under reduced pressure, and purify the obtained crude product by a chromatography column to obtain product 2-2 (9.92 g, yield: 59%).

[0066] Elemental analysis of its structure (C 52 H 60 N 2 O 4 ): Theoretical values: C, 80.38; H, 7.78; N, 3.61; O, 8.24; Measured values: C, 80.37; H, 7.79; N, 3.60; O, 8.25.

[0067] MALDI-TOF-MS: Theoretical value 776.3; Experimental value 776.5.

[0068] In a 500 mL single-necked flask, add 2-2 (2.00 g, 2.58 mmol), 50 mL of tetrahydrofuran, 25 mL of methanol, 25 mL of water, and sodium hydroxide (0.62 g, 15.45 mmol). Stir at 80 °C for 16 hours. The reaction system changes from a suspension to a clear liquid. Cool the reaction solution to room temperature, rotary evaporate the solvent, then add 50 mL of water to suspend the solid in water, and adjust the pH to 1 with concentrated hydrochloric acid. Filter the suspension by suction and wash it with 100 mL of deionized water. The filter cake is dried in a vacuum oven to obtain a yellow solid product 2-3 (1.86 g, yield: 100%), which is directly used for the next step without purification.

[0069] Under an argon atmosphere, add 2-3 (1.86 g, 2.58 mmol) and 75 mL of dichloromethane to a 500 mL two-necked flask. Then, dropwise add oxalyl chloride (10.00 mL, 118.18 mmol) and N,N-dimethylformamide (2.50 mL, 32.29 mmol) sequentially. After the addition is complete, stir at 45 °C for 3 hours. Cool the reaction to room temperature, and dropwise add tin(IV) chloride (6.04 mL, 51.60 mmol). After the addition is complete, stir at 45 °C for 21 hours. Cool the reaction to room temperature. Under an ice-water bath condition, adjust the pH to 10 with 2 M sodium hydroxide solution, then add 100 mL of dichloromethane for dilution, and wash it with deionized water three times (100 mL × 3). Then dry it with anhydrous sodium sulfate. The concentrated solution obtained after removing the solvent from the organic phase is purified by a chromatography column to obtain the product 2-4 (1.27 g, yield: 72%).

[0070] Elemental analysis of its structure (C 48 H 48 N 2 O 2 ): Theoretical values: C, 84.17; H, 7.06; N, 4.09; O, 4.67; Measured values: C, 84.18; H, 7.05; N, 4.08; O, 4.68.

[0071] MALDI-TOF-MS: Theoretical value 684.4; Experimental value 684.3.

[0072] Add 2-4 (1.27 g, 1.86 mmol) and Lawson's reagent (1.20 g, 2.97 mmol) to a 250 mL two-necked flask, add 40 mL of toluene and stir to dissolve. Bubble argon into the reaction flask for 30 minutes, then heat the reaction solution to 110 °C and react for 1 hour. After the reaction is completed, cool to room temperature, rotary evaporate the reaction solvent under reduced pressure. The obtained crude product is purified by a chromatography column to obtain the product 2-5 (0.91 g, yield: 68%) (i.e., compound A1-2).

[0073] Elemental analysis of its structure (C 48 H 48 N 2 S 2 ): Theoretical values: C, 80.40; H, 6.75; N, 3.91; S, 8.94; Test values: C, 80.42; H, 6.77; N, 3.89; S, 8.92.

[0074] MALDI-TOF-MS: Theoretical value 716.3; Experimental value 716.3.

[0075] 1 H NMR (400 MHz, CDCl 3 ): δ ppm 8.95 (s, 2H), 8.41 (s, 2H), 8.36 (s, 2H), 7.62 (d, 2H), 7.50 (d, 2H), 7.21 (s, 2H), 1.45 (s, 18H), 1.43 (s, 18H).

[0076] Example 3

[0077]

[0078] Under an argon atmosphere, 3-1 (5.00 g, 11.59 mmol), 1-2 (2.10 g, 5.57 mmol), anhydrous potassium carbonate (3.04 g, 22.02 mmol), copper(I) iodide (0.42 g, 2.20 mmol), 18-crown-6-ether (0.58 g, 2.20 mmol) and 13 mL of o-dichlorobenzene were added to a 100 mL two-necked flask. After stirring at 180 °C for 24 hours, it was cooled to room temperature. The reaction solution was poured into 100 mL of ice water and extracted with dichloromethane (100 mL × 3). The organic phase was dried over anhydrous sodium sulfate, and then the filtrate was concentrated under reduced pressure. The obtained crude product was purified by a chromatography column to obtain product 3-2 (3.44 g, yield: 55%).

[0079] Elemental analysis of its structure (C 76 H 76 N 2 O 4 ):Theoretical values: C, 84.41; H, 7.08; N, 2.59; O, 5.92; Test values: C, 84.42; H, 7.07; N, 2.58; O, 5.93.

[0080] MALDI-TOF-MS: Theoretical value 1080.5; Experimental value 1080.6.

[0081] Add 3-2 (2.00 g, 1.85 mmol), 37 mL of tetrahydrofuran, 19 mL of methanol, 19 mL of water and sodium hydroxide (0.44 g, 11.11 mmol) into a 500 mL single-necked flask. Stir at 80 °C for 16 hours. The reaction system changes from a suspension to a clear liquid. Cool the reaction solution to room temperature, rotary evaporate the solvent, then add 50 mL of water to suspend the solid in water, and adjust the pH to 1 with concentrated hydrochloric acid. Filter the suspension by suction and wash it with 100 mL of deionized water. The filter residue is dried in a vacuum oven to obtain a yellow solid product 3-3 (1.90 g, yield: 100%). This product is directly used for the next step without purification.

[0082] Under an argon atmosphere, add 3-3 (1.90 g, 1.85 mmol) and 61 mL of dichloromethane into a 500 mL two-necked flask. Then, dropwise add oxalyl chloride (7.20 mL, 84.75 mmol) and N,N-dimethylformamide (1.80 mL, 23.15 mmol) successively drop by drop. After the addition is completed, stir at 45 °C for 3 hours. Cool the reaction to room temperature, dropwise add tin(IV) chloride (4.34 mL, 37.09 mmol). After the addition is completed, stir at 45 °C for 21 hours. Cool the reaction to room temperature. Under the condition of an ice-water bath, adjust the pH to 10 with 2 M sodium hydroxide solution, then add 100 mL of dichloromethane for dilution, and wash it with deionized water three times (100 mL × 3). Then dry it with anhydrous sodium sulfate. The concentrated solution obtained after removing the solvent from the organic phase is purified by a chromatography column to obtain the product 3-4 (1.13 g, yield: 62%).

[0083] Elemental analysis of its structure (C 72 H 64 N 2 O 2 ): Theoretical values: C, 87.41; H, 6.52; N, 2.83; O, 3.23; Measured values: C, 87.40; H, 6.53; N, 2.82; O, 3.24.

[0084] MALDI-TOF-MS: Theoretical value 988.6; Experimental value 988.5.

[0085] Add 3-4 (1.13 g, 1.14 mmol) and Lawson's reagent (0.74 g, 1.83 mmol) into a 250 mL two-necked flask. Add 30 mL of toluene and stir to dissolve. Bubble argon into the reaction flask for 30 minutes. Then heat the reaction solution to 110 °C and react for 1 hour. After the reaction is completed, cool to room temperature and rotary evaporate the reaction solvent under reduced pressure. The obtained crude product is purified by a chromatography column to obtain the product 3-5 (0.72 g, yield: 62%) (i.e., compound A1-3).

[0086] Elemental analysis of its structure (C72 H 64 N 2 S 2 ):Theoretical values: C, 84.66; H, 6.32; N, 2.74; S, 6.28; Measured values: C, 84.65; H, 6.33; N, 2.75; S, 6.27.

[0087] MALDI-TOF-MS: Theoretical value 1020.6; Experimental value 1020.5.

[0088] Example 4

[0089]

[0090] Under an argon atmosphere, 4-1 (5.00 g, 12.40 mmol), 1-2 (2.25 g, 5.95 mmol), anhydrous potassium carbonate (3.26 g, 23.56 mmol), copper(I) iodide (0.45 g, 2.36 mmol), 18-crown-6-ether (0.62 g, 2.36 mmol) and 13 mL of o-dichlorobenzene were added to a 100 mL two-necked flask. After stirring at 180 °C for 24 hours, it was cooled to room temperature. The reaction solution was poured into 100 mL of ice water and extracted with dichloromethane (100 mL × 3). The organic phase was dried over anhydrous sodium sulfate, and then the filtrate was concentrated under reduced pressure. The crude product obtained was purified by a chromatography column to obtain product 4-2 (3.56 g, yield: 56%).

[0091] Elemental analysis of its structure (C 72 H 68 N 2 O 4 ):Theoretical values: C, 84.34; H, 6.68; N, 2.73; O, 6.24; Measured values: C, 84.33; H, 6.69; N, 2.74; O, 6.23.

[0092] MALDI-TOF-MS: Theoretical value 1024.5; Experimental value 1024.4.

[0093] 4-2 (2.00 g, 1.95 mmol), 39 mL of tetrahydrofuran, 20 mL of methanol, 20 mL of water and sodium hydroxide (0.47 g, 11.71 mmol) were added to a 250 mL single-necked flask. It was stirred at 80 °C for 16 hours, and the reaction system changed from a suspension to a clear liquid. The reaction solution was cooled to room temperature, the solvent was rotary-evaporated, and then 50 mL of water was added to suspend the solid in water. The pH was adjusted to 1 with concentrated hydrochloric acid. The suspension was filtered by suction and washed with 100 mL of deionized water. The filter cake was dried in a vacuum oven to obtain a yellow solid product 4-3 (1.89 g, yield: 100%), which was directly used for the next step without purification.

[0094] Under an argon atmosphere, 4-3 (1.89 g, 1.95 mmol) and 57 mL of dichloromethane were added to a 250 mL two-necked flask. Then, oxalyl chloride (7.57 mL, 89.46 mmol) and N,N-dimethylformamide (1.90 mL, 24.54 mmol) were added dropwise in sequence. After the addition was complete, the mixture was stirred at 45 °C for 3 hours. The reaction was cooled to room temperature, and tin(IV) chloride (4.56 mL, 51.60 mmol) was added dropwise. After the addition was complete, the mixture was stirred at 45 °C for 21 hours. The reaction was cooled to room temperature, and under ice-water bath conditions, the pH was adjusted to 10 with 2 M sodium hydroxide solution. Then, 100 mL of dichloromethane was added for dilution, and the mixture was washed three times with deionized water (100 mL × 3). After that, it was dried over anhydrous sodium sulfate. The concentrated solution obtained after removing the solvent from the organic phase was purified by a chromatography column to obtain the product 4-4 (1.10 g, yield: 60%).

[0095] Elemental analysis of its structure (C 68 H 56 N 2 O 2 ): Theoretical values: C, 87.52; H, 6.05; N, 3.00; O, 3.43; Measured values: C, 87.51; H, 6.06; N, 3.01; O, 3.42.

[0096] MALDI-TOF-MS: Theoretical value 932.3; Experimental value 932.4.

[0097] 4-4 (1.10 g, 1.18 mmol) and Lawson's reagent (0.76 g, 1.89 mmol) were added to a 250 mL two-necked flask. 30 mL of toluene was added and stirred until dissolved. Argon was bubbled into the reaction flask for 30 minutes. Then, the reaction solution was heated to 110 °C and reacted for 1 hour. After the reaction was completed, it was cooled to room temperature, and the reaction solvent was removed by rotary evaporation under reduced pressure. The obtained crude product was purified by a chromatography column to obtain the product 4-5 (0.79 g, yield: 79%) (i.e., compound A1-4).

[0098] Elemental analysis of its structure (C 68 H 56 N 2 S 2 ): Theoretical values: C, 84.61; H, 5.85; N, 2.90; S, 6.64; Measured values: C, 84.60; H, 5.86; N, 2.90; S, 6.64.

[0099] MALDI-TOF-MS: Theoretical value 964.4; Experimental value 964.5.

[0100] Example 5

[0101]

[0102] Under an argon atmosphere, 5-1 (5.00 g, 29.58 mmol), 1-2 (5.36 g, 14.20 mmol), anhydrous potassium carbonate (7.77 g, 56.20 mmol), copper(I) iodide (1.07 g, 5.62 mmol), 18-crown-6-ether (1.49 g, 5.62 mmol) and 34 mL of o-dichlorobenzene were added to a 100 mL two-necked flask. After stirring at 180 °C for 24 h, the mixture was cooled to room temperature. The reaction solution was poured into 100 mL of ice water and extracted with dichloromethane (100 mL × 3). The organic phase was dried over anhydrous sodium sulfate, and then the filtrate was concentrated under reduced pressure. The crude product obtained was purified by column chromatography to give product 5-2 (5.35 g, yield: 65%).

[0103] Elemental analysis of its structure (C 32 H 24 N 6 O 4 ): Theoretical values: C, 69.06; H, 4.35; N, 15.10; O, 11.50; Measured values: C, 69.05; H, 4.36; N, 15.11; O, 11.49.

[0104] MALDI-TOF-MS: Theoretical value 566.1; Experimental value 566.2.

[0105] 5-2 (5.00 g, 8.99 mmol), 180 mL of tetrahydrofuran, 92 mL of methanol, 92 mL of water and sodium hydroxide (2.16 g, 53.94 mmol) were added to a 500 mL single-necked flask. The mixture was stirred at 80 °C for 16 h, and the reaction system changed from a suspension to a clear liquid. The reaction solution was cooled to room temperature, the solvent was rotary-evaporated, and then 50 mL of water was added to suspend the solid in water. The pH was adjusted to 1 with concentrated hydrochloric acid. The suspension was filtered by suction and washed with 100 mL of deionized water. The filter cake was dried in a vacuum oven to obtain a solid product 5-3 (4.50 g, yield: 100%), which was used directly in the next step without purification.

[0106] Under an argon atmosphere, 5-3 (4.50 g, 8.99 mmol) and 296 mL of dichloromethane were added to a 500 mL two-necked flask. Then, oxalyl chloride (34.84 mL, 411.72 mmol) and N,N-dimethylformamide (8.70 mL, 112.34 mmol) were added dropwise in sequence. After the addition was complete, the mixture was stirred at 45 °C for 3 hours. The reaction was cooled to room temperature, and tin(IV) chloride (21.04 mL, 179.8 mmol) was added dropwise. After the addition was complete, the mixture was stirred at 45 °C for 21 hours. The reaction was cooled to room temperature, and under ice-water bath conditions, the pH was adjusted to 10 with 2 M sodium hydroxide solution. Then, 100 mL of dichloromethane was added for dilution, and the mixture was washed three times with deionized water (100 mL × 3). After drying with anhydrous sodium sulfate, the concentrated solution obtained after removing the solvent from the organic phase was purified by a chromatography column to obtain product 5-4 (2.25 g, yield: 54%).

[0107] Elemental analysis of its structure (C 28 H 12 N 6 O 2 ): Theoretical values: C, 72.41; H, 2.60; N, 18.10; O, 6.89; Measured values: C, 72.40; H, 2.61; N, 18.09; O, 6.90.

[0108] MALDI-TOF-MS: Theoretical value 464.1; Experimental value 464.0.

[0109] 5-4 (2.00 g, 4.31 mmol) and Lawson's reagent (2.77 g, 6.85 mmol) were added to a 100 mL two-necked flask. 80 mL of toluene was added and stirred until dissolved. Argon was bubbled into the reaction flask for 30 minutes. Then, the reaction solution was heated to 110 °C and reacted for 1 hour. After the reaction was completed, it was cooled to room temperature, and the reaction solvent was removed by rotary evaporation under reduced pressure. The obtained crude product was purified by a chromatography column to obtain product 5-5 (1.41 g, yield: 66%) (i.e., compound A1-5).

[0110] Elemental analysis of its structure (C 28 H 12 N 6 S 2 ): Theoretical values: C, 67.73; H, 2.44; N, 16.92; S, 12.91; Measured values: C, 67.72; H, 2.45; N, 16.91; S, 12.92.

[0111] MALDI-TOF-MS: Theoretical value 496.1; Experimental value 496.2.

[0112] Example 6

[0113]

[0114] Under argon atmosphere, 6-1 (5.00 g, 18.70 mmol), 1-2 (3.39 g, 8.98 mmol), anhydrous potassium carbonate (4.91 g, 35.53 mmol), cuprous iodide (0.68 g, 3.55 mmol), 18-crown-6-ether (0.94 g, 3.55 mmol) and 21 mL of o-dichlorobenzene were added to a 100 mL two-necked flask. The mixture was stirred at 180 ° C for 24 hours and then cooled to room temperature. The reaction solution was poured into 100 mL of ice water and extracted with dichloromethane (100 mL×3). The organic phase was dried over anhydrous sodium sulfate, and the filtrate was then concentrated under reduced pressure. The crude product was purified by chromatography to obtain product 6-2 (4.57 g, yield: 65%).

[0115] Elemental analysis of its structure (C 52 H 36 N 2 O 4 ): Theoretical value: C, 82.96; H, 4.82; N, 3.72; O, 8.50; Test value: C, 82.95; H, 4.83; N, 3.71; O, 8.51.

[0116] MALDI-TOF-MS: theoretical value 752.3; experimental value 752.3.

[0117] In a 500mL single-mouth bottle, 6-2 (5.00g, 6.65mmol), 133mL tetrahydrofuran, 69mL methanol, 69mL water and sodium hydroxide (1.60g, 39.88mmol) were added, and stirred at 80°C for 16 hours. The reaction system changed from a suspension to a clear liquid. The reaction solution was cooled to room temperature, the solvent was spun out, and 50mL of water was added to suspend the solid in the water, and the pH was adjusted to 1 with concentrated hydrochloric acid. The suspension was filtered and washed with 100mL of deionized water, and the filter residue was dried in a vacuum oven to obtain a solid product 6-3 (4.63g, yield: 100%), which was directly used in the next step without purification.

[0118] Under an argon atmosphere, 6-3 (4.00 g, 5.75 mmol) and 190 mL of dichloromethane were added to a 500 mL two-necked flask. Then, oxalyl chloride (22.29 mL, 263.36 mmol) and N,N-dimethylformamide (5.56 mL, 71.86 mmol) were added dropwise in sequence. After the addition was complete, the mixture was stirred at 45 °C for 3 hours. The reaction was cooled to room temperature, and tin(IV) chloride (13.46 mL, 115 mmol) was added dropwise. After the addition was complete, the mixture was stirred at 45 °C for 21 hours. The reaction was cooled to room temperature, and under ice-water bath conditions, the pH was adjusted to 10 with 2 M sodium hydroxide solution. Then, 100 mL of dichloromethane was added for dilution, and the mixture was washed three times with deionized water (100 mL × 3). After drying with anhydrous sodium sulfate, the concentrated solution obtained after removing the solvent from the organic phase was purified by a chromatography column to obtain the product 6-4 (2.00 g, yield: 53%).

[0119] Elemental analysis of its structure (C 48 H 24 N 2 O 2 ): Theoretical values: C, 87.26; H, 3.66; N, 4.24; O, 4.84; Measured values: C, 87.26; H, 3.66; N, 4.25; O, 4.83.

[0120] MALDI-TOF-MS: Theoretical value 660.1; Experimental value 660.2.

[0121] 6-4 (2.00 g, 4.31 mmol) and Lawson's reagent (1.95 g, 4.82 mmol) were added to a 100 mL two-necked flask. 60 mL of toluene was added and stirred until dissolved. The reaction flask was purged with argon for 30 minutes. Then, the reaction solution was heated to 110 °C and reacted for 1 hour. After the reaction was completed, it was cooled to room temperature, and the reaction solvent was removed by rotary evaporation under reduced pressure. The obtained crude product was purified by a chromatography column to obtain the product 6-5 (1.36 g, yield: 65%) (i.e., compound A1-8).

[0122] Elemental analysis of its structure (C 48 H 24 N 2 S 2 ): Theoretical values: C, 83.21; H, 3.49; N, 4.04; S, 9.25; Measured values: C, 83.20; H, 3.50; N, 4.05; S, 9.24.

[0123] MALDI-TOF-MS: Theoretical value 692.1; Experimental value 692.0.

[0124] Example 7

[0125]

[0126] Under an argon atmosphere, 7-1 (5.00 g, 17.92 mmol), 1-2 (3.25 g, 8.60 mmol), anhydrous potassium carbonate (4.71 g, 34.05 mmol), copper(I) iodide (0.65 g, 3.41 mmol), 18-crown-6-ether (0.90 g, 3.41 mmol) and 21 mL of o-dichlorobenzene were added to a 100 mL two-necked flask. After stirring at 180 °C for 24 hours, the mixture was cooled to room temperature. The reaction solution was poured into 100 mL of ice water and extracted with dichloromethane (100 mL × 3). The organic phase was dried over anhydrous sodium sulfate, and then the filtrate was concentrated under reduced pressure. The crude product obtained was purified by column chromatography to give product 7-2 (4.38 g, yield: 63%).

[0127] Elemental analysis of its structure (C 44 H 28 N 2 O 4 S 4 ): Theoretical values: C, 68.02; H, 3.63; N, 3.61; O, 8.24; S, 16.51; Measured values: C, 68.01; H, 3.63; N, 3.62; O, 8.25; S, 16.50.

[0128] MALDI-TOF-MS: Theoretical value 776.1; Experimental value 776.0.

[0129] 7-2 (4.00 g, 5.15 mmol), 104 mL of tetrahydrofuran, 54 mL of methanol, 54 mL of water and sodium hydroxide (1.24 g, 30.92 mmol) were added to a 500 mL single-necked flask. The mixture was stirred at 80 °C for 16 hours, and the reaction system changed from a suspension to a clear liquid. The reaction solution was cooled to room temperature, the solvent was removed by rotary evaporation, and then 50 mL of water was added to suspend the solid in water. The pH was adjusted to 1 with concentrated hydrochloric acid. The suspension was filtered by suction and washed with 100 mL of deionized water. The filter cake was dried in a vacuum oven to obtain the solid product 7-3 (3.71 g, yield: 100%), which was used directly in the next step without purification.

[0130] Under an argon atmosphere, 7-3 (3.00 g, 4.17 mmol) and 140 mL of dichloromethane were added to a 500 mL two-necked flask. Then, oxalyl chloride (16.16 mL, 191.02 mmol) and N,N-dimethylformamide (4.03 mL, 52.08 mmol) were added dropwise in sequence. After the addition was completed, the mixture was stirred at 45 °C for 3 hours. The reaction was cooled to room temperature, and tin(IV) chloride (9.75 mL, 83.33 mmol) was added dropwise. After the addition was completed, the mixture was stirred at 45 °C for 21 hours. The reaction was cooled to room temperature, and under ice-water bath conditions, the pH was adjusted to 10 with 2 M sodium hydroxide solution. Then, 100 mL of dichloromethane was added for dilution, and the mixture was washed three times with deionized water (100 mL × 3). After drying with anhydrous sodium sulfate, the concentrated solution obtained after removing the solvent from the organic phase was purified by a chromatography column to obtain the product 7-4 (1.49 g, yield: 52%).

[0131] Elemental analysis of its structure (C 40 H 16 N 2 O 2 S 4 ): Theoretical values: C, 70.16; H, 2.36; N, 4.09; O, 4.67; S, 18.73; Measured values: C, 70.15; H, 2.37; N, 4.09; O, 4.68; S, 18.72.

[0132] MALDI-TOF-MS: Theoretical value 684.0; Experimental value 684.1.

[0133] 7-4 (1.00 g, 1.46 mmol) and Lawson's reagent (0.94 g, 2.32 mmol) were added to a 100 mL two-necked flask. 30 mL of toluene was added and stirred until dissolved. The reaction flask was purged with argon for 30 minutes. Then, the reaction solution was heated to 110 °C and reacted for 1 hour. After the reaction was completed, it was cooled to room temperature, and the reaction solvent was removed by rotary evaporation under reduced pressure. The obtained crude product was purified by a chromatography column to obtain the product 7-5 (0.67 g, yield: 64%) (i.e., compound A1-12).

[0134] Elemental analysis of its structure (C 40 H 16 N 2 S 6 ): Theoretical values: C, 67.01; H, 2.25; N, 3.91; S, 26.83; Measured values: C, 67.02; H, 2.24; N, 3.90; S, 26.84.

[0135] MALDI-TOF-MS: Theoretical value 716.0; Experimental value 716.0.

[0136] Example 8

[0137]

[0138] Under an argon atmosphere, 8-1 (10.00 g, 20.11 mmol), 1-2 (3.65 g, 9.65 mmol), anhydrous potassium carbonate (5.28 g, 38.21 mmol), copper(I) iodide (0.73 g, 3.82 mmol), 18-crown-6-ether (1.00 g, 3.82 mmol) and 23 mL of o-dichlorobenzene were added to a 100 mL two-necked flask. After stirring at 180 °C for 24 hours, the mixture was cooled to room temperature. The reaction solution was poured into 100 mL of ice water and extracted with dichloromethane (100 mL × 3). The organic phase was dried over anhydrous sodium sulfate, and then the filtrate was concentrated under reduced pressure. The crude product obtained was purified by column chromatography to give product 8-2 (8.05 g, yield: 66%).

[0139] Elemental analysis of its structure (C 84 H 56 N 6 O 4 ): Theoretical values: C, 83.15; H, 4.65; N, 6.93; O, 5.27; Measured values: C, 83.16; H, 4.64; N, 6.91; O, 5.29.

[0140] MALDI-TOF-MS: Theoretical value 1212.4; Experimental value 1212.3.

[0141] 8-2 (8.00 g, 6.60 mmol), 133 mL of tetrahydrofuran, 69 mL of methanol, 69 mL of water and sodium hydroxide (1.60 g, 39.88 mmol) were added to a 500 mL single-necked flask. The mixture was stirred at 80 °C for 16 hours, and the reaction system changed from a suspension to a clear liquid. The reaction solution was cooled to room temperature, the solvent was removed by rotary evaporation, and then 50 mL of water was added to suspend the solid in water. The pH was adjusted to 1 with concentrated hydrochloric acid. The suspension was filtered by suction and washed with 100 mL of deionized water. The filter cake was dried in a vacuum oven to obtain the solid product 8-3 (7.63 g, yield: 100%), which was used directly in the next step without purification.

[0142] Under an argon atmosphere, 8-3 (7.63 g, 6.60 mmol) and 220 mL of dichloromethane were added to a 500 mL two-necked flask. Subsequently, oxalyl chloride (25.58 mL, 302.26 mmol) and N,N-dimethylformamide (6.38 mL, 82.38 mmol) were added dropwise in sequence. After the addition was complete, the mixture was stirred at 45 °C for 3 hours. The reaction was cooled to room temperature, and tin(IV) chloride (15.45 mL, 132.00 mmol) was added dropwise. After the addition was complete, the mixture was stirred at 45 °C for 21 hours. The reaction was cooled to room temperature, and under ice-water bath conditions, the pH was adjusted to 10 with 2 M sodium hydroxide solution. Then, 100 mL of dichloromethane was added for dilution, and the mixture was washed three times with deionized water (100 mL × 3). After drying with anhydrous sodium sulfate, the concentrated solution obtained after removing the solvent from the organic phase was purified by column chromatography to obtain the product 8-4 (4.07 g, yield: 55%).

[0143] Elemental analysis of its structure (C 80 H 44 N 6 O 2 ): Theoretical values: C, 85.70; H, 3.96; N, 7.50; O, 2.85; Measured values: C, 85.71; H, 3.95; N, 7.51; O, 2.84.

[0144] MALDI-TOF-MS: Theoretical value 1120.4; Experimental value 1120.5.

[0145] In a 100 mL two-necked flask, 8-4 (2.00 g, 1.79 mmol) and Lawson's reagent (1.15 g, 2.84 mmol) were added. 31 mL of toluene was added and stirred until dissolved. The reaction flask was purged with argon for 30 minutes. Then, the reaction solution was heated to 110 °C and reacted for 1 hour. After the reaction was completed, it was cooled to room temperature, and the reaction solvent was removed by rotary evaporation under reduced pressure. The obtained crude product was purified by column chromatography to obtain the product 8-5 (1.34 g, yield: 65%) (i.e., compound A1-18).

[0146] Elemental analysis of its structure (C 80 H 44 N 6 S 2 ): Theoretical values: C, 83.31; H, 3.85; N, 7.29; S, 5.56; Measured values: C, 83.32; H, 3.84; N, 7.30; S, 5.55.

[0147] MALDI-TOF-MS: Theoretical value 1152.3; Experimental value 1152.4.

[0148] Example 9

[0149]

[0150] Under an argon atmosphere, 9-1 (5.00 g, 27.31 mmol), 1-2 (4.95 g, 13.11 mmol), anhydrous potassium carbonate (7.17 g, 51.89 mmol), copper(I) iodide (1.00 g, 5.19 mmol), 18-crown-6-ether (1.37 g, 5.19 mmol) and 33 mL of o-dichlorobenzene were added to a 100 mL two-necked flask. After stirring at 180 °C for 24 hours, it was cooled to room temperature. The reaction solution was poured into 100 mL of ice water and extracted with dichloromethane (100 mL × 3). The organic phase was dried over anhydrous sodium sulfate, and then the filtrate was concentrated under reduced pressure. The obtained crude product was purified by a chromatography column to obtain product 9-2 (5.26 g, yield: 66%).

[0151] Elemental analysis of its structure (C 36 H 28 N 2 O 6 ): Theoretical values: C, 73.96; H, 4.83; N, 4.79; O, 16.42; Measured values: C, 73.97; H, 4.82; N, 4.80; O, 16.41.

[0152] MALDI-TOF-MS: Theoretical value 584.2; Experimental value 584.2.

[0153] 9-2 (5.00 g, 8.56 mmol), 172 mL of tetrahydrofuran, 89 mL of methanol, 89 mL of water and sodium hydroxide (2.05 g, 51.35 mmol) were added to a 500 mL single-necked flask. It was stirred at 80 °C for 16 hours. The reaction system changed from a suspension to a clear liquid. The reaction solution was cooled to room temperature, the solvent was rotary-evaporated, and then 50 mL of water was added to suspend the solid in water. The pH was adjusted to 1 with concentrated hydrochloric acid. The suspension was filtered by suction and washed with 100 mL of deionized water. The filter cake was dried in a vacuum oven to obtain a solid product 9-3 (4.52 g, yield: 100%), and this product was directly used for the next step without purification.

[0154] Under an argon atmosphere, 9-3 (4.00 g, 7.57 mmol) and 250 mL of dichloromethane were added to a 500 mL two-necked flask. Subsequently, oxalyl chloride (29.20 mL, 347.11 mmol) and N,N-dimethylformamide (7.40 mL, 94.79 mmol) were added dropwise in sequence. After the addition was complete, the mixture was stirred at 45 °C for 3 hours. The reaction was cooled to room temperature, and tin(IV) chloride (17.70 mL, 151.40 mmol) was added dropwise. After the addition was complete, the mixture was stirred at 45 °C for 21 hours. The reaction was cooled to room temperature, and under ice-water bath conditions, the pH was adjusted to 10 with 2 M sodium hydroxide solution. Then, 100 mL of dichloromethane was added for dilution, and the mixture was washed three times with deionized water (100 mL × 3). After that, it was dried over anhydrous sodium sulfate. The concentrated solution obtained after removing the solvent from the organic phase was purified by a chromatography column to obtain the product 9-4 (2.01 g, yield: 54%).

[0155] Elemental analysis of its structure (C 32 H 16 N 2 O 4 ): Theoretical values: C, 78.04; H, 3.27; N, 5.69; O, 12.99; Measured values: C, 78.03; H, 3.28; N, 5.70; O, 12.98.

[0156] MALDI-TOF-MS: Theoretical value 492.1; Experimental value 492.0.

[0157] 9-4 (2.00 g, 4.06 mmol) and Lawson's reagent (2.61 g, 6.46 mmol) were added to a 250 mL two-necked flask. 74 mL of toluene was added and stirred until dissolved. Argon was bubbled into the reaction flask for 30 minutes. Then, the reaction solution was heated to 110 °C and reacted for 1 hour. After the reaction was completed, it was cooled to room temperature, and the reaction solvent was removed by rotary evaporation under reduced pressure. The obtained crude product was purified by a chromatography column to obtain the product 9-5 (2.13 g, yield: 64%) (i.e., compound A2-1).

[0158] Elemental analysis of its structure (C 32 H 16 N 2 O 2 S 2 ): Theoretical values: C, 73.26; H, 3.07; N, 5.34; O, 6.10; S, 12.22; Measured values: C, 73.27; H, 3.06; N, 5.34; O, 6.11; S, 12.21.

[0159] MALDI-TOF-MS: Theoretical value 524.1; Experimental value 524.2.

[0160] Example 10

[0161]

[0162] Under an argon atmosphere, 10-1 (5.00 g, 15.10 mmol), 1-2 (2.74 g, 7.25 mmol), anhydrous potassium carbonate (3.97 g, 28.69 mmol), copper(I) iodide (0.55 g, 2.87 mmol), 18-crown-6-ether (0.76 g, 2.87 mmol) and 17 mL of o-dichlorobenzene were added to a 100 mL two-necked flask. After stirring at 180 °C for 24 hours and cooling to room temperature, the reaction solution was poured into 100 mL of ice water and extracted with dichloromethane (100 mL × 3). The organic phase was dried over anhydrous sodium sulfate, and then the filtrate was concentrated under reduced pressure. The crude product obtained was purified by a chromatography column to give product 10-2 (4.32 g, yield: 65%).

[0163] Elemental analysis of its structure (C 62 H 44 N 2 O 4 ): Theoretical values: C, 84.52; H, 5.03; N, 3.18; O, 7.26; Measured values: C, 84.52; H, 5.03; N, 3.17; O, 7.27.

[0164] MALDI-TOF-MS: Theoretical value 880.3; Experimental value 880.2.

[0165] 10-2 (4.00 g, 4.54 mmol), 91 mL of tetrahydrofuran, 47 mL of methanol, 47 mL of water and sodium hydroxide (1.09 g, 27.24 mmol) were added to a 500 mL single-necked flask. The mixture was stirred at 80 °C for 16 hours, and the reaction system changed from a suspension to a clear liquid. The reaction solution was cooled to room temperature, the solvent was removed by rotary evaporation, and then 50 mL of water was added to suspend the solid in water. The pH was adjusted to 1 with concentrated hydrochloric acid. The suspension was filtered by suction and washed with 100 mL of deionized water. The filter cake was dried in a vacuum oven to obtain the solid product 10-3 (3.74 g, yield: 100%), which was used directly for the next step without purification.

[0166] Under an argon atmosphere, 10-3 (3.00 g, 3.64 mmol) and 121 mL of dichloromethane were added to a 500 mL two-necked flask. Subsequently, oxalyl chloride (14.11 mL, 166.75 mmol) and N,N-dimethylformamide (3.52 mL, 45.46 mmol) were added dropwise in sequence. After the addition was complete, the mixture was stirred at 45 °C for 3 hours. The reaction was cooled to room temperature, and tin(IV) chloride (8.52 mL, 72.79 mmol) was added dropwise. After the addition was complete, the mixture was stirred at 45 °C for 21 hours. The reaction was cooled to room temperature, and under ice-water bath conditions, the pH was adjusted to 10 with 2 M sodium hydroxide solution. Then, 100 mL of dichloromethane was added for dilution, and the mixture was washed three times with deionized water (100 mL × 3). After that, it was dried over anhydrous sodium sulfate. The concentrated solution obtained after removing the solvent from the organic phase was purified by a chromatography column to obtain product 10-4 (1.55 g, yield: 54%).

[0167] Elemental analysis of its structure (C 58 H 32 N 2 O 2 ): Theoretical values: C, 88.30; H, 4.09; N, 3.55; O, 4.06; Measured values: C, 88.30; H, 4.09; N, 3.56; O, 4.05.

[0168] MALDI-TOF-MS: Theoretical value 788.3; Experimental value 788.4.

[0169] In a 100 mL two-necked flask, 10-4 (1.00 g, 1.27 mmol) and Lawson's reagent (0.82 g, 2.02 mmol) were added. 25 mL of toluene was added and stirred until dissolved. Argon was bubbled into the reaction flask for 30 minutes. Then, the reaction solution was heated to 110 °C and reacted for 1 hour. After the reaction was completed, it was cooled to room temperature, and the reaction solvent was removed by rotary evaporation under reduced pressure. The obtained crude product was purified by a chromatography column to obtain product 10-5 (0.67 g, yield: 64%) (i.e., compound A2-11).

[0170] Elemental analysis of its structure (C 58 H 32 N 2 S 2 ): Theoretical values: C, 84.85; H, 3.93; N, 3.41; S, 7.81; Measured values: C, 84.85; H, 3.93; N, 3.42; S, 7.80.

[0171] MALDI-TOF-MS: Theoretical value 820.2; Experimental value 820.1.

[0172] Example 11

[0173]

[0174] 1-5 (2.00 g, 4.35 mmol), malononitrile (0.69 g, 10.44 mmol), 40 mL of DCM, and triethylamine (1.32 g, 13.05 mmol) were added to a 100 mL round-bottom flask. Then the mixture was cooled to 0 °C and titanium tetrachloride (0.30 mL, 2.74 mmol) was added dropwise. The reaction mixture was stirred at room temperature until thin-layer chromatography showed that 1-5 had completely reacted. After the reaction was completed, the reaction solution was quenched with 10% sodium hydroxide solution and filtered. The organic layer was washed with saturated sodium bicarbonate and saturated sodium chloride, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The organic layer was purified by column chromatography to obtain product 11-1 (1.72 g, yield: 71%) (i.e., compound A3-1).

[0175] Elemental analysis of its structure (C 38 H 16 N 6 ): Theoretical values: C, 82.00; H, 2.90; N, 15.10; Measured values: C, 82.00; H, 2.89; N, 15.11.

[0176] MALDI-TOF-MS: Theoretical value 556.1; Experimental value 556.1.

[0177] Example 12

[0178]

[0179] Under an argon atmosphere, 12-1 (5.00 g, 24.62 mmol), 1-2 (4.23 g, 11.19 mmol), anhydrous potassium carbonate (6.19 g, 44.76 mmol), copper(I) iodide (0.85 g, 4.48 mmol), 18-crown-6-ether (1.18 g, 4.48 mmol), and 28 mL of o-dichlorobenzene were added to a 100 mL two-necked flask. After stirring at 180 °C for 24 hours and cooling to room temperature, the reaction solution was poured into 100 mL of ice water and extracted with dichloromethane (100 mL × 3). The organic phase was dried over anhydrous sodium sulfate, and then the filtrate was concentrated under reduced pressure. The crude product obtained was purified by a chromatography column to obtain product 12-2 (10.30 g, yield: 67%).

[0180] Elemental analysis of its structure (C 36 H 24 F 4 N 2 O 4):Theoretical values: C, 69.23; H, 3.87; N, 4.49; O, 10.25; Measured values: C, 69.25; H, 3.85; N, 4.51; O, 10.23.

[0181] MALDI-TOF-MS: Theoretical value 624.2; Experimental value 624.1.

[0182] Add 12-2 (4.00 g, 6.41 mmol), 128 mL of tetrahydrofuran, 66 mL of methanol, 66 mL of water, and sodium hydroxide (1.54 g, 38.46 mmol) to a 500 mL single-necked flask. Stir at 80 °C for 16 hours. The reaction system changes from a suspension to a clear liquid. Cool the reaction solution to room temperature, rotary evaporate the solvent, then add 50 mL of water to suspend the solid in water, and adjust the pH to 1 with concentrated hydrochloric acid. Filter the suspension by suction and wash with 100 mL of deionized water. The filter cake is dried in a vacuum oven to obtain the solid product 12-3 (3.64 g, yield: 100%), which is directly used for the next step without purification.

[0183] Under an argon atmosphere, add 12-3 (3.00 g, 5.28 mmol) and 175 mL of dichloromethane to a 500 mL two-necked flask. Then, dropwise add oxalyl chloride (20.11 mL, 237.60 mmol) and N,N-dimethylformamide (4.91 mL, 63.36 mmol) successively. After the addition is complete, stir at 45 °C for 3 hours. Cool the reaction to room temperature, dropwise add tin(IV) chloride (12.36 mL, 105.60 mmol). After the addition is complete, stir at 45 °C for 21 hours. Cool the reaction to room temperature. Under ice-water bath conditions, adjust the pH to 10 with 2 M sodium hydroxide solution, then add 100 mL of dichloromethane for dilution, and wash with deionized water three times (100 mL × 3). Then dry with anhydrous sodium sulfate. The concentrated solution obtained after removing the solvent from the organic phase is purified by a chromatography column to obtain the product 12-4 (1.55 g, yield: 55%).

[0184] Elemental analysis of its structure (C 32 H 12 F 4 N 2 O 2 ):Theoretical values: C, 72.19; H, 2.27; N, 5.26; O, 6.01; Measured values: C, 72.18; H, 2.28; N, 5.24; O, 6.01.

[0185] MALDI-TOF-MS: Theoretical value 532.1; Experimental value 532.0.

[0186] Add 12-4 (2.00 g, 3.76 mmol), malononitrile (0.60 g, 9.02 mmol), 40 mL of DCM and triethylamine (1.14 g, 11.28 mmol) into a 100 mL round-bottom flask. Then cool the mixture to 0 °C and add titanium tetrachloride (0.25 mL, 2.26 mmol) dropwise. Stir the reaction mixture at room temperature until thin-layer chromatography shows that 12-4 has completely reacted. After the reaction is completed, quench the reaction solution with 10% sodium hydroxide solution and filter. Wash the organic layer with saturated sodium bicarbonate and saturated sodium chloride, dry over anhydrous sodium sulfate, and concentrate the organic layer under reduced pressure. Purify by column chromatography to obtain product 12-5 (1.84 g, yield: 78%) (i.e., compound A3-2).

[0187] Elemental analysis of its structure (C 38 H 12 F 4 N 6 ): Theoretical values: C, 72.61; H, 1.92; N, 13.37; Measured values: C, 72.63; H, 2.87; N, 13.35.

[0188] MALDI-TOF-MS: Theoretical value 628.1; Experimental value 628.1.

[0189] Example 13

[0190]

[0191] Under an argon atmosphere, add 13-1 (5.00 g, 16.50 mmol), 1-2 (2.83 g, 7.50 mmol), anhydrous potassium carbonate (4.15 g, 30.00 mmol), copper(I) iodide (0.57 g, 3.00 mmol), 18-crown-6-ether (0.79 g, 3.00 mmol) and 19 mL of o-dichlorobenzene into a 100 mL two-necked flask. Stir at 180 °C for 24 hours and then cool to room temperature. Pour the reaction solution into 100 mL of ice water and extract with dichloromethane (100 mL × 3). Dry the organic phase over anhydrous sodium sulfate, and then concentrate the filtrate under reduced pressure. Purify the obtained crude product by column chromatography to obtain product 13-2 (4.01 g, yield: 65%).

[0192] Elemental analysis of its structure (C 40 H 24 F 12 N 2 O 4 ): Theoretical values: C, 58.26; H, 2.93; N, 3.40; O, 7.76; Measured values: C, 58.25; H, 2.95; N, 3.41; O, 7.74.

[0193] MALDI-TOF-MS: Theoretical value 824.1; Experimental value 824.2.

[0194] Add 13-2 (4.00 g, 4.85 mmol), 97 mL of tetrahydrofuran, 50 mL of methanol, 50 mL of water and sodium hydroxide (1.16 g, 29.10 mmol) into a 500 mL single-necked flask, stir at 80 °C for 16 hours. The reaction system changes from a suspension to a clear liquid. Cool the reaction solution to room temperature, rotary evaporate the solvent, then add 50 mL of water to suspend the solid in water, and adjust the pH to 1 with concentrated hydrochloric acid. Filter the suspension and wash it with 100 mL of deionized water. The filter cake is dried in a vacuum oven to obtain the solid product 13-3 (3.73 g, Yield: 100%), and this product is directly used for the next step without purification.

[0195] Under an argon atmosphere, add 13-3 (3.00 g, 3.91 mmol) and 129 mL of dichloromethane into a 500 mL two-necked flask. Then, dropwise add oxalyl chloride (14.89 mL, 175.95 mmol) and N,N-dimethylformamide (3.63 mL, 46.92 mmol) successively. After the addition, stir at 45 °C for 3 hours. Cool the reaction to room temperature, dropwise add tin(IV) chloride (9.15 mL, 78.20 mmol). After the addition, stir at 45 °C for 21 hours. Cool the reaction to room temperature. Under the condition of an ice-water bath, adjust the pH to 10 with 2 M sodium hydroxide solution, then add 100 mL of dichloromethane for dilution, and wash it three times with deionized water (100 mL × 3). Then dry it with anhydrous sodium sulfate. The concentrated solution obtained after removing the solvent from the organic phase is purified by a chromatography column to obtain the product 13-4 (1.72 g, Yield: 60%).

[0196] Elemental analysis of its structure (C 36 H 12 F 12 N 2 O 2 ): Theoretical values: C, 59.03; H, 1.65; N, 3.82; O, 4.37; Measured values: C, 59.05; H, 1.67; N, 3.80; O, 4.34.

[0197] MALDI-TOF-MS: Theoretical value 732.1; Experimental value 732.0.

[0198] 13-4 (2.00 g, 2.73 mmol), malononitrile (0.43 g, 6.56 mmol), 30 mL of DCM and triethylamine (0.83 g, 8.19 mmol) were added to a 100 mL round-bottom flask. The mixture was then cooled to 0 °C and titanium tetrachloride (0.18 mL, 1.64 mmol) was added dropwise. The reaction mixture was stirred at room temperature until thin-layer chromatography showed that 13-4 had completely reacted. After completion of the reaction, the reaction solution was quenched with 10% sodium hydroxide solution and filtered. The organic layer was washed with saturated sodium bicarbonate and saturated sodium chloride, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The organic layer was purified by column chromatography to obtain product 13-5 (1.63 g, yield: 72%) (i.e., compound A3-3).

[0199] Elemental analysis of its structure (C 42 H 12 F 12 N 6 ): Theoretical values: C, 60.88; H, 1.46; N, 10.14; Measured values: C, 60.86; H, 1.45; N, 10.17.

[0200] MALDI-TOF-MS: Theoretical value 828.1; Experimental value 828.2.

[0201] Example 14

[0202]

[0203] 9-4 (2.00 g, 4.06 mmol), malononitrile (0.64 g, 9.75 mmol), 35 mL of DCM and triethylamine (1.23 g, 12.18 mmol) were added to a 100 mL round-bottom flask. The mixture was then cooled to 0 °C and titanium tetrachloride (0.27 mL, 2.44 mmol) was added dropwise. The reaction mixture was stirred at room temperature until thin-layer chromatography showed that 9-4 had completely reacted. After completion of the reaction, the reaction solution was quenched with 10% sodium hydroxide solution and filtered. The organic layer was washed with saturated sodium bicarbonate and saturated sodium chloride, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The organic layer was purified by column chromatography to obtain product 14-1 (1.79 g, yield: 75%) (i.e., compound A3-5).

[0204] Elemental analysis of its structure (C 38 H 16 N 6 O 2 ): Theoretical values: C, 77.54; H, 2.74; N, 14.28; O, 5.44; Measured values: C, 77.53; H, 2.75; N, 14.26; O, 5.46.

[0205] MALDI-TOF-MS: Theoretical value 588.1; Experimental value 588.2.

[0206] Example 15

[0207]

[0208] Add 1-5 (2 g, 4.35 mmol), 15-1 (0.98 g, 10.44 mmol), 40 mL of DCM and triethylamine (1.32 g, 13.05 mmol) to a 100 mL round-bottom flask. Then cool the mixture to 0 °C and add titanium tetrachloride (2.74 mmol, 0.30 mL) dropwise. Stir the reaction mixture at room temperature until thin-layer chromatography shows that 1-5 has completely reacted. After the reaction is completed, quench the reaction solution with 10% sodium hydroxide solution and filter. Wash the organic layer with saturated sodium bicarbonate and saturated sodium chloride, dry over anhydrous sodium sulfate, and concentrate the organic layer under reduced pressure. After purification by column chromatography, the product 15-2 (1.88 g, yield: 71%) (i.e., compound A3-6) is obtained.

[0209] Elemental analysis of its structure (C 44 H 26 N 4 ): Theoretical values: C, 86.53; H, 4.29; N, 9.17; Test values: C, 86.53; H, 4.28; N, 9.18.

[0210] MALDI-TOF-MS: Theoretical value 610.2; Experimental value 610.1.

[0211] Example 16

[0212]

[0213] Add 1-5 (2 g, 4.35 mmol), ethyl cyanoacetate (1.18 g, 10.44 mmol), 40 mL of DCM and triethylamine (1.32 g, 13.05 mmol) to a 100 mL round-bottom flask. Then cool the mixture to 0 °C and add titanium tetrachloride (2.74 mmol, 0.30 mL) dropwise. Stir the reaction mixture at room temperature until thin-layer chromatography shows that 1-5 has completely reacted. After the reaction is completed, quench the reaction solution with 10% sodium hydroxide solution and filter. Wash the organic layer with saturated sodium bicarbonate and saturated sodium chloride, dry over anhydrous sodium sulfate, and concentrate the organic layer under reduced pressure. After purification by column chromatography, the product 16-1 (2.00 g, yield: 71%) (i.e., compound A3-7) is obtained.

[0214] Elemental analysis of its structure (C 42 H 26 N 4 O4 ):Theoretical values: C, 77.53; H, 4.03; N, 8.61; O, 9.84; Measured values: C, 77.53; H, 4.03; N, 8.62; O, 9.83.

[0215] MALDI-TOF-MS: Theoretical value 650.2; Experimental value 650.3.

[0216] Example 17

[0217]

[0218] Add 1-5 (2.00 g, 4.35 mmol), 17-1 (4.21 g, 26.08 mmol), 87 mL of acetic acid and 87 mL of acetic anhydride to a 500 mL round-bottom flask, and reflux overnight. After the reaction is completed, remove acetic acid and acetic anhydride in vacuo. Dissolve the mixture in DCM, wash twice with water, and then wash with saturated sodium bicarbonate. The crude product obtained is purified by Combiflash to obtain Product 17-2 (1.66 g, yield: 51%) (i.e., Compound A3-8).

[0219] Elemental analysis of its structure (C 42 H 26 N 4 O 2 S 4 ):Theoretical values: C, 67.54; H, 3.51; N, 7.50; O, 4.28; S, 17.17; Measured values: C, 67.55; H, 3.50; N, 7.50; O, 4.29; S, 17.16.

[0220] MALDI-TOF-MS: Theoretical value 746.1; Experimental value 746.0.

[0221] Example 18

[0222]

[0223] Add 1-5 (2.00 g, 4.35 mmol), 18-1 (4.07 g, 26.08 mmol), 87 mL of acetic acid and 87 mL of acetic anhydride to a 500 mL round-bottom flask, and reflux overnight. After the reaction is completed, remove acetic acid and acetic anhydride in vacuo. Dissolve the mixture in DCM, wash twice with water, and then wash with saturated sodium bicarbonate. The crude product obtained is purified by Combiflash to obtain Product 18-2 (1.63 g, yield: 51%) (i.e., Compound A3-12).

[0224] Elemental analysis of its structure (C 44 H 28 N6 O 6 ): Theoretical values: C, 71.73; H, 3.83; N, 11.41; O, 13.03; Measured values: C, 71.73; H, 3.83; N, 11.42; O, 13.02.

[0225] MALDI-TOF-MS: Theoretical value 736.2; Experimental value 736.1.

[0226] Example 19

[0227]

[0228] Add 1-5 (2.00 g, 4.35 mmol), 19-1 (3.81 g, 26.08 mmol), 87 mL of acetic acid and 87 mL of acetic anhydride to a 500 mL round-bottom flask, and reflux overnight. After the reaction is completed, remove acetic acid and acetic anhydride in vacuo. Dissolve the mixture in DCM, wash twice with water, and then wash with saturated sodium bicarbonate. The crude product obtained is purified by Combiflash to obtain Product 19-2 (1.59 g, yield: 51%) (i.e., Compound A3-13).

[0229] Elemental analysis of its structure (C 50 H 24 N 2 O 4 ): Theoretical values: C, 83.79; H, 3.38; N, 3.91; O, 8.93; Measured values: C, 83.78; H, 3.39; N, 3.90; O, 8.94.

[0230] MALDI-TOF-MS: Theoretical value 716.2; Experimental value 716.1.

[0231] Example 20

[0232]

[0233] Add 20-1 (15.0 g, 57.27 mmol), 360 mL of pyridine and 150 mL of deionized water to a 1000 mL two-necked flask. Heat the reaction to 120 °C and add potassium permanganate (24.00 g, 151.50 mmol) in portions. React at 120 °C for 2 days. When the reaction temperature drops to about 80 °C, perform hot filtration while it is hot. Wash the filter cake several times with hot water at 80 °C. Remove the solvent from the obtained filtrate by rotary evaporation under reduced pressure. Immediately place the obtained solid and sodium hydroxide (10.00 g, 250.00 mmol) in a 250 mL two-necked flask, add 150 mL of deionized water, heat to reflux. After all the solids in the reaction flask dissolve, add potassium permanganate (24.00 g, 151.50 mmol) in portions. Lower the reaction temperature to 90 °C and stir for 1 day. After the reaction is completed, cool to room temperature, slowly add 25 mL of absolute ethanol dropwise to the reaction flask to quench the unreacted potassium permanganate. Then filter the reaction mixture, acidify the filtrate with 300 mL of 5 M hydrochloric acid solution, and remove the solvent by rotary evaporation under reduced pressure. Subsequently, add 100 mL of acetone, stir at room temperature for 1 day, filter again, and concentrate the filtrate under reduced pressure to obtain the white solid product 20-2 (12.17 g, yield: 66%).

[0234] Elemental analysis of its structure (C 8 H 4 Br 2 O 4 ): Theoretical values: C, 29.66; H, 1.24; O, 19.76; Measured values: C, 29.66; H, 1.25; O, 19.75.

[0235] MALDI-TOF-MS: Theoretical value 321.9; Experimental value 321.9.

[0236] Add 20-2 (12.17 g, 37.81 mmol), 320 mL of methanol and 65 mL of concentrated sulfuric acid to a 1000 mL two-necked flask. Stir at 65 °C for 1 week, and white solids will gradually form in the reaction flask. After the reaction is completed, cool the reaction to room temperature. Then filter the reaction mixture and wash it with cold methanol. The filter cake is the product 20-3. Evaporate a part of the methanol in the filtrate by rotary evaporation under reduced pressure, add dichloromethane and water for extraction. Wash the organic phase three times with deionized water (250 mL × 3), dry it with anhydrous sodium sulfate, filter, remove the solvent, and purify the obtained crude product by column chromatography. Finally, obtain the white solid product 20-3 (7.14 g, yield: 54%).

[0237] Elemental analysis of its structure (C 10 H 8 Br 2 O 4Theory values: C, 34.12; H, 2.29; O, 18.18; Test values: C, 34.13; H, 2.29; O, 18.17.

[0238] MALDI-TOF-MS: Theory value 349.9; Experimental value 349.8.

[0239] Under an argon atmosphere, 1-1 (5.00 g, 29.93 mmol), 20-3 (5.03 g, 14.37 mmol), anhydrous potassium carbonate (7.86 g, 56.87 mmol), copper(I) iodide (1.08 g, 5.69 mmol), 18-crown-6-ether (1.50 g, 5.69 mmol) and 34 mL of o-dichlorobenzene were added to a 100 mL two-necked flask. After stirring at 180 °C for 24 hours, the mixture was cooled to room temperature. The reaction solution was poured into 100 mL of ice water and extracted with dichloromethane (100 mL × 3). The organic phase was dried over anhydrous sodium sulfate, and then the filtrate was concentrated under reduced pressure. The crude product obtained was purified by column chromatography to give product 20-4 (4.70 g, yield: 60%).

[0240] Elemental analysis of its structure (C 34 H 24 N 2 O 4 ):Theory values: C, 77.85; H, 4.61; N, 5.34; O, 12.20; Test values: C, 77.86; H, 4.60; N, 5.35; O, 12.19.

[0241] MALDI-TOF-MS: Theory value 524.2; Experimental value 524.0.

[0242] In a 500 mL single-necked flask, 20-4 (4.00 g, 7.63 mmol), 153 mL of tetrahydrofuran, 79 mL of methanol, 79 mL of water and sodium hydroxide (1.83 g, 45.79 mmol) were added. The mixture was stirred at 80 °C for 16 hours, and the reaction system changed from a suspension to a clear liquid. The reaction solution was cooled to room temperature, the solvent was removed by rotary evaporation, and then 50 mL of water was added to suspend the solid in water. The pH was adjusted to 1 with concentrated hydrochloric acid. The suspension was filtered by suction and washed with 100 mL of deionized water. The filter cake was dried in a vacuum oven to obtain a yellow solid product 20-5 (3.79 g, yield: 100%), which was used directly in the next step without purification.

[0243] Under an argon atmosphere, 20-5 (3.59 g, 7.64 mmol) and 220 mL of dichloromethane were added to a 500 mL two-necked flask. Then, oxalyl chloride (30.00 mL, 354.53 mmol) and N,N-dimethylformamide (7.40 mL, 95.64 mmol) were added dropwise successively. After the addition was complete, the mixture was stirred at 45 °C for 3 hours. The reaction was cooled to room temperature, and tin(IV) chloride (17.90 mL, 152.83 mmol) was added dropwise. After the addition was complete, the mixture was stirred at 45 °C for 21 hours. The reaction was cooled to room temperature, and under ice-water bath conditions, the pH was adjusted to 10 with 2 M sodium hydroxide solution. Then, 100 mL of dichloromethane was added for dilution, and it was washed three times with deionized water (100 mL × 3). After that, it was dried over anhydrous sodium sulfate. The concentrated solution obtained after removing the solvent from the organic phase was purified by a chromatography column to obtain product 20-6 (2.64 g, yield: 75%).

[0244] Elemental analysis of its structure (C 32 H 16 N 2 O 2 ): Theoretical values: C, 83.47; H, 3.50; N, 6.08; O, 6.95; Measured values: C, 83.46; H, 3.49; N, 6.07; O, 6.98.

[0245] MALDI-TOF-MS: Theoretical value 460.1; Experimental value 460.1.

[0246] In a 100 mL two-necked flask, 20-6 (2.00 g, 4.03 mmol) and Lawson's reagent (2.59 g, 6.41 mmol) were added. 70 mL of toluene was added and stirred until dissolved. Argon was bubbled into the reaction flask for 30 minutes. Then, the reaction solution was heated to 110 °C and reacted for 1 hour. After the reaction was completed, it was cooled to room temperature, and the reaction solvent was removed by rotary evaporation under reduced pressure. The obtained crude product was purified by a chromatography column to obtain product 20-7 (1.27 g, yield: 64%) (i.e., compound B1-1).

[0247] Elemental analysis of its structure (C 32 H 16 N 2 S 2 ): Theoretical values: C, 78.02; H, 3.27; N, 5.69; S, 13.02; Measured values: C, 78.01; H, 3.28; N, 5.70; S, 13.01.

[0248] MALDI-TOF-MS: Theoretical value 492.1; Experimental value 492.0.

[0249] Example 21

[0250]

[0251] Under an argon atmosphere, 9-1 (5.00 g, 27.31 mmol), 20-3 (4.59 g, 13.11 mmol), anhydrous potassium carbonate (7.17 g, 51.89 mmol), copper(I) iodide (1.00 g, 5.19 mmol), 18-crown-6-ether (1.37 g, 5.19 mmol) and 33 mL of o-dichlorobenzene were added to a 100 mL two-necked flask. After stirring at 180 °C for 24 hours, it was cooled to room temperature. The reaction solution was poured into 100 mL of ice water and extracted with dichloromethane (100 mL × 3). The organic phase was dried over anhydrous sodium sulfate. Subsequently, the filtrate was concentrated under reduced pressure. The obtained crude product was purified by a chromatography column to obtain product 21-1 (5.01 g, yield: 66%).

[0252] Elemental analysis of its structure (C 34 H 24 N 2 O 6 ): Theoretical values: C, 73.37; H, 4.35; N, 5.03; O, 17.25; Measured values: C, 73.36; H, 4.36; N, 5.04; O, 17.24.

[0253] MALDI-TOF-MS: Theoretical value 556.2; Experimental value 556.1.

[0254] 21-1 (5.00 g, 8.99 mmol), 180 mL of tetrahydrofuran, 94 mL of methanol, 94 mL of water and sodium hydroxide (2.16 g, 53.93 mmol) were added to a 500 mL single-necked flask. It was stirred at 80 °C for 16 hours. The reaction system changed from a suspension to a clear liquid. The reaction solution was cooled to room temperature, the solvent was rotary-evaporated, and then 50 mL of water was added to suspend the solid in water. The pH was adjusted to 1 with concentrated hydrochloric acid. The suspension was filtered by suction and washed with 100 mL of deionized water. The filter cake was dried in a vacuum oven to obtain a solid product 21-2 (4.70 g, yield: 100%), which was directly used for the next step without purification.

[0255] Under an argon atmosphere, 21-2 (4.00 g, 7.57 mmol) and 250 mL of dichloromethane were added to a 500 mL two-necked flask. Then, oxalyl chloride (29.2 mL, 347.11 mmol) and N,N-dimethylformamide (7.4 mL, 94.79 mmol) were added dropwise in sequence. After the addition was completed, the mixture was stirred at 45 °C for 3 hours. The reaction was cooled to room temperature, and tin(IV) chloride (17.7 mL, 151.40 mmol) was added dropwise. After the addition was completed, the mixture was stirred at 45 °C for 21 hours. The reaction was cooled to room temperature, and under the condition of an ice-water bath, the pH was adjusted to 10 with 2 M sodium hydroxide solution. Then, 100 mL of dichloromethane was added for dilution, and the mixture was washed three times with deionized water (100 mL × 3). After that, it was dried over anhydrous sodium sulfate. The concentrated solution obtained after removing the solvent from the organic phase was purified by a chromatography column to obtain the product 21-3 (2.01 g, yield: 54%).

[0256] Elemental analysis of its structure (C 32 H 16 N 2 O 4 ): Theoretical values: C, 78.04; H, 3.27; N, 5.69; O, 12.99; Measured values: C, 78.03; H, 3.28; N, 5.70; O, 12.98.

[0257] MALDI-TOF-MS: Theoretical value 492.1; Experimental value 492.1.

[0258] 21-3 (2.00 g, 4.06 mmol) and Lawson's reagent (2.61 g, 6.46 mmol) were added to a 250 mL two-necked flask. 74 mL of toluene was added and stirred until dissolved. Argon was bubbled into the reaction flask for 30 minutes. Then, the reaction solution was heated to 110 °C and reacted for 1 hour. After the reaction was completed, it was cooled to room temperature, and the reaction solvent was removed by rotary evaporation under reduced pressure. The obtained crude product was purified by a chromatography column to obtain the product 21-4 (2.13 g, yield: 64%) (i.e., compound B1-8).

[0259] Elemental analysis of its structure (C 32 H 16 N 2 O 2 S 2 ): Theoretical values: C, 73.26; H, 3.07; N, 5.34; O, 6.10; S, 12.22; Measured values: C, 73.27; H, 3.06; N, 5.34; O, 6.11; S, 12.21.

[0260] MALDI-TOF-MS: Theoretical value 524.1; Experimental value 524.1.

[0261] Example 22

[0262]

[0263] 20-6 (2 g, 4.35 mmol), malononitrile (0.69 g, 10.44 mmol), 40 mL of DCM and triethylamine (1.32 g, 13.05 mmol) were added to a 100 mL round-bottom flask. Then the mixture was cooled to 0 °C and titanium tetrachloride (2.74 mmol, 0.30 mL) was added dropwise. The reaction mixture was stirred at room temperature until thin-layer chromatography showed that 20-6 had completely reacted. After the reaction was completed, the reaction solution was quenched with 10% sodium hydroxide solution and filtered. The organic layer was washed with saturated sodium bicarbonate and saturated sodium chloride, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The organic layer was purified by column chromatography to obtain product 22-1 (1.72 g, yield: 71%) (i.e., compound B1-11).

[0264] Elemental analysis of its structure (C 38 H 16 N 6 ): Theoretical values: C, 82.00; H, 2.90; N, 15.10; Measured values: C, 82.00; H, 2.89; N, 15.11.

[0265] MALDI-TOF-MS: Theoretical value 556.1; Experimental value 556.0.

[0266] Example 23

[0267]

[0268] 20-6 (2.00 g, 4.35 mmol), 17-1 (4.21 g, 26.08 mmol), 87 mL of acetic acid and 87 mL of acetic anhydride were added to a 500 mL round-bottom flask and refluxed overnight. After the reaction was completed, acetic acid and acetic anhydride were removed in vacuo. The mixture was dissolved in DCM, washed twice with water, and then washed with saturated sodium bicarbonate. The crude product obtained was purified by Combiflash to obtain product 23-1 (1.66 g, yield: 51%) (i.e., compound B1-13).

[0269] Elemental analysis of its structure (C 42 H 26 N 4 O 2 S 4 ): Theoretical values: C, 67.54; H, 3.51; N, 7.50; O, 4.28; S, 17.17; Measured values: C, 67.55; H, 3.50; N, 7.50; O, 4.29; S, 17.16.

[0270] MALDI-TOF-MS: Theoretical value 746.1; Experimental value 746.1.

[0271] Example 24

[0272]

[0273] Add 24-1 (15.0 g, 57.27 mmol), 360 mL of pyridine and 150 mL of deionized water into a 1000 mL two-necked flask. Heat the reaction to 120 °C and add potassium permanganate (24.00 g, 151.50 mmol) in batches. React at 120 °C for 2 days. When the reaction temperature drops to about 80 °C, filter while it is hot. Wash the filter cake with hot water at 80 °C several times. Evaporate the solvent from the obtained filtrate under reduced pressure. Immediately place the obtained solid and sodium hydroxide (10.00 g, 250.00 mmol) into a 250 mL two-necked flask, add 150 mL of deionized water, heat to reflux. After the solid in the reaction flask has dissolved, add potassium permanganate (24.00 g, 151.50 mmol) in batches. Lower the reaction temperature to 90 °C and stir for 1 day. After the reaction is completed, cool to room temperature and slowly add 25 mL of absolute ethanol dropwise to quench the unreacted potassium permanganate. Then filter the reaction mixture. Acidify the filtrate with 300 mL of 5 M hydrochloric acid solution and evaporate the solvent under reduced pressure. Subsequently, add 100 mL of acetone and stir at room temperature for 1 day. Filter again and concentrate the filtrate under reduced pressure to obtain a white solid product 24-2 (12.17 g, Yield: 66%).

[0274] Elemental analysis of its structure (C 8 H 4 Br 2 O 4 ) : Theoretical values: C, 29.66; H, 1.24; O, 19.76; Measured values: C, 29.66; H, 1.25; O, 19.75.

[0275] MALDI-TOF-MS: Theoretical value 321.9; Experimental value 322.0.

[0276] Add 24-2 (12.17 g, 37.81 mmol), 320 mL of methanol and 65 mL of concentrated sulfuric acid into a 1000 mL two-necked flask, stir at 65 °C for 1 week, and white solid will gradually form in the reaction flask. After the reaction is completed, cool the reaction to room temperature, then filter the reaction solution by suction and wash it with cold methanol. The filter residue is the product 24-3. Evaporate a part of the methanol in the filtrate by rotary evaporation under reduced pressure, add dichloromethane and water for extraction. Wash the organic phase with deionized water three times (250 mL × 3), dry it with anhydrous sodium sulfate, filter by suction, remove the solvent, and purify the obtained crude product by column chromatography. Finally, obtain the white solid product 24-3 (7.14 g, yield: 54%).

[0277] Elemental analysis of its structure (C 10 H 8 Br 2 O 4 ): Theoretical values: C, 34.12; H, 2.29; O, 18.18; Measured values: C, 34.13; H, 2.29; O, 18.17.

[0278] MALDI-TOF-MS: Theoretical value 349.9; Experimental value 349.9.

[0279] Under an argon atmosphere, add 1-1 (5.00 g, 29.93 mmol), 24-3 (5.03 g, 14.37 mmol), anhydrous potassium carbonate (7.86 g, 56.87 mmol), copper(I) iodide (1.08 g, 5.69 mmol), 18-crown-6-ether (1.50 g, 5.69 mmol) and 34 mL of o-dichlorobenzene into a 100 mL two-necked flask. Stir at 180 °C for 24 hours and then cool to room temperature. Pour the reaction solution into 100 mL of ice water, extract with dichloromethane (100 mL × 3), dry the organic phase with anhydrous sodium sulfate, and then concentrate the filtrate under reduced pressure. Purify the obtained crude product by column chromatography to obtain the product 24-4 (4.70 g, yield: 60%).

[0280] Elemental analysis of its structure (C 34 H 24 N 2 O 4 ): Theoretical values: C, 77.85; H, 4.61; N, 5.34; O, 12.20; Measured values: C, 77.86; H, 4.60; N, 5.35; O, 12.19.

[0281] MALDI-TOF-MS: Theoretical value 524.2; Experimental value 524.1.

[0282] In a 500 mL single-necked flask, add 24-4 (4.00 g, 7.63 mmol), 153 mL of tetrahydrofuran, 79 mL of methanol, 79 mL of water, and sodium hydroxide (1.83 g, 45.79 mmol). Stir at 80 °C for 16 hours. The reaction system changes from a suspension to a clear liquid. Cool the reaction solution to room temperature, rotary evaporate the solvent, then add 50 mL of water to suspend the solid in water, and adjust the pH to 1 with concentrated hydrochloric acid. Filter the suspension by suction and wash it with 100 mL of deionized water. The filter cake is dried in a vacuum oven to obtain a yellow solid product 24-5 (3.79 g, yield: 100%), which is directly used for the next step without purification.

[0283] Under an argon atmosphere, add 24-5 (3.59 g, 7.64 mmol) and 220 mL of dichloromethane to a 500 mL two-necked flask. Then, dropwise add oxalyl chloride (30.00 mL, 354.53 mmol) and N,N-dimethylformamide (7.40 mL, 95.64 mmol) in sequence. After the addition is complete, stir at 45 °C for 3 hours. Cool the reaction to room temperature, dropwise add stannic chloride (17.90 mL, 152.83 mmol). After the addition is complete, stir at 45 °C for 21 hours. Cool the reaction to room temperature. Under an ice-water bath condition, adjust the pH to 10 with 2 M sodium hydroxide solution, then add 100 mL of dichloromethane for dilution, and wash with deionized water three times (100 mL × 3). Then dry with anhydrous sodium sulfate. The concentrated solution obtained after removing the solvent from the organic phase is purified by a chromatography column to obtain product 24-6 (2.64 g, yield: 75%).

[0284] Elemental analysis of its structure (C 32 H 16 N 2 O 2 ): Theoretical values: C, 83.47; H, 3.50; N, 6.08; O, 6.95; Measured values: C, 83.46; H, 3.49; N, 6.07; O, 6.98.

[0285] MALDI-TOF-MS: Theoretical value 460.1; Experimental value 460.0.

[0286] Add 24-6 (2.00 g, 4.03 mmol) and Lawson's reagent (2.59 g, 6.41 mmol) to a 100 mL two-necked flask, add 70 mL of toluene and stir to dissolve. Bubble argon into the reaction flask for 30 minutes, then heat the reaction solution to 110 °C and react for 1 hour. After the reaction is completed, cool to room temperature, rotary evaporate the reaction solvent under reduced pressure. The obtained crude product is purified by a chromatography column to obtain product 24-7 (1.27 g, yield: 64%) (i.e., compound C1-1).

[0287] Elemental analysis of its structure (C 32 H 16 N 2 S 2 ): Theoretical values: C, 78.02; H, 3.27; N, 5.69; S, 13.02; Test values: C, 78.01; H, 3.28; N, 5.70; S, 13.01.

[0288] MALDI-TOF-MS: Theoretical value 492.1; Experimental value 492.1.

[0289] Example 25

[0290]

[0291] Under an argon atmosphere, 9-1 (5.00 g, 27.31 mmol), 24-3 (4.59 g, 13.11 mmol), anhydrous potassium carbonate (7.17 g, 51.89 mmol), copper(I) iodide (1.00 g, 5.19 mmol), 18-crown-6-ether (1.37 g, 5.19 mmol) and 33 mL of o-dichlorobenzene were added to a 100 mL two-necked flask. After stirring at 180 °C for 24 hours, it was cooled to room temperature. The reaction solution was poured into 100 mL of ice water and extracted with dichloromethane (100 mL × 3). The organic phase was dried over anhydrous sodium sulfate, and then the filtrate was concentrated under reduced pressure. The crude product obtained was purified by a chromatography column to obtain product 25-1 (5.01 g, yield: 66%).

[0292] Elemental analysis of its structure (C 34 H 24 N 2 O 6 ): Theoretical values: C, 73.37; H, 4.35; N, 5.03; O, 17.25; Test values: C, 73.36; H, 4.36; N, 5.04; O, 17.24.

[0293] MALDI-TOF-MS: Theoretical value 556.2; Experimental value 556.1.

[0294] In a 500 mL single-necked flask, add 25-1 (5.00 g, 8.99 mmol), 180 mL of tetrahydrofuran, 94 mL of methanol, 94 mL of water, and sodium hydroxide (2.16 g, 53.93 mmol). Stir at 80 °C for 16 hours. The reaction system changes from a suspension to a clear liquid. Cool the reaction solution to room temperature, rotary evaporate the solvent, then add 50 mL of water to suspend the solid in water, and adjust the pH to 1 with concentrated hydrochloric acid. Filter the suspension by suction and wash it with 100 mL of deionized water. The filter cake is dried in a vacuum oven to obtain the solid product 25-2 (4.70 g, yield: 100%), which is directly used in the next step without purification.

[0295] Under an argon atmosphere, add 25-2 (4.00 g, 7.57 mmol) and 250 mL of dichloromethane to a 500 mL two-necked flask. Then, dropwise add oxalyl chloride (29.2 mL, 347.11 mmol) and N,N-dimethylformamide (7.4 mL, 94.79 mmol) successively. After the addition is complete, stir at 45 °C for 3 hours. Cool the reaction to room temperature, and dropwise add tin(IV) chloride (17.7 mL, 151.40 mmol). After the addition is complete, stir at 45 °C for 21 hours. Cool the reaction to room temperature. Under ice-water bath conditions, adjust the pH to 10 with 2 M sodium hydroxide solution, then add 100 mL of dichloromethane for dilution, and wash with deionized water three times (100 mL × 3). Then dry with anhydrous sodium sulfate. The concentrated solution obtained after removing the solvent from the organic phase is purified by a chromatography column to obtain the product 25-3 (2.01 g, yield: 54%).

[0296] Elemental analysis of its structure (C 32 H 16 N 2 O 4 ): Theoretical values: C, 78.04; H, 3.27; N, 5.69; O, 12.99; Measured values: C, 78.03; H, 3.28; N, 5.70; O, 12.98.

[0297] MALDI-TOF-MS: Theoretical value 492.0; Experimental value 492.1.

[0298] Add 25-3 (2.00 g, 4.06 mmol) and Lawson's reagent (2.61 g, 6.46 mmol) to a 250 mL two-necked flask, add 74 mL of toluene and stir to dissolve. Bubble argon into the reaction flask for 30 minutes, then heat the reaction solution to 110 °C and react for 1 hour. After the reaction is completed, cool to room temperature and rotary evaporate the reaction solvent under reduced pressure. The obtained crude product is purified by a chromatography column to obtain the product 25-4 (2.13 g, yield: 64%) (i.e., compound C1-8).

[0299] Elemental analysis of its structure (C 32 H 16 N 2 O 2 S 2 ): Theoretical values: C, 73.26; H, 3.07; N, 5.34; O, 6.10; S, 12.22; Test values: C, 73.27; H, 3.06; N, 5.34; O, 6.11; S, 12.21.

[0300] MALDI-TOF-MS: Theoretical value 524.1; Experimental value 524.1.

[0301] Example 26

[0302]

[0303] Add 24-6 (2 g, 4.35 mmol), malononitrile (0.69 g, 10.44 mmol), 40 mL of DCM and triethylamine (1.32 g, 13.05 mmol) to a 100 mL round-bottom flask. Then cool the mixture to 0 °C and dropwise add titanium tetrachloride (2.74 mmol, 0.30 mL). Stir the reaction mixture at room temperature until thin-layer chromatography shows that 24-6 has completely reacted. After the reaction is completed, quench the reaction solution with 10% sodium hydroxide solution and filter. Wash the organic layer with saturated sodium bicarbonate and saturated sodium chloride, dry over anhydrous sodium sulfate, and concentrate the organic layer under reduced pressure. After purification by column chromatography, product 26-1 (1.72 g, yield: 71%) (i.e., compound C1-11) is obtained.

[0304] Elemental analysis of its structure (C 38 H 16 N 6 ): Theoretical values: C, 82.00; H, 2.90; N, 15.10; Test values: C, 82.00; H, 2.89; N, 15.11.

[0305] MALDI-TOF-MS: Theoretical value 556.2; Experimental value 556.1.

[0306] Example 27

[0307]

[0308] 24-6 (2.00 g, 4.35 mmol), 17-1 (4.21 g, 26.08 mmol), 87 mL of acetic acid and 87 mL of acetic anhydride were added to a 500 mL round-bottom flask and refluxed overnight. After the reaction was completed, acetic acid and acetic anhydride were removed in vacuo. The mixture was dissolved in DCM, washed twice with water, and then washed with saturated sodium bicarbonate. The crude product obtained was purified by Combiflash to give product 27-1 (1.66 g, yield: 51%) (i.e., compound C1-13).

[0309] Elemental analysis of its structure (C 42 H 26 N 4 O 2 S 4 ): Theoretical values: C, 67.54; H, 3.51; N, 7.50; O, 4.28; S, 17.17; Measured values: C, 67.55; H, 3.50; N, 7.50; O, 4.29; S, 17.16.

[0310] MALDI-TOF-MS: Theoretical value 746.1; Experimental value 746.1.

[0311] See Table 1. Table 1 shows the photophysical properties of the nitrogen-containing heteroaromatic fused-ring compounds prepared in the examples of the present invention.

[0312] Table 1 Photophysical properties of the nitrogen-containing heteroaromatic fused-ring compounds prepared in the examples of the present invention

[0313]

[0314] Note: The delayed fluorescence lifetime in the table was obtained by doping the compound at a concentration of 1 wt% in polystyrene to make the test sample and measuring it with a time-resolved fluorescence spectrometer. The test instrument was Edinburgh fluorescence spectrometer (FLS-1000, UK).

[0315] As can be seen from Table 1, the nitrogen-containing heteroaromatic fused-ring compounds in the examples provided by the present invention exhibit a delayed fluorescence effect, and their delayed fluorescence lifetimes are in the range of 48 - 89 μs.

[0316] Device example

[0317] The process of preparing the device by vacuum evaporation for the organic light-emitting layer is as follows: On indium tin oxide loaded on a glass substrate, 4×10 -4Under a vacuum of [[Pa]], TAPC, TCTA, EML (the invented luminescent compound is co-evaporated with SIMCP2 and DPAc-DtCzBN in a mass ratio of 1:2:7), TmPyPB, and LiF / Al cathode are deposited in sequence to obtain an organic electroluminescent device, where TAPC and TmPyPB serve as the hole transport layer and the electron transport layer respectively, and TCTA is the exciton blocking layer. The structural formula is shown as follows:

[0318]

[0319] The specific device structure (device structure A) of the device prepared by vacuum evaporation process is:

[0320] ITO / TAPC(50nm) / TCTA(5nm) / EML(30nm) / TmPyPB(30nm) / LiF(0.8nm) / Al(100nm).

[0321] The process of preparing the device with the organic light-emitting layer by solution processing technology is as follows: Poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid) (PEDOT:PSS) is spin-coated on indium tin oxide loaded on a glass substrate and annealed at 120 °C for 30 minutes. Subsequently, a toluene solution of the invented luminescent compound mixed with SIMCP2 and DPAc-DtCzBN in a mass ratio of 1:2:7 is spin-coated at a speed of 1500 rpm for 1 minute and annealed at 80 °C for 30 minutes. Then, under a vacuum of 4×10 -4 Pa, TSPO1, TmPyPB, and LiF / Al cathode are deposited in sequence to obtain an organic electroluminescent device, where TSPO1 and TmPyPB serve as the hole blocking layer, the electron transport layer, and the host material respectively. The structural formula is shown as follows:

[0322]

[0323] The specific device structure (device structure B) of the device prepared by solution processing technology is:

[0324] ITO / PEDOT:PSS(40nm) / EML(30nm) / TSPO1(8nm) / TmPyPB(42nm) / LiF(1nm) / Al(100nm).

[0325] Example 28

[0326] Taking the heteroaromatic condensed ring compound A1-1 as the implementation object, the heteroaromatic condensed ring compound A1-1, SIMCP2, and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. The organic light-emitting layer adopts the solution processing technology, and an organic electroluminescent device is prepared using the structure described in "device structure B", and the obtained device is tested.

[0327] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with the azabicyclic fused-ring compound A1-1 provided by the present invention.

[0328] Example 29

[0329] Taking the azabicyclic fused-ring compound A1-2 as the object of implementation, the azabicyclic fused-ring compound A1-2, SIMCP2, and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, and an organic electroluminescent device is prepared using the structure described in "Device Structure A", and the obtained device is tested.

[0330] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with the azabicyclic fused-ring compound A1-2 provided by the present invention.

[0331] Example 30

[0332] Taking the azabicyclic fused-ring compound A1-3 as the object of implementation, the azabicyclic fused-ring compound A1-3, SIMCP2, and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, and an organic electroluminescent device is prepared using the structure described in "Device Structure A", and the obtained device is tested.

[0333] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with the azabicyclic fused-ring compound A1-3 provided by the present invention.

[0334] Example 31

[0335] Taking the azabicyclic fused-ring compound A1-4 as the object of implementation, the azabicyclic fused-ring compound A1-4, SIMCP2, and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. The organic light-emitting layer adopts a solution processing process, and an organic electroluminescent device is prepared using the structure described in "Device Structure B", and the obtained device is tested.

[0336] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with the azabicyclic fused-ring compound A1-4 provided by the present invention.

[0337] Example 32

[0338] Taking the azabicyclic fused-ring compound A1-5 as the object of implementation, the azabicyclic fused-ring compound A1-5, SIMCP2, and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, and an organic electroluminescent device is prepared using the structure described in "Device Structure A", and the obtained device is tested.

[0339] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with the azabicyclic fused-ring compound A1-5 provided by the present invention.

[0340] Example 33

[0341] Taking the azabicyclic fused-ring compound A1-8 as the implementation object, the azabicyclic fused-ring compound A1-8, SIMCP2 and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. The organic light-emitting layer adopts a solution processing technology, and an organic electroluminescent device is prepared by using the structure described in "Device Structure B", and the obtained device is tested.

[0342] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with the azabicyclic fused-ring compound A1-8 provided by the present invention.

[0343] Example 34

[0344] Taking the azabicyclic fused-ring compound A1-12 as the implementation object, the azabicyclic fused-ring compound A1-12, SIMCP2 and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, and an organic electroluminescent device is prepared by using the structure described in "Device Structure A", and the obtained device is tested.

[0345] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with the azabicyclic fused-ring compound A1-12 provided by the present invention.

[0346] Example 35

[0347] Taking the azabicyclic fused-ring compound A1-18 as the implementation object, the azabicyclic fused-ring compound A1-18, SIMCP2 and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. The organic light-emitting layer adopts a solution processing technology, and an organic electroluminescent device is prepared by using the structure described in "Device Structure B", and the obtained device is tested.

[0348] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with the azabicyclic fused-ring compound A1-18 provided by the present invention.

[0349] Example 36

[0350] Taking the azabicyclic fused-ring compound A2-1 as the implementation object, the azabicyclic fused-ring compound A2-1, SIMCP2 and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, and an organic electroluminescent device is prepared by using the structure described in "Device Structure A", and the obtained device is tested.

[0351] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with the azabicycloaromatic compound A2-1 provided by the present invention.

[0352] Example 37

[0353] Taking the azabicycloaromatic compound A2-11 as the implementation object, the azabicycloaromatic compound A2-11, SIMCP2 and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, and an organic electroluminescent device is prepared by using the structure described in "Device Structure A", and the obtained device is tested.

[0354] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with the azabicycloaromatic compound A2-11 provided by the present invention.

[0355] Example 38

[0356] Taking the azabicycloaromatic compound A3-1 as the implementation object, the azabicycloaromatic compound A3-1, SIMCP2 and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, and an organic electroluminescent device is prepared by using the structure described in "Device Structure A", and the obtained device is tested.

[0357] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with the azabicycloaromatic compound A3-1 provided by the present invention.

[0358] Example 39

[0359] Taking the azabicycloaromatic compound A3-2 as the implementation object, the azabicycloaromatic compound A3-2, SIMCP2 and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, and an organic electroluminescent device is prepared by using the structure described in "Device Structure A", and the obtained device is tested.

[0360] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with the azabicycloaromatic compound A3-2 provided by the present invention.

[0361] Example 40

[0362] Taking the azabicycloaromatic compound A3-3 as the implementation object, the azabicycloaromatic compound A3-3, SIMCP2 and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. The organic light-emitting layer adopts a solution processing technology, and an organic electroluminescent device is prepared by using the structure described in "Device Structure B", and the obtained device is tested.

[0363] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with the azabenzannulated polycyclic compound A3-3 provided by the present invention.

[0364] Example 41

[0365] Taking the azabenzannulated polycyclic compound A3-5 as the object of implementation, the azabenzannulated polycyclic compound A3-5, SIMCP2, and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, and an organic electroluminescent device is prepared using the structure described in "Device Structure A", and the obtained device is tested.

[0366] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with the azabenzannulated polycyclic compound A3-5 provided by the present invention.

[0367] Example 42

[0368] Taking the azabenzannulated polycyclic compound A3-6 as the object of implementation, the azabenzannulated polycyclic compound A3-6, SIMCP2, and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. The organic light-emitting layer adopts a solution processing process, and an organic electroluminescent device is prepared using the structure described in "Device Structure B", and the obtained device is tested.

[0369] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with the azabenzannulated polycyclic compound A3-6 provided by the present invention.

[0370] Example 43

[0371] Taking the azabenzannulated polycyclic compound A3-7 as the object of implementation, the azabenzannulated polycyclic compound A3-7, SIMCP2, and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. The organic light-emitting layer adopts a solution processing process, and an organic electroluminescent device is prepared using the structure described in "Device Structure B", and the obtained device is tested.

[0372] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with the azabenzannulated polycyclic compound A3-7 provided by the present invention.

[0373] Example 44

[0374] Taking the azabenzannulated polycyclic compound A3-8 as the object of implementation, the azabenzannulated polycyclic compound A3-8, SIMCP2, and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. The organic light-emitting layer adopts a solution processing process, and an organic electroluminescent device is prepared using the structure described in "Device Structure B", and the obtained device is tested.

[0375] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with the azabicyclic fused-ring compound A3-8 provided by the present invention.

[0376] Example 45

[0377] Taking the azabicyclic fused-ring compound A3-12 as the implementation object, the azabicyclic fused-ring compound A3-12, SIMCP2, and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. The organic light-emitting layer adopts a solution processing technology, and an organic electroluminescent device is prepared using the structure described in "Device Structure B", and the obtained device is tested.

[0378] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with the azabicyclic fused-ring compound A3-12 provided by the present invention.

[0379] Example 46

[0380] Taking the azabicyclic fused-ring compound A3-13 as the implementation object, the azabicyclic fused-ring compound A3-13, SIMCP2, and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. The organic light-emitting layer adopts a solution processing technology, and an organic electroluminescent device is prepared using the structure described in "Device Structure B", and the obtained device is tested.

[0381] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with the azabicyclic fused-ring compound A3-13 provided by the present invention.

[0382] Example 47

[0383] Taking the azabicyclic fused-ring compound B1-1 as the implementation object, the azabicyclic fused-ring compound B1-1, SIMCP2, and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. The organic light-emitting layer adopts a solution processing technology, and an organic electroluminescent device is prepared using the structure described in "Device Structure B", and the obtained device is tested.

[0384] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with the azabicyclic fused-ring compound B1-1 provided by the present invention.

[0385] Example 48

[0386] Taking the azabicyclic fused-ring compound B1-8 as the implementation object, the azabicyclic fused-ring compound B1-8, SIMCP2, and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. The organic light-emitting layer adopts a solution processing technology, and an organic electroluminescent device is prepared using the structure described in "Device Structure B", and the obtained device is tested.

[0387] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with the aza-aromatic fused-ring compound B1-8 provided by the present invention.

[0388] Example 49

[0389] Taking the aza-aromatic fused-ring compound B1-11 as the implementation object, the aza-aromatic fused-ring compound B1-11, SIMCP2 and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. The organic light-emitting layer adopts a solution processing technology, and an organic electroluminescent device is prepared by using the structure described in "Device Structure B", and the obtained device is tested.

[0390] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with the aza-aromatic fused-ring compound B1-11 provided by the present invention.

[0391] Example 50

[0392] Taking the aza-aromatic fused-ring compound B1-13 as the implementation object, the aza-aromatic fused-ring compound B1-13, SIMCP2 and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, and an organic electroluminescent device is prepared by using the structure described in "Device Structure A", and the obtained device is tested.

[0393] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with the aza-aromatic fused-ring compound B1-13 provided by the present invention.

[0394] Example 51

[0395] Taking the aza-aromatic fused-ring compound C1-1 as the implementation object, the aza-aromatic fused-ring compound C1-1, SIMCP2 and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. The organic light-emitting layer adopts a solution processing technology, and an organic electroluminescent device is prepared by using the structure described in "Device Structure B", and the obtained device is tested.

[0396] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with the aza-aromatic fused-ring compound C1-1 provided by the present invention.

[0397] Example 52

[0398] Taking the aza-aromatic fused-ring compound C1-8 as the implementation object, the aza-aromatic fused-ring compound C1-8, SIMCP2 and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. The organic light-emitting layer adopts a solution processing technology, and an organic electroluminescent device is prepared by using the structure described in "Device Structure B", and the obtained device is tested.

[0399] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with the azabicyclic aromatic condensed ring compound C1-8 provided by the present invention.

[0400] Example 53

[0401] Taking the azabicyclic aromatic condensed ring compound C1-11 as the implementation object, the azabicyclic aromatic condensed ring compound C1-11, SIMCP2 and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. The organic light-emitting layer adopts a solution processing technology, and an organic electroluminescent device is prepared by using the structure described in "Device Structure B", and the obtained device is tested.

[0402] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with the azabicyclic aromatic condensed ring compound C1-11 provided by the present invention.

[0403] Example 54

[0404] Taking the azabicyclic aromatic condensed ring compound C1-13 as the implementation object, the azabicyclic aromatic condensed ring compound C1-13, SIMCP2 and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, and an organic electroluminescent device is prepared by using the structure described in "Device Structure A", and the obtained device is tested.

[0405] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with the azabicyclic aromatic condensed ring compound C1-13 provided by the present invention.

[0406] Table 2 Performance parameters of electroluminescent devices prepared with the azabicyclic aromatic condensed ring compounds provided by the present invention

[0407]

[0408]

[0409] Note: The turn-on voltage in the table is the driving voltage of the device when the brightness is 1 cd m -2 ; the maximum external quantum efficiency is obtained according to the calculation method described in the literature (Jpn. J. Appl. Phys. 2001, 40, L783) based on the current-voltage curve and electroluminescent spectrum of the device; the full width at half maximum is the peak width at half of the peak height of the electroluminescent spectrum at room temperature, that is, a straight line parallel to the peak bottom is drawn through the midpoint of the peak height, and the distance between the two intersection points of this straight line and the two sides of the peak.

[0410] As can be seen from Table 2, the device prepared with the azabenzene-fused ring compound provided by the present invention has a very narrow electroluminescence spectrum, with a full width at half maximum of less than 50 nm, overcoming the problem of the relatively wide electroluminescence spectrum (70 - 100 nm) of the traditional D-A structured TADF compound. At the same time, the devices prepared with the azabenzene-fused ring compound provided by the present invention all have high device efficiency, and the maximum external quantum efficiency reaches 34.5%.

[0411] Obviously, the above embodiments are merely examples given for clear illustration and are not limitations on the implementation manners. For those of ordinary skill in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation manners here. And the obvious changes or modifications derived therefrom are still within the protection scope of the present invention.

Claims

1. A nitrogen heteroaromatic fused ring compound, characterized in that: It has a structure shown in any one of formula (I) to formula (III): Wherein, in formula (I), a and d are independently integers of 0 to 3, and b and c are independently integers of 0 to 4; in formula (II), a and b are independently integers of 0 to 3, and c and d are independently integers of 0 to 4; in formula (III), a and b are independently integers of 0 to 3, and c and d are independently integers of 0 to 4; X1 and X2 are independently selected from a single bond, O, S, Se, Te, N(R 1 )、B(R 1 )、C(R 1 R 2 )、Si(R 1 R 2 ), O=S=O or (R 1 )P=O; Y1 and Y2 are independently selected from S, N(R 1 ) or one of the following structures: Among them, R a ~R d Independently selected from H, D, C1-C30 straight chain, C3-C30 branched chain, C1-C30 ether chain, C1-C30 thioether chain, C1-C30 ester chain or C3-C30 cycloalkyl; Ar1 to Ar4 are independently selected from C6 to C60 aromatic groups or C5 to C60 heteroaromatic groups, wherein the heteroatoms in the heteroaromatic groups are selected from one or more of Si, Ge, N, P, O, S and Se; R1, R2, R3 and R4 are independently selected from H, D, F, Cl, Br, I, -CN, -NO2, -OR 1 、-SR 1 , -Se-R 1 , C3-C30 cycloalkyl, C3-C30 cycloalkenyl, C2-C30 heterocycloalkyl, C2-C30 heterocycloalkenyl, C6-C60 aromatic or C5-C60 heteroaromatic, wherein the heteroatoms in the heterocycloalkyl, heterocycloalkenyl and heteroaromatic are selected from one or more of Si, Ge, N, P, O, S and Se; The R 1 , R 2 and R 3 independently selected from H, D, F, Cl, Br, I, CN, OH, SH, NH2, C1-C30 straight chain, C3-C30 branched chain, C1-C30 ether chain, C1-C30 thioether chain, C1-C30 ester chain, C3-C30 cycloalkyl, C3-C30 cycloalkenyl, C2-C30 heterocycloalkyl, C2-C30 heterocycloalkenyl, C6-C60 aromatic, C4-C60 aromatic or C4-C60 heteroaromatic; the heteroatoms in the heterocycloalkyl, heterocycloalkenyl and heteroaromatic are selected from one or more of Si, Ge, N, P, O, S and Se; or R 1 and R 2 The bridging is performed through a single bond or a heteroatom, and the bridging heteroatom is selected from one or more of Si, Ge, N, P, O, S and Se.

2. The nitrogen heteroaromatic fused ring compound according to claim 1, characterized in that: The Ar1 to Ar4 are independently selected from one of the groups represented by A1 to A20: L1, L2 and L3 are independently selected from H, D, F, Cl, Br, I, CN, OH, SH, NH2, C1-C30 straight chain, C3-C30 branched chain, C1-C30 ether chain, C1-C30 thioether chain, C1-C30 ester chain, C3-C30 cycloalkyl, C3-C30 cycloalkenyl, C2-C30 heterocycloalkyl, C2-C30 heterocycloalkenyl, C6-C60 aromatic, C4-C60 aromatic or C4-C60 heteroaromatic; the heteroatoms in the heterocycloalkyl, heterocycloalkenyl and heteroaromatic groups are selected from one or more of Si, Ge, N, P, O, S and Se.

3. The nitrogen heteroaromatic fused ring compound according to claim 1, characterized in that: X1 and X2 are independently selected from a single bond, O, S, Se, N(R 1 )、C(R 1 R 2 ) or Si(R 1 R 2 ).

4. The nitrogen heteroaromatic fused ring compound according to claim 1, characterized in that: Said Y1 and Y2 are independently selected from one of the following structures:

5. The nitrogen heteroaromatic fused ring compound according to claim 1, characterized in that: It has any one of the structures shown in formula (A) to formula (C):

6. An organic electroluminescent device, comprising an anode, a cathode and an organic thin film layer located between the anode and the cathode, characterized in that: The organic thin film layer comprises the nitrogen heteroaromatic condensed ring compound according to any one of claims 1 to 5.

7. The organic electroluminescent device according to claim 6, characterized in that: The organic thin film layer comprises a light-emitting layer, and the light-emitting layer comprises the nitrogen heteroaromatic condensed ring compound according to any one of claims 1 to 5.

8. The organic electroluminescent device according to claim 7, characterized in that: The organic thin film layer further includes one or more layers of a hole injection layer, a hole transport layer and an electron blocking layer.

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