Fused heterocyclic compound and organic electroluminescent device containing same

Abstract

The invention discloses a fused heterocyclic compound and an organic electroluminescent device containing the compound. The compound provided by the invention is used as a guest material of a luminescent layer of an organic electroluminescent device, and an electron withdrawing group is introduced to a specific position in a green light boron-nitrogen aromatic fused ring structure, so that the HOMO energy level of molecules is reduced under the condition of not changing a spectrum, and the stability of the compound in the device is improved.

Description

Technical Field

[0001] The present invention relates to the technical field of organic electroluminescence, and particularly to a novel boron-nitrogen fused heterocyclic compound and its application, as well as an organic electroluminescent device comprising the compound. Background Art

[0002] An organic electroluminescent device (OLED: Organic Light Emitting Devices) is a current-driven thin film device with a sandwich-like structure, in which a single layer or multiple layers of organic functional material layers are sandwiched between an anode and a cathode. Under the action of an electric field, holes generated by the anode and electrons generated by the cathode will move, and are respectively injected into the hole transport layer and the electron transport layer, and migrate to the light-emitting layer. When the two meet and recombine in the light-emitting layer, energy excitons are generated, which can excite light-emitting molecules to finally generate visible light. OLEDs have the characteristics of self-luminescence, wide viewing angle, wide color gamut, short response time, etc., and can be made into large-size and / or flexible ultra-thin panels. It is a new display technology with rapid development and high process integration. Currently, it has been widely used in display products such as TVs, smartphones, tablets, vehicle-mounted displays, lighting, etc., and will be further applied in creative display products such as large-size displays and flexible screens.

[0003] In OLED devices, the material that plays a key role in luminous efficiency, device lifetime, luminous spectrum, etc. is the light-emitting layer material therein, especially the guest material doped in the light-emitting layer. In recent years, multi-resonant thermally activated delayed fluorescence (MR-TADF) materials have the advantages of high color purity and high luminous efficiency, which have attracted extensive attention in the scientific research community and the industrial community (Adv. Mater. 2016, 28, 2777–2781). Summary of the Invention

[0004] As described above, MR-TADF materials have attracted extensive attention in the scientific research community and the industrial community due to their high color purity and high luminous efficiency. However, currently, the light color of MR-TADF materials has been limited to the blue-deep blue region, and highly efficient, narrow-emission full-color luminescent dopant materials are very scarce, thus restricting further applications in the display field.

[0005] To solve the above problems, one of the objectives of the present invention is to provide a novel fused heterocyclic compound. Specifically, the present application provides: 1) a fused heterocyclic compound, wherein the compound is composed of the following general formulas (1) to (4):

[0006]

[0007] R 1 ~R 5 、R 11 ~R14 Each independently selected from a hydrogen atom, a deuterium atom, a chlorine atom, a bromine atom, a fluorine atom, a cyano group, a substituted silyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, and a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms;

[0008] X 1 -X 4 Each independently selected from the following groups:

[0009]

[0010] Said R 21 -R 26 Is hydrogen, deuterium, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 ring carbon atoms, a deuterated alkyl group having 1 to 20 carbon atoms, a deuterated cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted phenyl group.

[0011] 2) The fused heterocyclic compound according to 1) above, wherein said R 1 ~R 5 、R 11 ~R 14 、R 21 -R 26 The substituents are each independently selected from: a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, a substituted silyl group, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted n-propyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted n-butyl group, a substituted or unsubstituted isobutyl group, a substituted or unsubstituted sec-butyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted 2-methylbutyl group, a substituted or unsubstituted n-pentyl group, a substituted or unsubstituted sec-pentyl group, a substituted or unsubstituted cyclopropyl group, a substituted or unsubstituted cyclobutyl group, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted adamantyl group, a substituted or unsubstituted thiophenyl group, a substituted or unsubstituted indolyl group,, a substituted or unsubstituted furyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted spirobifluorenyl group, a substituted or unsubstituted indenofluorenyl group, a substituted or unsubstituted fluoranthenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted perylenyl group, a substituted or unsubstituted tetraphenyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzoselenophenyl group, and a substituted or unsubstituted carbazolyl group.

[0012] 3) The fused heterocyclic compound according to 1) or 2) above, wherein the "substitution" in the "substituted or unsubstituted" of the fused heterocyclic compound means that the substituents are independently selected from a deuterium atom, a tritium atom, a halogen atom, a cyano group, a hydroxyl group, a monovalent alkyl group or cycloalkyl group having 1 to 10 carbon atoms, a monovalent monocyclic aryl group or fused polycyclic aryl group having 6 to 30 carbon atoms, a monovalent heterocyclic group or fused polycyclic heteroaryl group having 2 to 50 carbon atoms.

[0013] 4) The fused heterocyclic compound according to any one of 1) to 3) above, wherein the fused heterocyclic compound is selected from the following structures:

[0014]

[0015]

[0016]

[0017]

[0018]

[0019]

[0020]

[0021]

[0022]

[0023]

[0024]

[0025]

[0026]

[0027]

[0028]

[0029]

[0030]

[0031]

[0032]

[0033]

[0034]

[0035]

[0036] 5) An organic electroluminescent device, wherein the organic electroluminescent device includes an anode, a cathode, and at least one organic thin film located between the anode and the cathode, and the organic thin film contains the compound described in any one of the above 1)-4).

[0037] 6) The organic electroluminescent device according to the above 5), wherein the organic thin film includes any one or at least two combinations of a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, an exciton blocking layer, a hole blocking layer, an electron transport layer, and an electron injection layer, and at least one layer of the light emitting layer contains the compound described in any one of the above 1)-4).

[0038] 7) The organic electroluminescent device according to the above 5) or 6), wherein the compound is used as a light emitting material in the organic electroluminescent device and is applied to the light emitting layer.

[0039] The specific reason why the compound of the present invention has excellent performance as a light emitting layer material in an organic electroluminescent device is determined by the following structural design: an electron-withdrawing group is introduced at the peripheral position of carbazole in the green light boron-nitrogen aromatic condensed ring structure, which can effectively reduce the HOMO energy level of the molecule without changing the molecular emission spectrum, avoid it becoming a trap for capturing holes, and allow it to exist only as a light emitting molecule in the light emitting layer without participating in carrier transport. In this way, the probability of the exciton-polaron side reaction of the light emitting molecule can be greatly reduced, thereby improving the device stability.

[0040] The electroluminescence spectrum of the OLED device prepared from the compound of the present invention has a narrow full width at half maximum and the property of thermally activated delayed fluorescence, thereby greatly improving the color purity of the material with multiple resonance-thermally activated delayed fluorescence. It has a low turn-on voltage, high luminous efficiency, and good service life, can meet the requirements of the current display industry for high-performance materials, and shows good application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] The drawings described herein are used to provide a further understanding of the present application and constitute a part of the present application. The schematic embodiments of the present application and their descriptions are used to explain the present application and do not constitute an improper limitation of the present application. In the drawings:

[0042] Figure 1 It is a schematic structural diagram of an organic electroluminescent device to which the compound of the present invention is applied. Among them, the meanings represented by the structures of each layer of the device are as follows:

[0043] 1. Transparent substrate layer, 2. ITO anode layer, 3. Hole injection layer, 4. Hole transport layer A, 5. Hole transport layer B (or electron blocking layer), 6. Light-emitting layer, 7. Electron transport layer B (or hole blocking layer), 8. Electron transport layer A, 9. Electron injection layer, 10. Cathode reflective electrode layer Detailed implementation mode

[0044] Term

[0045] In the present invention, the alkyl group can be straight-chain or branched. The number of carbon atoms in the alkyl group is not particularly limited, for example, it is 1 to 50, preferably 1 to 20, and more preferably 1 to 6. Specific examples of the alkyl group include, but are not limited to, methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methylbutyl, 1-ethylbutyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, nonyl, 2,2-dimethylheptyl, 1-ethylpropyl, 1,1-dimethylpropyl, isohexyl, 4-methylhexyl, and 5-methylhexyl.

[0046] Alkoxy refers to -O-alkyl, and the number of carbon atoms therein is not particularly limited, for example, it is 1 to 50, preferably 1 to 20, and more preferably 1 to 6. Examples of the alkoxy group include, but are not limited to, methoxy, ethoxy, propoxy (such as n-propoxy and isopropoxy), and tert-butoxy.

[0047] In the present invention, the above alkyl group or alkoxy group can be substituted. For example, in the fluoroalkyl group and fluoroalkoxy group after being substituted by fluorine, the number of carbon atoms is not particularly limited, for example, it is 1 to 20, and more preferably 1 to 6. Examples of the fluoroalkyl group include, but are not limited to, fluoromethyl, difluoromethyl, trifluoromethyl, trichloromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, and heptafluoropropyl. Examples of the fluoroalkoxy group include, but are not limited to, trifluoromethoxy, 2,2,2-trifluoroethoxy, and pentafluoroethoxy.

[0048] The cycloalkyl group can be monocyclic or polycyclic, and the number of carbon atoms therein is not particularly limited, for example, it is 3 to 50, preferably 3 to 20, and more preferably 3 to 6. As specific examples, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and adamantyl can be cited, and cyclohexyl is preferably cited.

[0049] The aryl group can be a monocyclic or polycyclic aryl group, and there is no particular limitation on the number of carbon atoms therein, for example, it is 6 to 50, preferably 6 to 20. Examples of the monocyclic aryl group include, but are not limited to, phenyl, biphenyl, terphenyl, and triphenyl. Examples of the polycyclic aryl group include naphthyl, anthracenyl, phenanthryl, pyrenyl, perylenyl, tetraphenyl, fluorenyl, acenaphathcenyl, triphenylenyl, and fluoranthenyl, but the scope of the present invention is not limited thereto. The heteroaryl group refers to an aryl group in which other elements (such as nitrogen, oxygen, sulfur, etc.) replace carbon atoms in the aromatic ring. There is no particular limitation on the number of carbon atoms therein, for example, it is 2 to 50, preferably 4 to 20.

[0050] "Heterocyclic group" refers to a cyclic compound group in which one or more ring atoms are replaced by heteroatoms other than carbon (such as nitrogen, oxygen, sulfur, etc.). The fused heterocyclic aryl group refers to a cyclic compound group in which at least two rings (where at least one is an aromatic ring) share one or more carbon atoms and at least one ring contains one or more heteroatoms. Examples of the heterocyclic group and the fused heterocyclic aryl group include, but are not limited to, thienyl, furyl, pyrrolyl, imidazolyl, triazolyl, oxazolyl, dioxazolyl, triazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, triazolyl, acridinyl, pyridazinyl, pyrazinyl, quinolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinolinyl, indolyl, carbazolyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothienyl, benzofuryl, dibenzofuryl, thiazolyl, isoxazolyl, dioxazolyl, thiadiazolyl, benzothiazolyl, and phenothiazinyl.

[0051] The silyl group is intended to include alkyl-substituted silyl and aryl-substituted silyl. Specific examples of such silyl groups include trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, dimethoxyphenylsilyl, diphenylmethylsilyl, diphenylvinylsilyl, methylcyclobutylsilyl, and dimethylfurylsilyl.

[0052] "Deuterated" means one or more deuterated or fully deuterated.

[0053] Hereinafter, multiple synthesis examples will be given to further illustrate the principles and features of the present invention. The examples given are only for explaining the present invention, but not for limiting the scope of the present invention.

[0054] Synthesis Example:

[0055] Synthesis Example 1: Synthesis of Compound 5

[0056]

[0057] Synthesis of Intermediate 1a: Weigh 7.0 g (25 mmol) of di-tert-butylcarbazole, 9.5 g (25 mmol) of 2,4-dibromo-5-fluoroiodobenzene, and 9.8 g (30 mmol) of cesium carbonate into a flask. Add 80 ml of dry N,N-dimethylformamide, evacuate and refill with gas, and react at 140 °C for 6 h under nitrogen protection. Stop the reaction, cool to room temperature, pour into 200 ml of water, and a yellow solid precipitates. Filter. Collect the solid and purify it by silica gel column chromatography to obtain 13.7 g of the product with a yield of 86%. The molecular weight measured by mass spectrometry is m / z = 637.0 (M+H) +

[0058] Synthesis of Intermediate 1b: Weigh 12.7 g (20 mmol) of Intermediate 1a, 3.7 g (25 mmol) of 4-tert-butylaniline, 0.95 g (1 mmol) of tris(dibenzylideneacetone)dipalladium, 1.1 g (2 mmol) of DPPF, and 2.95 g (30 mmol) of sodium tert-butoxide into a flask. Add 200 ml of toluene, evacuate and refill with gas, and reflux at 110 °C for 20 h under nitrogen protection. Stop the reaction, cool to room temperature, extract with ethyl acetate and water, and concentrate by rotary evaporation. Then purify it by silica gel column chromatography to obtain approximately 9.64 g of the product with a yield of 73%. The molecular weight measured by mass spectrometry is m / z = 658.5 (M+H) +

[0059] Synthesis of Intermediate 1c: Weigh 9.24 g (14 mmol) of Intermediate 1b into a flask. Add 100 ml of anhydrous THF, protect with nitrogen, slowly add 0.38 g (16 mmol) of sodium hydride, react at room temperature for 10 min, then add 3.92 g (18 mmol) of di-tert-butyl dicarbonate, and react at 70 °C for 6 h. Stop the reaction, cool to room temperature, extract with ethyl acetate and water, and concentrate by rotary evaporation. Then purify it by silica gel column chromatography to obtain approximately 9.9 g of the product with a yield of 70%. The molecular weight measured by mass spectrometry is m / z = 758.4 (M+H) +

[0060] Synthesis of Intermediate 1d: Weigh 7.6 g (10 mmol) of Intermediate 1c and dissolve it in dry tetrahydrofuran, and stir at -78 °C for 10 minutes. Under nitrogen protection, add 8.4 ml of a n-hexane solution of n-butyllithium (21 mmol, 2.5 M) dropwise to the reaction solution. After the addition is complete, maintain low-temperature stirring for 1 h. At -78 °C, weigh 4.14 g (23 mmol) of 9-fluorenone and add it to the reaction solution, and let it return to room temperature naturally, and react for 10 h. Add 20 ml of water to quench the reaction, extract with ethyl acetate / water three times, collect the organic phase, evaporate the solvent under reduced pressure, and separate by silica gel column chromatography to obtain the crude product. Dissolve the crude product in 50 ml of dichloromethane, stir at room temperature, and under nitrogen protection, add 1.2 ml (10 mmol) of boron trifluoride diethyl etherate dropwise. Stir at room temperature for 1 h, stop the reaction, add sodium carbonate solution to neutralize the reaction solution, and extract with dichloromethane three times. Evaporate the solvent under reduced pressure, and separate by silica gel column chromatography to obtain 4.88 g of the product, with a yield of 59%, and the molecular weight measured by mass spectrometry is m / z = 826.9 (M + H) +

[0061] Synthesis of Intermediate 1e: Weigh 8.27 g (10 mmol) of Intermediate 1d, 3.8 g (12 mmol) of 2-bromo-4-chloro-1-iodobenzene, 0.45 g (0.5 mmol) of tris(dibenzylideneacetone)dipalladium, 1.1 g (2 mmol) of DPPF, and 1.9 g (20 mmol) of sodium tert-butoxide into a flask, add 80 ml of toluene, evacuate and replace the gas, and reflux at 110 °C for 24 h under nitrogen protection. Stop the reaction, cool to room temperature, extract with dichloromethane and water, and concentrate by evaporation under reduced pressure. Then separate and purify by silica gel column chromatography to obtain about 5.38 g of the product, with a yield of 53%, and the molecular weight measured by mass spectrometry is m / z = 1014.8 (M + H) +

[0062] Synthesis of Intermediate 1f: Weigh 5.0 g (5 mmol) of Intermediate 1e, 0.09 g (0.2 mmol) of palladium acetate, 0.11 g (0.4 mmol) of tricyclohexylphosphine, and 2.1 g (15 mmol) of potassium carbonate into a flask, add 60 ml of DMAc, evacuate and replace the gas, and react at 140 °C for 24 h under nitrogen protection. Stop the reaction, cool to room temperature, add 50 ml of water to precipitate a solid, and filter to collect the filter cake. Then separate and purify by silica gel column chromatography to obtain about 3.04 g of the product, with a yield of 65%, and the molecular weight measured by mass spectrometry is m / z = 934.6 (M + H) +

[0063] Synthesis of Intermediate 1g: Weigh 9.35 g (10 mmol) of Intermediate 1f and 1.98 g (11 mmol) of NBS into a flask, add 30 ml of chloroform, heat the reaction at 60 °C for 5 h, stop the reaction, cool to room temperature, extract with dichloromethane and water, and rotary evaporate to concentrate the organic phase. Then, purify by silica gel column chromatography to obtain approximately 8.8 g of the product with a yield of 87%. The molecular weight measured by mass spectrometry is m / z = 1012.8 (M+H). +

[0064] Synthesis of Intermediate 1h: Weigh 6.07 g (6 mmol) of Intermediate 1g and dissolve it in 40 ml of dry xylene. Under nitrogen protection, add 3.2 ml of n-butyllithium solution (8 mmol, 2.5 M) dropwise at -20 °C, stir at low temperature for 1 h, and then stir at room temperature for 1 h. Return to -20 °C, add 3.0 g (12 mmol) of boron tribromide, stir at low temperature for 1 h, and then stir at room temperature for 2 h. Then add 2.3 g (18 mmol) of diisopropylethylamine and heat the reaction at 110 °C for 6 h. Stop the reaction, cool to room temperature, add sodium carbonate solution to neutralize to neutral, extract with dichloromethane three times, collect the organic phase, rotary evaporate the solvent, separate by silica gel column chromatography to obtain the crude product, and then recrystallize with dichloromethane / ethanol to obtain 1.41 g of the target product. Orange-red solid, yield 25%, and the molecular weight measured by mass spectrometry is m / z = 942.6 (M+H)+

[0065] Synthesis of Compound 5: Weigh 0.94 g (1 mmol) of Intermediate 1h, 0.18 g (1.5 mmol) of 3-boronic acid pyridine, 0.04 g (0.05 mmol) of tris(dibenzylideneacetone)dipalladium, 0.09 g (0.2 mmol) of 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl, and 0.35 g (2.5 mmol) of potassium carbonate into a flask, add 10 ml of toluene, 1 ml of ethanol, and 1 ml of water, evacuate and replace the gas, under nitrogen protection, react at 90 °C for 12 h. Stop the reaction, extract with dichloromethane and water, rotary evaporate to concentrate, and purify by silica gel column chromatography to obtain approximately 0.89 g of the target product with a yield of 86%. The molecular weight measured by mass spectrometry is m / z = 986.1 (M+H). +

[0066] Synthesis Example 2: Synthesis of Compound 17

[0067]

[0068] Synthesis of Intermediates 2a - 2h: The same as the synthesis of 1a - 1h.

[0069] Synthesis of Compound 17: Weigh 0.94 g (1 mmol) of Intermediate 2h, 0.22 g (1.5 mmol) of 1-cyano-3-phenylboronic acid, 0.04 g (0.05 mmol) of tris(dibenzylideneacetone)dipalladium, 0.09 g (0.2 mmol) of 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl, and 0.35 g (2.5 mmol) of potassium carbonate into a flask. Add 10 ml of toluene, 1 ml of ethanol, and 1 ml of water. Evacuate and refill with gas, and react under nitrogen protection at 90 °C for 12 h. Stop the reaction, extract with dichloromethane and water, concentrate by rotary evaporation, and purify by silica gel column chromatography to obtain approximately 0.9 g of the target product with a yield of 89%. The molecular weight measured by mass spectrometry is m / z = 1010.1 (M+H). +

[0070] Synthesis Example 3: Synthesis of Compound 137

[0071]

[0072] Synthesis of Intermediate 3a: Weigh 7.0 g (25 mmol) of di-tert-butylcarbazole, 9.8 g (25 mmol) of 2,4-dibromo-5-fluoroiodotoluene, and 9.8 g (30 mmol) of cesium carbonate into a flask. Add 80 ml of dry N,N-dimethylformamide. Evacuate and refill with gas, and react under nitrogen protection at 140 °C for 6 h. Stop the reaction, cool to room temperature, pour into 200 ml of water, precipitate a yellow solid, and filter. Collect the solid and purify by silica gel column chromatography to obtain 13.2 g of the product with a yield of 81%. The molecular weight measured by mass spectrometry is m / z = 653.2 (M+H). +

[0073] Synthesis of Intermediate 3b: Weigh 13 g (20 mmol) of Intermediate 3a, 3.7 g (25 mmol) of 4-tert-butylaniline, 0.95 g (1 mmol) of tris(dibenzylideneacetone)dipalladium, 1.1 g (2 mmol) of DPPF, and 2.95 g (30 mmol) of sodium tert-butoxide into a flask. Add 200 ml of toluene. Evacuate and refill with gas, and reflux at 110 °C for 20 h under nitrogen protection. Stop the reaction, cool to room temperature, extract with ethyl acetate and water, and concentrate by rotary evaporation. Then purify by silica gel column chromatography to obtain approximately 9.6 g of the product with a yield of 71%. The molecular weight measured by mass spectrometry is m / z = 674.6 (M+H). +

[0074] Synthesis of Intermediate 3c: Weigh 9.4 g (14 mmol) of Intermediate 3b into a flask, add 100 ml of anhydrous THF, protect it with nitrogen, slowly add 0.38 g (16 mmol) of sodium hydride, react at room temperature for 10 min, then add 3.92 g (18 mmol) of di-tert-butyl dicarbonate, and react at 70 °C for 6 h. Stop the reaction, cool it to room temperature, extract with ethyl acetate and water, and concentrate by rotary evaporation. Then purify it by silica gel column chromatography to obtain about 8.4 g of the product, with a yield of 78%. The molecular weight measured by mass spectrometry is m / z = 774.7 (M+H) +

[0075] Synthesis of Intermediate 3d: Weigh 7.7 g (10 mmol) of Intermediate 3c and dissolve it in dry tetrahydrofuran, stir at -78 °C for 10 minutes. Under nitrogen protection, add 8.4 ml of a n-hexane solution of n-butyllithium (21 mmol, 2.5 M) dropwise to the reaction solution. After the addition is complete, keep stirring at low temperature for 1 h. At -78 °C, weigh 4.14 g (23 mmol) of 9-fluorenone and add it to the reaction solution, and let it return to room temperature naturally, and react for 10 h. Add 20 ml of water to quench the reaction, extract with ethyl acetate / water three times, collect the organic phase, evaporate the solvent by rotary evaporation, and separate by silica gel column chromatography to obtain the crude product. Dissolve the crude product in 50 ml of dichloromethane, stir at room temperature, and under nitrogen protection, add 1.2 ml (10 mmol) of boron trifluoride diethyl etherate dropwise. Stir at room temperature for 1 h, stop the reaction, add sodium carbonate solution to neutralize the reaction solution, and extract with dichloromethane three times. Evaporate the solvent by rotary evaporation, and separate by silica gel column chromatography to obtain 5.5 g of the product, with a yield of 66%. The molecular weight measured by mass spectrometry is m / z = 841.1 (M+H) +

[0076] Synthesis of Intermediate 3e: Weigh 8.4 g (10 mmol) of Intermediate 3d, 3.8 g (12 mmol) of 2-bromo-4-chloro-1-iodobenzene, 0.45 g (0.5 mmol) of tris(dibenzylideneacetone)dipalladium, 1.1 g (2 mmol) of DPPF, and 1.9 g (20 mmol) of sodium tert-butoxide into a flask, add 80 ml of toluene, evacuate and replace the gas, and reflux at 110 °C for 24 h under nitrogen protection. Stop the reaction, cool it to room temperature, extract with dichloromethane and water, and concentrate by rotary evaporation. Then purify it by silica gel column chromatography to obtain about 5.6 g of the product, with a yield of 55%. The molecular weight measured by mass spectrometry is m / z = 1030.6 (M+H) +

[0077] Synthesis of Intermediate 3f: Weigh 5.1 g (5 mmol) of Intermediate 3e, 0.09 g (0.2 mmol) of palladium acetate, 0.11 g (0.4 mmol) of tricyclohexylphosphine, and 2.1 g (15 mmol) of potassium carbonate into a flask. Add 60 ml of DMAc, evacuate and replace the gas, and react at 140 °C for 24 h under nitrogen protection. Stop the reaction, cool to room temperature, add 50 ml of water to precipitate the solid, and filter to collect the filter cake. Then, purify by silica gel column chromatography to obtain about 2.9 g of the product with a yield of 62%. The molecular weight measured by mass spectrometry is m / z = 949.7 (M+H). +

[0078] Synthesis of Intermediate 3g: Weigh 9.5 g (10 mmol) of Intermediate 3f and 1.98 g (11 mmol) of NBS into a flask, add 30 ml of chloroform, heat and react at 60 °C for 5 h. Stop the reaction, cool to room temperature, extract with dichloromethane and water, and rotary evaporate to concentrate the organic phase. Then, purify by silica gel column chromatography to obtain about 8.4 g of the product with a yield of 82%. The molecular weight measured by mass spectrometry is m / z = 1028.6 (M+H). +

[0079] Synthesis of Intermediate 3h: Weigh 6.2 g (6 mmol) of Intermediate 3g and dissolve it in 40 ml of dry xylene. Under nitrogen protection, dropwise add 3.2 ml of n-butyllithium solution (8 mmol, 2.5 M) at -20 °C, stir at low temperature for 1 h, and stir at room temperature for 1 h. Return to -20 °C, add 3.0 g (12 mmol) of boron tribromide, stir at low temperature for 1 h, and stir at room temperature for 2 h. Then add 2.3 g (18 mmol) of diisopropylethylamine, heat to 110 °C and react for 6 h. Stop the reaction, cool to room temperature, add sodium carbonate solution to neutralize to neutrality, extract with dichloromethane three times, collect the organic phase, rotary evaporate the solvent, separate by silica gel column to obtain the crude product, and then recrystallize with dichloromethane / ethanol to obtain 2.4 g of the target product. Orange-red solid, yield 42%, and the molecular weight measured by mass spectrometry is m / z = 957.5 (M+H)+

[0080] Synthesis of Compound 137: Weigh 0.96 g (1 mmol) of Intermediate 3h, 0.26 g (1.5 mmol) of isoquinoline-4-boronic acid, 0.04 g (0.05 mmol) of tris(dibenzylideneacetone)dipalladium, 0.09 g (0.2 mmol) of 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl, and 0.35 g (2.5 mmol) of potassium carbonate into a flask. Add 10 ml of toluene, 1 ml of ethanol, and 1 ml of water, evacuate and replace the gas, and react at 90 °C for 12 h under nitrogen protection. Stop the reaction, extract with dichloromethane and water, rotary evaporate to concentrate, and purify by silica gel column chromatography to obtain about 0.8 g of the target product with a yield of 77%. The molecular weight measured by mass spectrometry is m / z = 1050.2 (M+H). +

[0081] Synthesis Example 4: Synthesis of Compound 178

[0082]

[0083] Synthesis of Intermediate 4a: Weigh 7.0 g (25 mmol) of di-tert-butylcarbazole, 9.8 g (25 mmol) of 2,4-dibromo-5-fluoroiododide methylbenzene, and 9.8 g (30 mmol) of cesium carbonate into a flask. Add 80 ml of dry N,N-dimethylformamide, evacuate and replace the gas, and react at 140 °C for 6 h under nitrogen protection. Stop the reaction, cool to room temperature, pour into 200 ml of water, precipitate a yellow solid, and filter. Collect the solid, separate and purify it by silica gel column chromatography to obtain 12.9 g of the product with a yield of 80%. The molecular weight measured by mass spectrometry is m / z = 656.2 (M+H) +

[0084] Synthesis of Intermediate 4b: Weigh 13.1 g (20 mmol) of Intermediate 4a, 3.7 g (25 mmol) of 4-tert-butylaniline, 0.95 g (1 mmol) of tris(dibenzylideneacetone)dipalladium, 1.1 g (2 mmol) of DPPF, and 2.95 g (30 mmol) of sodium tert-butoxide into a flask. Add 200 ml of toluene, evacuate and replace the gas, and reflux at 110 °C for 20 h under nitrogen protection. Stop the reaction, cool to room temperature, extract with ethyl acetate and water, and concentrate by rotary evaporation. Then separate and purify it by silica gel column chromatography to obtain about 10.8 g of the product with a yield of 80%. The molecular weight measured by mass spectrometry is m / z = 677.6 (M+H) +

[0085] Synthesis of Intermediate 4c: Weigh 10.2 g (15 mmol) of Intermediate 4b into a flask, add 100 ml of anhydrous THF, protect with nitrogen, slowly add 0.38 g (16 mmol) of sodium hydride, react at room temperature for 10 min, then add 3.92 g (18 mmol) of di-tert-butyl dicarbonate, and react at 70 °C for 6 h. Stop the reaction, cool to room temperature, extract with ethyl acetate and water, and concentrate by rotary evaporation. Then separate and purify it by silica gel column chromatography to obtain about 8.4 g of the product with a yield of 72%. The molecular weight measured by mass spectrometry is m / z = 777.7 (M+H) +

[0086] Synthesis of Intermediate 4d: Weigh 7.8 g (10 mmol) of Intermediate 4c and dissolve it in dry tetrahydrofuran. Stir at -78 °C for 10 minutes. Under nitrogen protection, add 8.4 ml of a n-hexane solution of n-butyllithium (21 mmol, 2.5 M) dropwise to the reaction solution. After the addition is complete, maintain low-temperature stirring for 1 h. At -78 °C, weigh 4.14 g (23 mmol) of 9-fluorenone and add it to the reaction solution. Let it return to room temperature naturally and react for 10 h. Add 20 ml of water to quench the reaction. Extract with ethyl acetate / water three times, collect the organic phase, evaporate the solvent under reduced pressure, and separate by silica gel column chromatography to obtain the crude product. Dissolve the crude product in 50 ml of dichloromethane, stir at room temperature, and under nitrogen protection, add 1.2 ml (10 mmol) of boron trifluoride diethyl etherate dropwise. Stir at room temperature for 1 h, stop the reaction, add sodium carbonate solution to neutralize the reaction solution, and extract with dichloromethane three times. Evaporate the solvent under reduced pressure and separate by silica gel column chromatography to obtain 6.3 g of the product with a yield of 75%. The molecular weight measured by mass spectrometry is m / z = 847.1 (M+H) +

[0087] Synthesis of Intermediate 4e: Weigh 8.4 g (10 mmol) of Intermediate 4d, 3.8 g (12 mmol) of 2-bromo-3-chloro-1-iodobenzene, 0.45 g (0.5 mmol) of tris(dibenzylideneacetone)dipalladium, 1.1 g (2 mmol) of DPPF, and 1.9 g (20 mmol) of sodium tert-butoxide into a flask. Add 80 ml of toluene, evacuate and replace the gas. Under nitrogen protection, reflux at 110 °C for 24 h. Stop the reaction, cool to room temperature, extract with dichloromethane and water, and concentrate by evaporation under reduced pressure. Then separate and purify by silica gel column chromatography to obtain about 5.6 g of the product with a yield of 55%. The molecular weight measured by mass spectrometry is m / z = 1037.6 (M+H) +

[0088] Synthesis of Intermediate 4f: Weigh 5.1 g (5 mmol) of Intermediate 4e, 0.09 g (0.2 mmol) of palladium acetate, 0.11 g (0.4 mmol) of tricyclohexylphosphine, and 2.1 g (15 mmol) of potassium carbonate into a flask. Add 60 ml of DMAc, evacuate and replace the gas. Under nitrogen protection, react at 140 °C for 24 h. Stop the reaction, cool to room temperature, add 50 ml of water to precipitate the solid, and filter to collect the filter cake. Then separate and purify by silica gel column chromatography to obtain about 3.3 g of the product with a yield of 69%. The molecular weight measured by mass spectrometry is m / z = 955.7 (M+H) +

[0089] Synthesis of Intermediate 4g: Weigh 9.56 g (10 mmol) of Intermediate 4f and 1.98 g (11 mmol) of NBS into a flask, add 30 ml of chloroform, heat the reaction at 60 °C for 5 h, stop the reaction, cool to room temperature, extract with dichloromethane and water, and rotary evaporate to concentrate the organic phase. Then separate and purify by silica gel column chromatography to obtain about 8.3 g of the product with a yield of 80%. The molecular weight measured by mass spectrometry is m / z = 1031.6 (M+H). +

[0090] Synthesis of Intermediate 4h: Weigh 6.2 g (6 mmol) of Intermediate 4g and dissolve it in 40 ml of dry xylene. Under nitrogen protection, add 3.2 ml of n-butyllithium solution (8 mmol, 2.5 M) dropwise at -20 °C, stir at low temperature for 1 h, and stir at room temperature for 1 h. Return to -20 °C, add 3.0 g (12 mmol) of boron tribromide, stir at low temperature for 1 h, and stir at room temperature for 2 h. Then add 2.3 g (18 mmol) of diisopropylethylamine and heat to 110 °C to react for 6 h. Stop the reaction, cool to room temperature, add sodium carbonate solution to neutralize to neutral, extract three times with dichloromethane, collect the organic phase, rotary evaporate the solvent, separate by silica gel column chromatography to obtain the crude product, and then recrystallize with dichloromethane / ethanol to obtain 2.9 g of the target product. Orange-red solid, yield 51%, and the molecular weight measured by mass spectrometry is m / z = 963.5 (M+H)+

[0091] Synthesis of Compound 178: Weigh 0.96 g (1 mmol) of Intermediate 3h, 0.4 g (1.5 mmol) of 4,6-diphenyl-1,3,5-triazine-2-boronic acid, 0.04 g (0.05 mmol) of tris(dibenzylideneacetone)dipalladium, 0.09 g (0.2 mmol) of 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl, and 0.35 g (2.5 mmol) of potassium carbonate into a flask, add 10 ml of toluene, 1 ml of ethanol, and 1 ml of water, evacuate and replace with nitrogen, and react at 90 °C for 12 h. Stop the reaction, extract with dichloromethane and water, rotary evaporate to concentrate, and separate and purify by silica gel column chromatography to obtain about 0.84 g of the target product with a yield of 73%. The molecular weight measured by mass spectrometry is m / z = 1157.3 (M+H). +

[0092] Synthesis Example 5: Synthesis of Compound 197

[0093]

[0094] Synthesis of Intermediate 5a: The same as the synthesis of 1a.

[0095] Synthesis of Intermediate 5b: Weigh 12.7 g (20 mmol) of Intermediate 5a, 4.2 g (25 mmol) of 4-phenylaniline, 0.95 g (1 mmol) of tris(dibenzylideneacetone)dipalladium, 1.1 g (2 mmol) of DPPF, and 2.95 g (30 mmol) of sodium tert-butoxide into a flask. Add 200 ml of toluene, evacuate and refill with gas, and reflux at 110 °C for 20 h under nitrogen protection. Stop the reaction, cool to room temperature, extract with ethyl acetate and water, and concentrate by rotary evaporation. Then purify by silica gel column chromatography to obtain approximately 10.7 g of the product with a yield of 79%. The molecular weight measured by mass spectrometry is m / z = 680.5 (M+H) +

[0096] Synthesis of Intermediate 5c: Weigh 8.2 g (12 mmol) of Intermediate 5b into a flask, add 100 ml of anhydrous THF, protect with nitrogen, slowly add 0.38 g (16 mmol) of sodium hydride, react at room temperature for 10 min, then add 3.92 g (18 mmol) of di-tert-butyl dicarbonate, and react at 70 °C for 6 h. Stop the reaction, cool to room temperature, extract with ethyl acetate and water, and concentrate by rotary evaporation. Then purify by silica gel column chromatography to obtain approximately 6.5 g of the product with a yield of 70%. The molecular weight measured by mass spectrometry is m / z = 780.6 (M+H) +

[0097] Synthesis of Intermediate 5d: Weigh 7.8 g (10 mmol) of Intermediate 5c and dissolve it in dry tetrahydrofuran, stir at -78 °C for 10 minutes. Under nitrogen protection, add 8.4 ml of a n-hexane solution of n-butyllithium (21 mmol, 2.5 M) dropwise to the reaction solution. After the addition is complete, maintain low-temperature stirring for 1 h. At -78 °C, weigh 4.14 g (23 mmol) of 9-fluorenone and add it to the reaction solution, and let it return to room temperature naturally and react for 10 h. Add 20 ml of water to quench the reaction, extract with ethyl acetate / water three times, collect the organic phase, evaporate the solvent by rotary evaporation, and separate by silica gel column chromatography to obtain the crude product. Dissolve the crude product in 50 ml of dichloromethane, stir at room temperature, and under nitrogen protection, add 1.2 ml (10 mmol) of boron trifluoride diethyl ether dropwise. Stir at room temperature for 1 h, stop the reaction, add sodium carbonate solution to neutralize the reaction solution, and extract with dichloromethane three times. Evaporate the solvent by rotary evaporation and separate by silica gel column chromatography to obtain 5.2 g of the product with a yield of 62%. The molecular weight measured by mass spectrometry is m / z = 847.1 (M+H) +

[0098] Synthesis of Intermediate 5e: Weigh 8.47 g (10 mmol) of Intermediate 5d, 3.8 g (12 mmol) of 2-bromo-4-chloro-1-iodobenzene, 0.45 g (0.5 mmol) of tris(dibenzylideneacetone)dipalladium, 1.1 g (2 mmol) of DPPF, and 1.9 g (20 mmol) of sodium tert-butoxide into a flask. Add 80 ml of toluene, evacuate and refill with gas, and reflux at 110 °C for 24 h under nitrogen protection. Stop the reaction, cool to room temperature, extract with dichloromethane and water, and concentrate by rotary evaporation. Then purify by silica gel column chromatography to obtain approximately 6.1 g of the product with a yield of 59%. The molecular weight measured by mass spectrometry is m / z = 1036.5 (M+H) +

[0099] Synthesis of Intermediate 5f: Weigh 5.1 g (5 mmol) of Intermediate 5e, 0.09 g (0.2 mmol) of palladium acetate, 0.11 g (0.4 mmol) of tricyclohexylphosphine, and 2.1 g (15 mmol) of potassium carbonate into a flask. Add 60 ml of DMAc, evacuate and refill with gas, and react at 140 °C for 24 h under nitrogen protection. Stop the reaction, cool to room temperature, add 50 ml of water to precipitate the solid, and filter to collect the cake. Then purify by silica gel column chromatography to obtain approximately 2.9 g of the product with a yield of 60%. The molecular weight measured by mass spectrometry is m / z = 955.6 (M+H) +

[0100] Synthesis of Intermediate 5g: Weigh 9.55 g (10 mmol) of Intermediate 5f and 1.98 g (11 mmol) of NBS into a flask, add 30 ml of chloroform, heat and react at 60 °C for 5 h. Stop the reaction, cool to room temperature, extract with dichloromethane and water, and concentrate the organic phase by rotary evaporation. Then purify by silica gel column chromatography to obtain approximately 8.5 g of the product with a yield of 82%. The molecular weight measured by mass spectrometry is m / z = 1034.5 (M+H) +

[0101] Synthesis of Intermediate 5h: Weigh 6.2 g (6 mmol) of Intermediate 5g and dissolve it in 40 ml of dry xylene. Under nitrogen protection, dropwise add 3.2 ml of n-butyllithium solution (8 mmol, 2.5 M) at -20 °C, stir at low temperature for 1 h, and then stir at room temperature for 1 h. Return to -20 °C, add 3.0 g (12 mmol) of boron tribromide, stir at low temperature for 1 h, and then stir at room temperature for 2 h. Then add 2.3 g (18 mmol) of diisopropylethylamine, heat to 110 °C and react for 6 h. Stop the reaction, cool to room temperature, add sodium carbonate solution to neutralize to neutral, extract three times with dichloromethane, collect the organic phase, evaporate the solvent, separate by silica gel column to obtain the crude product, and then recrystallize with dichloromethane / ethanol to obtain 1.7 g of the target product. Orange-red solid, yield 30%, and the molecular weight measured by mass spectrometry is m / z = 963.4 (M+H)+

[0102] Synthesis of Compound 197: Weigh 0.96 g (1 mmol) of Intermediate 5h, 0.18 g (1.5 mmol) of 3 - pyridineboronic acid, 0.04 g (0.05 mmol) of tris(dibenzylideneacetone)dipalladium, 0.09 g (0.2 mmol) of 2 - dicyclohexylphosphino - 2',4',6' - triisopropylbiphenyl, and 0.35 g (2.5 mmol) of potassium carbonate into a flask. Add 10 ml of toluene, 1 ml of ethanol, and 1 ml of water. Evacuate and replace the air, and react under nitrogen protection at 90 °C for 12 h. Stop the reaction, extract with dichloromethane and water, concentrate by rotary evaporation, and purify by silica gel column chromatography to obtain about 0.8 g of the target product with a yield of 81%. The molecular weight measured by mass spectrometry is m / z = 1006.1 (M + H) +

[0103] Synthesis Example 6: Synthesis of Compound 245

[0104]

[0105] Synthesis of Intermediate 6a: Weigh 7.0 g (25 mmol) of diphenylcarbazole, 9.5 g (25 mmol) of 2,4 - dibromo - 5 - fluoroiodobenzene, and 9.8 g (30 mmol) of cesium carbonate into a flask. Add 80 ml of dry N,N - dimethylformamide. Evacuate and replace the air, and react at 140 °C for 6 h under nitrogen protection. Stop the reaction, cool to room temperature, pour into 200 ml of water, precipitate a yellow solid, and filter. Collect the solid and purify by silica gel column chromatography to obtain 13.7 g of the product with a yield of 86%. The molecular weight measured by mass spectrometry is m / z = 679.2 (M + H) +

[0106] Synthesis of Intermediate 6b: Weigh 11.0 g (20 mmol) of Intermediate 6a, 4.2 g (25 mmol) of 4 - phenylaniline, 0.95 g (1 mmol) of tris(dibenzylideneacetone)dipalladium, 1.1 g (2 mmol) of DPPF, and 2.95 g (30 mmol) of sodium tert - butoxide into a flask. Add 200 ml of toluene. Evacuate and replace the air, and reflux at 110 °C for 20 h under nitrogen protection. Stop the reaction, cool to room temperature, extract with ethyl acetate and water, and concentrate by rotary evaporation. Then purify by silica gel column chromatography to obtain about 9.9 g of the product with a yield of 69%. The molecular weight measured by mass spectrometry is m / z = 720.5 (M + H) +

[0107] Synthesis of Intermediate 6c: Weigh 8.6 g (12 mmol) of Intermediate 6b into a flask, add 100 ml of anhydrous THF, protect it with nitrogen, slowly add 0.38 g (16 mmol) of sodium hydride, react at room temperature for 10 min, then add 3.92 g (18 mmol) of di-tert-butyl dicarbonate, and react at 70 °C for 6 h. Stop the reaction, cool it to room temperature, extract with ethyl acetate and water, and concentrate by rotary evaporation. Then purify it by silica gel column chromatography to obtain about 7.9 g of the product, with a yield of 80%. The molecular weight measured by mass spectrometry is m / z = 820.6 (M+H) +

[0108] Synthesis of Intermediate 6d: Weigh 8.2 g (10 mmol) of Intermediate 6c and dissolve it in dry tetrahydrofuran, stir at -78 °C for 10 minutes. Under nitrogen protection, add 8.4 ml of a n-hexane solution of n-butyllithium (21 mmol, 2.5 M) dropwise to the reaction solution. After the addition is complete, keep stirring at low temperature for 1 h. At -78 °C, weigh 4.14 g (23 mmol) of 9-fluorenone and add it to the reaction solution, and let it return to room temperature naturally, and react for 10 h. Add 20 ml of water to quench the reaction, extract with ethyl acetate / water three times, collect the organic phase, evaporate the solvent by rotary evaporation, and separate by silica gel column chromatography to obtain the crude product. Dissolve the crude product in 50 ml of dichloromethane, stir at room temperature, and under nitrogen protection, add 1.2 ml (10 mmol) of boron trifluoride diethyl etherate dropwise. Stir at room temperature for 1 h, stop the reaction, add sodium carbonate solution to neutralize the reaction solution, and extract with dichloromethane three times. Evaporate the solvent by rotary evaporation, and separate by silica gel column chromatography to obtain 5.3 g of the product, with a yield of 60%. The molecular weight measured by mass spectrometry is m / z = 887.1 (M+H) +

[0109] Synthesis of Intermediate 6e: Weigh 8.87 g (10 mmol) of Intermediate 6d, 3.8 g (12 mmol) of 2-bromo-4-chloro-1-iodobenzene, 0.45 g (0.5 mmol) of tris(dibenzylideneacetone)dipalladium, 1.1 g (2 mmol) of DPPF, and 1.9 g (20 mmol) of sodium tert-butoxide into a flask, add 80 ml of toluene, evacuate and replace the gas, and reflux at 110 °C for 24 h under nitrogen protection. Stop the reaction, cool it to room temperature, extract with dichloromethane and water, and concentrate by rotary evaporation. Then purify it by silica gel column chromatography to obtain about 6.1 g of the product, with a yield of 59%. The molecular weight measured by mass spectrometry is m / z = 1076.5 (M+H) +

[0110] Synthesis of Intermediate 6f: Weigh 5.4 g (5 mmol) of Intermediate 6e, 0.09 g (0.2 mmol) of palladium acetate, 0.11 g (0.4 mmol) of tricyclohexylphosphine, and 2.1 g (15 mmol) of potassium carbonate into a flask, add 60 ml of DMAc, evacuate and refill with gas, and react at 140 °C for 24 h under nitrogen protection. Stop the reaction, cool to room temperature, add 50 ml of water to precipitate the solid, and filter to collect the filter cake. Then, purify by silica gel column chromatography to obtain approximately 3.0 g of the product with a yield of 60%. The molecular weight measured by mass spectrometry is m / z = 995.6 (M+H). +

[0111] Synthesis of Intermediate 6g: Weigh 9.55 g (10 mmol) of Intermediate 6f and 1.98 g (11 mmol) of NBS into a flask, add 30 ml of chloroform, heat and react at 60 °C for 5 h. Stop the reaction, cool to room temperature, extract with dichloromethane and water, and rotary evaporate and concentrate the organic phase. Then, purify by silica gel column chromatography to obtain approximately 8.5 g of the product with a yield of 79%. The molecular weight measured by mass spectrometry is m / z = 1074.5 (M+H). +

[0112] Synthesis of Intermediate 6h: Weigh 6.4 g (6 mmol) of Intermediate 6g and dissolve it in 40 ml of dry xylene. Under nitrogen protection, add 3.2 ml of n-butyllithium solution (8 mmol, 2.5 M) dropwise at -20 °C, stir at low temperature for 1 h, and then stir at room temperature for 1 h. Return to -20 °C, add 3.0 g (12 mmol) of boron tribromide, stir at low temperature for 1 h, and then stir at room temperature for 2 h. Then add 2.3 g (18 mmol) of diisopropylethylamine, heat to 110 °C and react for 6 h. Stop the reaction, cool to room temperature, add sodium carbonate solution to neutralize to neutral, extract three times with dichloromethane, collect the organic phase, rotary evaporate the solvent, separate by silica gel column to obtain the crude product, and then recrystallize with dichloromethane / ethanol to obtain 2.1 g of the target product. Orange-red solid, yield 35%, and the molecular weight measured by mass spectrometry is m / z = 1003.4 (M+H)+

[0113] Synthesis of Compound 245: Weigh 1.0 g (1 mmol) of Intermediate 6h, 0.18 g (1.5 mmol) of 3-boropyridine, 0.04 g (0.05 mmol) of tris(dibenzylideneacetone)dipalladium, 0.09 g (0.2 mmol) of 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl, and 0.35 g (2.5 mmol) of potassium carbonate into a flask, add 10 ml of toluene, 1 ml of ethanol, and 1 ml of water, evacuate and refill with gas, and react at 90 °C for 12 h under nitrogen protection. Stop the reaction, extract with dichloromethane and water, rotary evaporate and concentrate, and purify by silica gel column chromatography to obtain approximately 0.87 g of the target product with a yield of 83%. The molecular weight measured by mass spectrometry is m / z = 1046.1 (M+H). +

[0114] Synthesis Example 7: Synthesis of Compound 435

[0115]

[0116] Synthesis of Intermediates 7a - 7h: The same as the synthesis of 1a - 1h.

[0117] Synthesis of Compound 435: Weigh 0.94 g (1 mmol) of Intermediate 2h, 0.2 g (1.5 mmol) of 1 - deuteromethyl - 4 - pyridineboronic acid, 0.04 g (0.05 mmol) of tris(dibenzylideneacetone)dipalladium, 0.09 g (0.2 mmol) of 2 - dicyclohexylphosphino - 2',4',6' - triisopropylbiphenyl, and 0.35 g (2.5 mmol) of potassium carbonate into a flask. Add 10 ml of toluene, 1 ml of ethanol, and 1 ml of water. Evacuate and replace the gas, protect with nitrogen, and react at 90 °C for 12 h. Stop the reaction, extract with dichloromethane and water, concentrate by rotary evaporation, and purify by silica gel column chromatography to obtain about 0.7 g of the target product with a yield of 70%. The molecular weight measured by mass spectrometry is m / z = 1002.5 (M + H) +

[0118] Synthesis Example 8: Synthesis of Compound 445

[0119]

[0120] Synthesis of Intermediates 8a - 8h: The same as the synthesis of 1a - 1h.

[0121] Synthesis of Compound 445: Weigh 0.94 g (1 mmol) of Intermediate 2h, 0.26 g (1.5 mmol) of isoquinoline - 3 - boronic acid, 0.04 g (0.05 mmol) of tris(dibenzylideneacetone)dipalladium, 0.09 g (0.2 mmol) of 2 - dicyclohexylphosphino - 2',4',6' - triisopropylbiphenyl, and 0.35 g (2.5 mmol) of potassium carbonate into a flask. Add 10 ml of toluene, 1 ml of ethanol, and 1 ml of water. Evacuate and replace the gas, protect with nitrogen, and react at 90 °C for 12 h. Stop the reaction, extract with dichloromethane and water, concentrate by rotary evaporation, and purify by silica gel column chromatography to obtain about 0.7 g of the target product with a yield of 72%. The molecular weight measured by mass spectrometry is m / z = 1036.1 (M + H) +

[0122] Device Examples 1 - 15: Fabrication of Organic Electroluminescent Devices Using as Light - Emitting Layer Materials

[0123] A glass substrate with indium tin oxide (ITO) transparent electrodes (anodes) having a thickness of 25 mm × 75 mm × 1.1 mm was ultrasonically cleaned in isopropyl alcohol for 5 minutes and then subjected to ultraviolet light (UV)-ozone cleaning for 30 minutes. The film thickness of ITO was 130 nm. The cleaned glass substrate was mounted on the substrate holder of a vacuum evaporation apparatus, and the vacuum was pumped down to 1×10 -5 ~1×10 -6 Pa. A hole injection layer (HIL) HATCN was evaporated on the ITO transparent conductive layer with a film thickness of 15 nm. A hole transport layer A (HTL) was evaporated on top of this hole injection layer with a film thickness of 60 nm. Then, an electron blocking layer (EBL) was evaporated on top of this hole transport layer A with a film thickness of 40 nm. Then, an emitting layer (EML) was co-evaporated on top of this electron blocking layer with a film thickness of 40 nm. The emitting layer (EML) was evaporated by co-evaporating the light-emitting material and the host material GH of the emitting layer in a multi-source co-evaporation method, where the doping concentration of the light-emitting material was 2 wt%. Then, a hole blocking layer (HBL) was evaporated on top of this emitting layer with a film thickness of 5 nm. Then, an electron transport material (ETL) and lithium 8-hydroxyquinoline (Liq) were evaporated on top of this hole blocking layer with a film thickness of 30 nm and a doping ratio of 1:1. Then, an electron injection electrode (EIL) Liq was evaporated on top of this ETL with a film thickness of 1 nm. Then, a metal cathode aluminum (Al) was evaporated on top of this EIL with a film thickness of 100 nm. The structure of the organic electroluminescent device of Example 1 is as Figure 1 shown, Figure 1 and also shows the stacking order and functions of each functional layer. The molecular structures of the materials used for the OLED are shown in Table 1.

[0124] Table 1 Materials for OLED

[0125]

[0126]

[0127] The specific device structure of Device Example 1 is: ITO(130) / HATCN(15) / HTL(60) / EBL(40) / GH: Chemical 1(40, 2 wt%) / HBL(5) / ETL:Liq(30, 40% by weight) / Liq(1) / Al(100). It should be noted that the numbers in parentheses represent the film thickness (unit: nm).

[0128] The differences between Device Examples 2 to 15 and Device Example 1 are only that the compound Chemical 1 used in the emitting layer is replaced with other compounds of the present invention. For details, see Table 2.

[0129] Comparative Example:

[0130] This comparative example is different from Device Example 1 in that Compound 1 in the organic electroluminescent device is changed to R-1 and R-2 well-known in the industry. The performance test data of the obtained device are shown in Table 2. The OLED is characterized by standard methods. For this purpose, the electroluminescent spectrum, current efficiency (measured in cd / A), power efficiency (measured in lm / W), and external quantum efficiency (EQE, measured in %) are determined, which are calculated as a function of the emission density from the current / voltage / emission density characteristic curve (IUL characteristic curve) showing Lambert emission characteristics. EQE1000 represents the external quantum efficiency at a working brightness of 1000 cd / m 2 and T95 represents the operating time when the device brightness decreases to 95% at the initial brightness of the device at 1000 cd / m 2 . The Peak and FWHM values represent the emission peak and the full width at half maximum of the spectrum of the device at 1000 cd / m 2 . The device performances of Examples 1 to 20 of the present invention and Comparative Example 1 are summarized in Table 2.

[0131]

[0132]

[0133] Compared with Device Comparative Example 1, the compound of the present invention shows narrow-band green light emission in the single-host system device (Examples 1-20), and the device lifetime becomes longer. The main reason is that an electron-withdrawing group is introduced at the peripheral position of carbazole in the green light boron-nitrogen aromatic fused ring structure, without changing the molecular emission spectrum, and the spectrum is still a dark green narrow spectrum. At the same time, the energy level of the molecule is deepened, the trap capture of holes is inhibited, and the possibility of side reactions of the luminescent molecules is reduced, thereby improving the device stability.

Claims

1. A fused heterocyclic compound, characterized in that: The compound is composed of the general formula (1) to (4): R1~R5、R 11 ~R 14 Each is independently selected from a hydrogen atom, a deuterium atom, a chlorine atom, a bromine atom, a fluorine atom, a cyano group, a substituted silyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, and a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms; X1-X4 are independently selected from the following groups: The R 21 -R 26 It is hydrogen, deuterium, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 ring carbon atoms, a deuterated alkyl group having 1 to 20 carbon atoms, a deuterated cycloalkyl group having 3 to 20 ring carbon atoms, or a substituted or unsubstituted phenyl group.

2. The fused heterocyclic compound according to claim 1, characterized in that: R1~R5, R 11 ~R 14 , R 21 -R 26 The substituent groups are independently selected from the group consisting of a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, a substituted silicon group, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted n-propyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted n-butyl group, a substituted or unsubstituted isobutyl group, a substituted or unsubstituted sec-butyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted 2-methylbutyl group, a substituted or unsubstituted n-pentyl group, a substituted or unsubstituted sec-pentyl group, a substituted or unsubstituted cyclopropyl group, a substituted or unsubstituted cyclobutyl group, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted adamantyl group, a substituted or unsubstituted substituted or unsubstituted indolyl, substituted or unsubstituted furanyl, substituted or unsubstituted phenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted fluorenyl, substituted or unsubstituted spirobifluorenyl, substituted or unsubstituted indenofluorenyl, substituted or unsubstituted fluoranthenyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted peryl, substituted or unsubstituted naphthacene, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzoselenophene, and substituted or unsubstituted carbazolyl.

3. The fused heterocyclic compound according to claim 1 or 2, characterized in that: The "substituted" in the "substituted or unsubstituted" in the fused heterocyclic compound means that the substituent is independently selected from a deuterium atom, a tritium atom, a halogen atom, a cyano group, a hydroxyl group, a monovalent alkyl group or a cycloalkyl group having 1 to 10 carbon atoms, a monovalent monocyclic aromatic group or a condensed aromatic group having 6 to 30 carbon atoms, and a monovalent heterocyclic group or a condensed heteroaryl group having 2 to 50 carbon atoms.

4. The fused heterocyclic compound according to any one of claims 1 to 3, characterized in that: The fused heterocyclic compound is selected from the following structures:

5. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises an anode, a cathode and at least one organic thin film between the anode and the cathode, wherein the organic thin film contains the compound according to any one of claims 1 to 4.

6. The organic electroluminescent device according to claim 5, characterized in that: The organic film comprises any one or a combination of at least two of a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, an exciton blocking layer, a hole blocking layer, an electron transport layer, and an electron injection layer, and at least one of the light-emitting layers contains the compound described in any one of claims 1 to 4.

7. The organic electroluminescent device according to claim 5 or 6, characterized in that: The compound is used as a light-emitting material in a light-emitting layer in an organic electroluminescent device.

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