Boron nitrogen compound, application and organic electroluminescent device containing the same

Abstract

The present invention discloses a boron nitrogen compound, an application and an organic electroluminescent device containing the same. The boron nitrogen compound has a structure as shown in formula (I) or formula (II). The boron nitrogen compound of the present invention is applied to an organic photoelectric device, especially an organic electroluminescent device (organic electroluminescent diode), to improve the current efficiency, reduce the operating voltage of components, and obtain an organic electroluminescent diode with a long life.

Description

Technical Field

[0001] The invention belongs to the technical field of organic light-emitting auxiliary materials, and in particular relates to a boron nitrogen compound, an application and an organic electroluminescent device containing the same. Background Art

[0002] As a new type of display technology, organic light-emitting diodes (OLEDs) have the unique advantages of self-luminescence, wide viewing angle, low energy consumption, high efficiency, thinness, rich colors, fast response speed, wide applicable temperature range, low driving voltage, flexible, bendable and transparent display panels, and environmental friendliness. They can be used in flat-panel displays and new generation lighting, and can also be used as LCD backlight sources.

[0003] Since the 1980s, organic electroluminescent devices have been used in industry. OLED light emission is divided into two modes: fluorescence and phosphorescence. According to theoretical speculation, the ratio of singlet excited state to triplet excited state formed by charge recombination is 1:3. Small molecule fluorescent materials can utilize 25% of the energy, and the remaining 75% of the energy is lost due to the non-luminescent mechanism of triplet excited state. Therefore, it is generally believed that the internal quantum efficiency limit of fluorescent materials is 25%. In 2016, Takuji Hatakeyama's team proposed a multi-resonance induced thermally activated delayed fluorescence (MR-TADF) material design strategy, which uses the multi-resonance effect based on boron and nitrogen atoms to cause the distribution of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) on different atoms to achieve a smaller S1 and triplet excited state (T1) energy level difference. At the same time, its rigid structure limits the vibration and rotation of the molecule, inhibits the distortion or deformation of the excited state structure, reduces the path of non-radiative relaxation, and is conducive to improving color purity and luminous efficiency. Therefore, MR-TADF materials exhibit high OLED device efficiency (maximum external quantum efficiency > 20%) and high color purity (full width at half maximum (FWHM) < 30 nm).

[0004] At present, almost all light-emitting layers in organic OLED components use a host-guest light-emitting system, that is, guest light-emitting materials are doped in the host material. Generally speaking, the energy system of the organic host material is larger than that of the guest material, that is, energy is transferred from the host to the guest, so that the guest material is excited and emits light. At present, MR-TADF has begun to be applied to commercial OLED materials, but there are still some technical difficulties, such as OLED requires high efficiency, long life, and lower operating voltage. Because the skeleton of MR-TADF molecules is a planar structure, it is easy for molecules to stack under solid conditions, and the strong interaction between luminescent molecules is easy to cause aggregation-induced fluorescence quenching, thereby reducing the luminescence efficiency of MR-TADF OLED devices. Therefore, how to solve the defects faced by the above materials through reasonable chemical structure design and provide an organic electroluminescent device with good efficiency, high life and reduced driving voltage. It has become one of the problems that many forward-looking researchers in the field need to solve. Summary of the invention

[0005] In view of this, the object of the present invention is to provide a boron nitrogen compound, application and organic electroluminescent device containing the same. The present invention provides a boron nitrogen compound containing a thiophene ring. When the boron nitrogen compound is used in an organic electroluminescent device, it has better efficiency, longer life and reduced driving voltage.

[0006] In order to achieve the purpose of the present invention, the technical solution of the present invention is as follows:

[0007] The present invention provides a boron nitrogen compound, wherein the boron nitrogen compound has a structure as shown in formula (I) or formula (II):

[0008]

[0009] Wherein, X1 and X2 are each independently selected from O, N, S or Se; wherein * indicates the position to be fused.

[0010] R1, R2, R3, R4, R5, R6 and R7 are each independently selected from hydrogen, deuterium, halogen, C1-C18 alkyl, C1-C18 alkoxy, C1-C18 alkylsilyl, C1-C18 alkoxysilyl, C6-C40 substituted or unsubstituted aryl, C1-C40 heteroaryl, C1-C60 substituted or unsubstituted heterospiro, C1-C60 substituted or unsubstituted spiro, substituted or unsubstituted The invention further comprises a substituted or unsubstituted aryl ether group, a substituted or unsubstituted heteroaryl ether group, a substituted or unsubstituted arylamine group, a substituted or unsubstituted heteroarylamine group, a substituted or unsubstituted arylsilyl group, a substituted or unsubstituted heteroarylsilyl group, a substituted or unsubstituted aryloxysilyl group, a substituted or unsubstituted arylacyl group, a substituted or unsubstituted heteroarylacyl group or a substituted or unsubstituted phosphinyl group; the groups not substituted by deuteration in the above structures may be partially or fully substituted by deuteration.

[0011] In the present invention, preferably, R1, R2, R3, R4, R5, R6 and R7 are each independently selected from C1 to C10 alkyl groups.

[0012] In the present invention, preferably, R1, R2, R3, R4, R5, R6 and R7 are each independently selected from H, methyl, isopropyl or tert-butyl.

[0013] In the present invention, more preferably, the boron nitrogen compound is selected from the group consisting of:

[0014]

[0015]

[0016]

[0017]

[0018]

[0019]

[0020]

[0021]

[0022]

[0023]

[0024]

[0025]

[0026]

[0027]

[0028]

[0029]

[0030]

[0031]

[0032]

[0033]

[0034]

[0035]

[0036]

[0037]

[0038]

[0039]

[0040]

[0041] The present invention also provides a use of the boron nitrogen compound described in the above technical solution in the preparation of an organic electroluminescent device.

[0042] Furthermore, the present invention also provides an organic electroluminescent device, which comprises a cathode layer, an anode layer and an organic functional layer, wherein the organic functional layer is a hole injection layer, a hole transport layer, a light-emitting layer, a hole blocking layer, an electron injection layer and an electron transport layer, wherein the organic functional layer comprises the above-mentioned boron nitrogen compound, wherein the structure of the boron nitrogen compound is as shown in formula (I) or formula (II):

[0043]

[0044] Wherein, X1 and X2 are each independently selected from O, N, S or Se; * indicates the position to be fused. R1, R2, R3, R4, R5, R6 and R7 are each independently selected from hydrogen, deuterium, halogen, C1-C18 alkyl, C1-C18 alkoxy, C1-C18 alkylsilyl, C1-C18 alkoxysilyl, C6-C40 substituted or unsubstituted aryl, C1-C40 heteroaryl, C1-C60 substituted or unsubstituted heterospiro, C1-C60 substituted or unsubstituted spiro, substituted or unsubstituted The above structures may be substituted with deuterium or a completely deuterated group, wherein the deuterated groups may be partially or completely deuterated.

[0045] Preferably, R1, R2, R3, R4, R5, R6 and R7 are each independently selected from C1 to C10 alkyl groups.

[0046] Preferably, R1, R2, R3, R4, R5, R6 and R7 are each independently selected from H, methyl, isopropyl or tert-butyl.

[0047] Preferably, the organic functional layer is a light-emitting layer, and the light-emitting layer further comprises a host compound, wherein the volume ratio of the boron nitrogen compound to the host compound is 1:1 to 1:99.

[0048] The present invention also provides a display device, which comprises the organic electroluminescent diode.

[0049] The invention also provides an application of the boron nitrogen compound in the preparation of an organic electroluminescent diode.

[0050] The present invention also provides a preparation, which comprises the boron nitrogen compound as described above and at least one solvent, the solvent is not particularly limited, and unsaturated hydrocarbon solvents known to those skilled in the art (such as toluene, xylene, mesitylene, tetralin, decahydronaphthalene, bicyclohexane, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, etc.), saturated hydrocarbon solvents (such as carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, hexyl chloride, bromohexane, chlorocyclohexane, bromocyclohexane, etc.), unsaturated hydrocarbon solvents (such as chlorobenzene, dichlorobenzene, trichlorobenzene, etc.), ether solvents (such as tetrahydrofuran, tetrahydropyran, etc.) and ester solvents (alkyl benzoate, etc.) can be used. The preparation is directly used to prepare organic electroluminescent diodes.

[0051] The present invention also provides an organic photoelectric device, comprising:

[0052] a first electrode;

[0053] a second electrode, facing the first electrode;

[0054] An organic functional layer, sandwiched between the first electrode and the second electrode;

[0055] Wherein, the organic functional layer comprises the boron nitrogen compound as described above.

[0056] The present invention also provides an organic photoelectric device, which includes a cathode layer, an anode layer and an organic functional layer, wherein the organic functional layer is at least one of a hole injection layer, a hole transport layer, a light-emitting layer (active layer), a hole blocking layer, an electron injection layer and an electron transport layer, wherein the organic functional layer contains the boron nitrogen compound.

[0057] Preferably, the organic functional layer is a light-emitting layer, and the light-emitting layer further comprises a host compound, wherein the volume ratio of the boron nitrogen compound to the host compound is 1:1-99;

[0058] The main compound is a compound known in the art.

[0059] The present invention also provides a display or lighting device, which comprises the organic electroluminescent diode.

[0060] The organic photoelectric element of the present invention is an organic photovoltaic device, an organic electroluminescent device (OLED), an organic solar cell (OSC), electronic paper (e-paper), an organic photoreceptor (OPC), an organic thin film transistor (OTFT) or an organic memory element.

[0061] The organic photoelectric element of the present invention is prepared as follows: first, a metal or conductive oxide and their alloys are evaporated on a substrate by a method such as sputtering coating, electron beam evaporation, vacuum evaporation, etc. to form an anode; secondly, a hole injection layer, a hole transport layer, a light-emitting layer, a hole blocking layer and an electron transport layer are evaporated in sequence on the surface of the prepared anode, and finally, a cathode is evaporated. In addition to the above method, an organic photoelectric element can also be prepared by evaporating a cathode, an organic functional layer and an anode in sequence on a substrate, and the organic functional layer is at least one of a hole injection layer, a hole transport layer, a light-emitting layer, a hole blocking layer and an electron transport layer. The organic functional layer in the present invention can also be prepared by using polymer materials according to solvent engineering (spin-coating, tape-casting, doctor-blading, screen-printing, inkjet printing or thermal-imaging, etc.) instead of the evaporation method, which can reduce the number of device layers.

[0062] The organic photoelectric element of the present invention can be classified as top emission, bottom emission or double-sided emission according to the materials used. The boron nitrogen compound of the present invention can be applied to electroluminescent devices such as organic solar cells, illuminated OLEDs, flexible OLEDs, organic photoreceptors or organic thin film transistors based on the principle similar to that of organic light-emitting devices.

[0063] The boron nitrogen compound of the present invention is applied to organic photoelectric devices, especially organic electroluminescent devices (organic electroluminescent diodes), to improve current efficiency, reduce the operating voltage of components, and obtain organic electroluminescent diodes with a long life. BRIEF DESCRIPTION OF THE DRAWINGS

[0064] Figure 1 It is a schematic structural diagram of the organic electroluminescent diode of the present invention. DETAILED DESCRIPTION

[0065] In order to make the purpose, technical solution and advantages of the present invention more clear, the present invention is further described in detail below in conjunction with specific embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention, rather than to limit the claims of the present invention.

[0066] The OLED device of the present invention contains a hole transport layer, and the hole transport material can be preferably selected from known materials, and is particularly preferably selected from the following structures, but it does not mean that the present invention is limited to the following structures:

[0067]

[0068] The hole transport layer contained in the OLED device of the present invention comprises one or more p-type dopants. The preferred p-type dopant of the present invention is the following structure, but it does not mean that the present invention is limited to the following structure:

[0069]

[0070] The electron transport layer contained in the OLED device of the present invention may be selected from at least one of the following compounds, but this does not mean that the present invention is limited to the following structures:

[0071]

[0072] Example 1: Preparation of Intermediate A

[0073] The synthetic route of intermediate A is as follows:

[0074]

[0075] (1) Synthesis of intermediate A-S1: 2-bromo-5-isopropylbenzoic acid methyl ester (100.00 g, 388.92 mmol, 1.20 equivalent), 4-bromo-3-thiopheneboronic acid (67.04 g, 324.10 mmol, 1 equivalent), DMF were added in sequence into a single-mouth bottle with a magnetic rotor. 800mL, 100mL of water, stirred at room temperature, potassium carbonate (44.72g, 324.10mmoL, 1 equivalent), nitrogen replacement three times, tetrakistriphenylphosphine palladium (7.48g, 6.48mmoL, 0.02 equivalent), heated to 100℃ for reaction, reacted for 12h, after the reaction, stopped heating, added dichloromethane for extraction, the aqueous layer was extracted three times with dichloromethane, the organic phases were combined, the organic phases were washed once with brine, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure. The obtained crude product was dissolved in dichloromethane and mixed with silica gel, dry loaded, separated and purified by column chromatography, the eluent was petroleum ether: dichloromethane = 20:1-10:1, and the product A-S1 83g was obtained with a yield of 75.49%, mass spectrum m / z, theoretical value 339.25; measured value M+H: 340.25.

[0076] (2) Synthesis of intermediate A-S2: A-S1 (83 g, 244.66 mmol, 1.0 equivalent) and 400 mL of THF were added to a three-necked flask equipped with a magnetic rotor, cooled to 0-5°C, and 2 M methylmagnesium bromide was added dropwise. THF solution (366.99 mL, 733.98 mmol, 3.0 equivalents) was maintained at this temperature for 3 hours, then naturally warmed to room temperature, reacted overnight, quenched with dilute hydrochloric acid aqueous solution, adjusted to weak acidity, extracted with ethyl acetate, the aqueous layer was extracted three times with ethyl acetate, the organic phases were combined, the organic phases were washed once with brine, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure. The obtained crude product was dissolved in dichloromethane and mixed with silica gel, dry-loaded, separated and purified by column chromatography, the eluent was petroleum ether: dichloromethane = 15:1-5:1, and the product A-S265g was obtained with a yield of 78.30%, mass spectrum m / z, theoretical value 339.29; measured value M+H: 340.29.

[0077] (3) Synthesis of intermediate A-S3: A-S2 (65 g, 191.58 mmol, 1.0 equivalent), acetic acid 500 mL, and trifluoromethanesulfonic acid (2.87 g, 19.16 mmol, 0.1 equivalent) were added to a single-mouth bottle with a magnetic rotor in sequence, and the temperature was raised to 80 degrees Celsius for 8 hours. After the reaction was completed, most of the acetic acid was concentrated under reduced pressure, and dichloromethane was added for extraction. The aqueous layer was extracted three times with dichloromethane, and the organic phases were combined, washed once with brine, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure. The crude product was dissolved in dichloromethane, mixed with silica gel, and dry-loaded. The product was separated and purified by column chromatography with the eluent being petroleum ether: dichloromethane = 20:1-5:1 to obtain 50.00 g of product A-S3 with a yield of 81.24%. Mass spectrum m / z, theoretical value 321.28; measured value M+H: 322.28.

[0078] (4) Synthesis of intermediate A-S4: A-S3 (50 g, 155.63 mmoL, 1.0 equivalent), 4-tert-butylaniline (30.2 g, 202.32 mmoL, 1.3 equivalent), toluene 500 mL, sodium tert-butoxide (22.43 g, 233.44 mmoL, 1.5 equivalent), Pd2(dba)3 (2.85 g, 3.11 mmoL, 0.0 2 equivalents), tri-tert-butylphosphine 10% toluene solution (31.4g, 15.55mmoL, 0.1 equivalents), nitrogen replacement three times, heating to 108 degrees Celsius, reacting for 2h, after the reaction, cooling to below 80 degrees Celsius, adding 200mL of water and stirring for 0.5h, standing for stratification, discarding the aqueous phase, washing the organic phase with brine once, drying over anhydrous sodium sulfate, filtering, and distilling under reduced pressure to remove the solvent, the obtained crude product was refluxed and slurried three times with 4 times the volume of n-heptane to obtain product A-S4 40.00g, yield 65.97%. Mass spectrum m / z, theoretical value 389.60; measured value M+H: 390.60.

[0079] Example 2: Preparation of Intermediate B

[0080] The synthetic route of intermediate B is as follows:

[0081]

[0082] (1) Synthesis of intermediate B-S1: 2-bromo-4,5-dichlorophenol (100.00 g, 413.4 mmol, 1.20 equivalent), 2-fluoro-4-tert-butylphenylboronic acid (67.53 g, 344.50 mmol, 1 equivalent), DMF 800 mL, water 100 mL were added in sequence to a single-mouth bottle with a magnetic rotor, and stirred at room temperature. Potassium carbonate (47.61 g, 344.5 mmol, 1 equivalent) was added. Nitrogen was replaced three times, and tetrakistriphenylphosphine palladium was added. (10g, 8.65mmoL, 0.025 equivalent), heated to 100℃ for reaction, reacted for 12h, after the reaction, stopped heating, added dichloromethane for extraction, the aqueous layer was extracted with dichloromethane three times, the organic phases were combined, the organic phases were washed once with brine, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure. The obtained crude product was dissolved in dichloromethane and mixed with silica gel, dry loaded, separated and purified by column chromatography, the eluent was petroleum ether: dichloromethane = 20:1-5:1, and the product B-S1 81g was obtained with a yield of 75.07%, mass spectrum m / z, theoretical value 313.19; measured value M+H: 314.19.

[0083] (2) Synthesis of intermediate B-S2: B-S1 (81 g, 258.63 mmol, 1.0 equivalent) was added to a single-mouth bottle with a magnetic rotor, followed by potassium carbonate (178.72 g, 1290 mmol, 5 equivalent) in 500 mL of DMF under stirring, and the temperature was raised to 100°C for reaction for 12 h. After the reaction was completed, heating was stopped and dichloromethane was added for extraction. The aqueous layer was extracted three times with dichloromethane, and the organic phases were combined, washed once with brine, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure. The crude product was dissolved in dichloromethane and mixed with silica gel. The product was dry-loaded and purified by column chromatography. The eluent was petroleum ether: dichloromethane = 20:1-5:1. 66 g of product B-S2 was obtained with a yield of 87.04%. Mass spectrum m / z, theoretical value 293.19; measured value M+H: 294.19.

[0084] (3) Synthesis of intermediate B-S3: B-S2 (66 g, 225.11 mmol, 1.0 equivalent) and THF 330 mL were added to a three-necked flask with a magnetic rotor in sequence, the temperature was lowered to -20°C to -30°C, a 2M THF solution of lithium diisopropylamide (135 mL, 270.13 mmol, 1.2 equivalent) was added dropwise, and the temperature was maintained for 3 hours. Then, 1,2-dibromoethane (54.98 g, 292.65 mmol, 1.3 equivalent) was added and the temperature was maintained for 3 hours. The temperature was naturally raised to room temperature, and the reaction was allowed to proceed overnight. The mixture was quenched with a dilute aqueous hydrochloric acid solution (5%), adjusted to weak acidity, and extracted with ethyl acetate. The aqueous layer was extracted three times with ethyl acetate, the organic phases were combined, the organic phases were washed once with brine, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure. The crude product was refluxed and slurried three times with n-heptane 5 times the mass to obtain the product B-S3. 65.40g, yield 78.08%, mass spectrum m / z, theoretical value 372.08; measured value M+H: 373.08.

[0085] Example 3: Preparation of Intermediate C

[0086] The synthetic route of intermediate C is as follows:

[0087]

[0088] (1) Synthesis of intermediate C-S1: 2-bromo-4,5-dichlorophenol (100.00 g, 413.4 mmol, 1.20 equivalent), 2-fluorophenylboric acid (48.2 g, 344.50 mmol, 1 equivalent), DMF were added in sequence into a single-mouth bottle with a magnetic rotor. 800mL, 100mL of water, stirred at room temperature, potassium carbonate (47.61g, 344.5mmoL, 1 equivalent), nitrogen replacement three times, tetrakistriphenylphosphine palladium (10g, 8.65mmoL, 0.025 equivalent), heated to 100℃ for reaction, reacted for 12h, after the reaction, stopped heating, added dichloromethane for extraction, the aqueous layer was extracted three times with dichloromethane, the organic phases were combined, the organic phases were washed once with brine, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure. The obtained crude product was dissolved in dichloromethane and mixed with silica gel, dry loaded, separated and purified by column chromatography, the eluent was petroleum ether: dichloromethane = 20:1-5:1, and the product C-S1 73.20g was obtained, the yield was 82.65%, mass spectrum m / z, theoretical value 257.09; measured value M+H: 258.09.

[0089] (2) Synthesis of intermediate C-S2: C-S1 (73.20 g, 284.73 mmol, 1.0 equivalent) was added to a single-mouth bottle with a magnetic rotor, followed by potassium carbonate (196.75 g, 1420 mmol, 5 equivalent) in 500 mL of DMF under stirring, and the temperature was raised to 100°C for reaction for 12 h. After the reaction was completed, heating was stopped and dichloromethane was added for extraction. The aqueous layer was extracted three times with dichloromethane, and the organic phases were combined, washed once with brine, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure. The crude product was dissolved in dichloromethane and mixed with silica gel. The product was dry-loaded and purified by column chromatography. The eluent was petroleum ether: dichloromethane = 20:1-5:1. 62 g of product B-S2 was obtained with a yield of 91.85%. Mass spectrum m / z, theoretical value 237.08; measured value M+H: 238.08.

[0090] (3) Synthesis of intermediate C-S3: C-S2 (62 g, 261.51 mmol, 1.0 equivalent) and THF 310 mL were added to a three-necked flask with a magnetic rotor in sequence, the temperature was cooled to -20°C to -30°C, a 2M THF solution of lithium diisopropylamide (157 mL, 313.82 mmol, 1.2 equivalent) was added dropwise, and the temperature was maintained for 3 hours. Then, 1,2-dibromoethane (63.87 g, 339.97 mmol, 1.3 equivalent) was added and the temperature was maintained for 3 hours. The temperature was naturally raised to room temperature, and the reaction was allowed to proceed overnight. The mixture was quenched with a dilute aqueous hydrochloric acid solution (5%), adjusted to weak acidity, extracted with ethyl acetate, and the aqueous layer was extracted three times with ethyl acetate. The organic phases were combined, washed once with brine, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure. The crude product was dissolved with 2 times the mass of dichloromethane, and 3 times the mass of n-heptane was added and refluxed for three times to obtain the product C-S3. 68.9 g, yield 83.38%, mass spectrum m / z, theoretical value 315.98; measured value M+H: 316.98.

[0091] Example 4: Preparation of Intermediate D

[0092] The synthetic route of intermediate D is as follows:

[0093]

[0094] (1) Synthesis of intermediate D-S1: Methyl 2-bromobenzoate (100.00 g, 465.02 mmol, 1.20 equivalent), 4-bromo-3-thiopheneboronic acid (80.16 g, 387.52 mmol, 1 equivalent), 800 mL of DMF, 100 mL of water were added in sequence to a single-mouth bottle equipped with a magnetic rotor, and stirred at room temperature. Potassium carbonate (53.56 g, 387.52 mmol, 1 equivalent) was added. The atmosphere was replaced with nitrogen three times. Tetrakistriphenylphosphine palladium (1 0.7g, 9.3mmoL, 0.02 equivalent), heated to 100℃ for reaction, reacted for 12h, after the reaction, stopped heating, added dichloromethane for extraction, the aqueous layer was extracted with dichloromethane three times, the organic phases were combined, the organic phases were washed once with brine, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure. The obtained crude product was dissolved in dichloromethane and mixed with silica gel, dry loaded, separated and purified by column chromatography, the eluent was petroleum ether: dichloromethane = 10:1-5:1, and the product D-S1 86.2g was obtained, the yield was 74.85%, mass spectrum m / z, theoretical value 297.17; measured value M+H: 298.17.

[0095] (2) Synthesis of intermediate D-S2: D-S1 (86.2 g, 290.07 mmol, 1.0 equivalent) and 400 mL of THF were added to a three-necked flask equipped with a magnetic rotor, cooled to 0-5°C, and 2 M methylmagnesium bromide was added dropwise. THF solution (435.1mL, 870.21mmoL, 3.0 equivalents) was maintained at this temperature for 3 hours, then naturally warmed to room temperature, reacted overnight, quenched with dilute hydrochloric acid aqueous solution, adjusted to weak acidity, extracted with ethyl acetate, the aqueous layer was extracted three times with ethyl acetate, the organic phases were combined, the organic phases were washed once with brine, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure. The obtained crude product was dissolved in dichloromethane and mixed with silica gel, dry-loaded, separated and purified by column chromatography, the eluent was petroleum ether: dichloromethane = 10:1-5:1, and the product D-S266.3g was obtained with a yield of 76.9%, mass spectrum m / z, theoretical value 297.21; measured value M+H: 298.21.

[0096] (3) Synthesis of intermediate D-S3: D-S2 (66.3 g, 223.07 mmol, 1.0 equivalent), acetic acid 500 mL, and trifluoromethanesulfonic acid (3.35 g, 22.31 mmol, 0.1 equivalent) were added to a single-mouth bottle with a magnetic rotor in sequence, and the temperature was raised to 80 degrees Celsius for 8 hours. After the reaction was completed, most of the acetic acid was concentrated under reduced pressure, and dichloromethane was added for extraction. The aqueous layer was extracted three times with dichloromethane, and the organic phases were combined, washed once with brine, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure. The crude product was dissolved in dichloromethane and mixed with silica gel. The sample was dry loaded and separated and purified by column chromatography. The eluent was petroleum ether: dichloromethane = 15:1-5:1, and 52.7 g of product D-S3 was obtained with a yield of 84.62%. Mass spectrum m / z, theoretical value 279.20; measured value M+H: 280.20.

[0097] (4) Synthesis of intermediate D-S4: D-S3 (52.7 g, 188.76 mmol, 1.0 equivalent), 4-tert-butylaniline (36.37 g, 245.38 mmol, 1.3 equivalent), toluene 500 mL, sodium tert-butoxide (27.21 g, 283.13 mmol, 1.5 equivalent), Pd2(dba)3 (3.45 g, 3.77 mmol, 0. 02 equivalent), tri-tert-butylphosphine 10% toluene solution (38.13g, 18.87mmoL, 0.1 equivalent), nitrogen replacement three times, heating to 108 degrees Celsius, reaction for 2h, after the reaction, cooling to below 80 degrees Celsius, adding 200mL of water and stirring for 0.5h, standing for stratification, discarding the aqueous phase, washing the organic phase with brine once, drying over anhydrous sodium sulfate, filtering, and distilling under reduced pressure to remove the solvent, the obtained crude product was refluxed and slurried three times with 3 times the mass of n-heptane to obtain product D-S4 46.00g, yield 70.13%. Mass spectrum m / z, theoretical value 347.52; measured value M+H: 348.52.

[0098] Example 5: Preparation of Intermediate E

[0099] The synthetic route of intermediate E is as follows:

[0100]

[0101] (1) Synthesis of intermediate E-S1: 2-bromo-5-tert-butylbenzoic acid methyl ester (100.00 g, 368.80 mmol, 1.20 equivalent), 4-bromo-3-thiopheneboronic acid (63.57 g, 307.33 mmol, 1 equivalent), DMF were added to a single-mouth bottle with a magnetic rotor. 800mL, 100mL of water, stirred at room temperature, potassium carbonate (42.48g, 307.33mmoL, 1 equivalent), nitrogen replacement three times, tetrakistriphenylphosphine palladium (7.09g, 6.14mmoL, 0.02 equivalent), heated to 100℃ for reaction, reacted for 12h, after the reaction, stopped heating, added dichloromethane for extraction, the aqueous layer was extracted three times with dichloromethane, the organic phases were combined, the organic phases were washed once with brine, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure. The crude product was dissolved in dichloromethane and mixed with silica gel, dry loaded, separated and purified by column chromatography, the eluent was petroleum ether: dichloromethane = 15:1-5:1, and the product E-S1 78.6g was obtained with a yield of 72.39%, mass spectrum m / z, theoretical value 353.27; measured value M+H: 354.27.

[0102] (2) Synthesis of intermediate E-S2: E-S1 (78.6 g, 222.49 mmol, 1.0 equivalent) and 400 mL of THF were added to a three-necked flask equipped with a magnetic rotor, cooled to 0-5°C, and 2 M methylmagnesium bromide was added dropwise. THF solution (333.73mL, 667.47mmoL, 3.0 equivalents) was maintained at this temperature for 3 hours, then naturally warmed to room temperature, reacted overnight, quenched with dilute hydrochloric acid aqueous solution, adjusted to weak acidity, extracted with ethyl acetate, the aqueous layer was extracted three times with ethyl acetate, the organic phases were combined, the organic phases were washed once with brine, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure. The crude product was dissolved in dichloromethane and mixed with silica gel, dry-loaded, separated and purified by column chromatography, the eluent was petroleum ether: ethyl acetate = 20:1-10:1, and the product E-S264.8g was obtained with a yield of 82.43%, mass spectrum m / z, theoretical value 353.32; measured value M+H: 353.32.

[0103] (3) Synthesis of intermediate E-S3: E-S2 (64.8 g, 183.40 mmol, 1.0 equivalent), acetic acid 500 mL, and trifluoromethanesulfonic acid (2.75 g, 18.34 mmol, 0.1 equivalent) were added to a single-mouth bottle with a magnetic rotor in sequence, and the temperature was raised to 80 degrees Celsius for 8 hours. After the reaction was completed, most of the acetic acid was concentrated under reduced pressure, and dichloromethane was added for extraction. The aqueous layer was extracted three times with dichloromethane, and the organic phases were combined, washed once with brine, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure. The crude product was dissolved in dichloromethane and mixed with silica gel. The sample was dry-loaded and purified by column chromatography. The eluent was petroleum ether: dichloromethane = 10:1-5:1, and 51.8 g of product E-S3 was obtained with a yield of 84.23%. Mass spectrum m / z, theoretical value 335.30; measured value M+H: 336.30.

[0104] (4) Synthesis of intermediate E-S4: E-S3 (51.8 g, 154.49 mmoL, 1.0 equivalent), 4-tert-butylaniline (29.97 g, 200.83 mmoL, 1.3 equivalent), toluene 500 mL, sodium tert-butoxide (22.27 g, 231.73 mmoL, 1.5 equivalent), Pd2(dba)3 (2.82 g, 3.09 mmoL, 0.02 equivalent), tri-tert-butylphosphine 10% in toluene were added in sequence into a single-mouth bottle equipped with a magnetic rotor. Liquid (31.2g, 15.44mmoL, 0.1 equivalent), nitrogen replacement three times, heating to 108 degrees Celsius, reaction for 2h, after the reaction, cooling to below 80 degrees Celsius, adding 200mL of water and stirring for 0.5h, standing for stratification, discarding the aqueous phase, washing the organic phase with brine once, drying over anhydrous sodium sulfate, filtering, and distilling under reduced pressure to remove the solvent, the obtained crude product was dissolved in dichloromethane and mixed with silica gel, dry loading, column chromatography separation and purification, eluent is petroleum ether: dichloromethane = 20:1-5:1, and the product E-S4 46.3g, yield 74.25%. Mass spectrum m / z, theoretical value 403.62; measured value M+H: 404.62.

[0105] Example 6: Preparation of Intermediate F

[0106] The synthetic route of intermediate F is as follows:

[0107]

[0108] (1) Synthesis of intermediate F-S1: 2-bromo-4,5-dichlorothiophenol (100.00 g, 413.4 mmol, 1.20 equivalent), 2-fluorophenylboric acid (54.24 g, 387.65 mmol, 1 equivalent), DMF 800 mL, water 100 mL, potassium carbonate (53.58 g, 387.65 mmol, 1 equivalent) were added to a single-mouth bottle with a magnetic rotor, stirred at room temperature, and the atmosphere was replaced with nitrogen three times. Tetrakistriphenylphosphine palladium (11 .19g, 9.69mmoL, 0.025 equivalent), heated to 100℃ for reaction, reacted for 12h, after the reaction, stopped heating, added dichloromethane for extraction, the aqueous layer was extracted with dichloromethane three times, the organic phases were combined, the organic phases were washed once with brine, dried over anhydrous sodium sulfate, filtered, and distilled under reduced pressure to remove the solvent, the obtained crude product was dissolved in dichloromethane and mixed with silica gel, dry loaded, separated and purified by column chromatography, the eluent was petroleum ether: dichloromethane = 10:1-3:1, and the product F-S1 79.85g was obtained, the yield was 75.41%, mass spectrum m / z, theoretical value 273.15; measured value M+H: 274.15.

[0109] (2) Synthesis of intermediate F-S2: F-S1 (79.85 g, 292.33 mmol, 1.0 equivalent) was added to a single-mouth bottle with a magnetic rotor, followed by potassium carbonate (202.01 g, 1460 mmol, 5 equivalent) under stirring with 500 mL of DMF, and the temperature was raised to 100°C for reaction for 12 h. After the reaction was completed, heating was stopped and dichloromethane was added for extraction. The aqueous layer was extracted three times with dichloromethane, and the organic phases were combined, washed once with brine, dried over anhydrous sodium sulfate, filtered, and distilled under reduced pressure to remove the solvent. The crude product was dissolved in dichloromethane and mixed with silica gel, and the sample was dry-loaded and separated and purified by column chromatography. The eluent was petroleum ether: dichloromethane = 15:1-5:1, and the product F-S2 was obtained. 63.9 g, yield 86.35%, mass spectrum m / z, theoretical value 253.15; measured value M+H: 254.15.

[0110] (3) Synthesis of intermediate F-S3: F-S2 (63.9 g, 252.42 mmol, 1.0 equivalent) and 320 mL of THF were added to a three-necked flask equipped with a magnetic rotor, cooled to -20°C to -30°C, and 2 M lithium diisopropylamide was added dropwise. THF solution (151.45mL, 302.9mmoL, 1.2 equivalents) was added and maintained at this temperature for 3 hours, and then 1,2-dibromoethane (61.65g, 328.15mmoL, 1.3 equivalents) was added and maintained at this temperature for 3 hours, and the temperature was naturally raised to room temperature. The reaction was allowed to proceed overnight, and the mixture was quenched with a dilute aqueous hydrochloric acid solution (5%), adjusted to weak acidity, extracted with ethyl acetate, and the aqueous layer was extracted three times with ethyl acetate. The organic phases were combined, washed once with brine, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure. The obtained crude product was dissolved in dichloromethane and mixed with silica gel, and the sample was loaded by dry method. The product was separated and purified by column chromatography, and the eluent was petroleum ether: ethyl acetate = 10:1-5:1 to obtain product F-S369.73g, with a yield of 83.19%, mass spectrum m / z, theoretical value 332.04; measured value M+H: 333.04.

[0111] Example 7: Preparation of Intermediate G

[0112] The synthetic route of intermediate G is as follows:

[0113]

[0114] (1) Synthesis of intermediate G-S1: 2-bromobenzaldehyde (100.00 g, 540.49 mmol, 1.20 equivalent), 4-bromo-3-thiopheneboronic acid (93.17 g, 450.41 mmol, 1 equivalent), DMF 800 mL, water 100 mL, potassium carbonate (62.25 g, 450.41 mmol, 1 equivalent) were added to a single-mouth bottle with a magnetic rotor, stirred at room temperature, and the atmosphere was replaced with nitrogen three times. Tetrakistriphenylphosphine palladium (1 0.4g, 9mmoL, 0.02 equivalent), heated to 100℃ for reaction, reacted for 12h, after the reaction, stopped heating, added dichloromethane for extraction, the aqueous layer was extracted with dichloromethane three times, the organic phases were combined, the organic phases were washed once with brine, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure. The obtained crude product was dissolved in dichloromethane and mixed with silica gel, dry loaded, separated and purified by column chromatography, the eluent was petroleum ether: dichloromethane = 10:1-5:1, and the product E-S1 86.6g was obtained, the yield was 71.97%, mass spectrum m / z, theoretical value 267.14; measured value M+H: 268.14.

[0115] (2) Synthesis of intermediate G-S2: G-S1 (86.6 g, 324.17 mmol, 1.0 equivalent) and 500 mL of THF were added to a three-necked flask equipped with a magnetic rotor, cooled to 0-5°C, and 2 M methylmagnesium bromide was added dropwise. THF solution (486.25mL, 972.51mmoL, 3.0 equivalents) was maintained at this temperature for 3 hours, then naturally heated to room temperature, reacted overnight, quenched with dilute hydrochloric acid aqueous solution, adjusted to weak acidity, extracted with ethyl acetate, the aqueous layer was extracted three times with ethyl acetate, the organic phases were combined, the organic phases were washed once with brine, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure. The obtained crude product was dissolved in dichloromethane and mixed with silica gel, dry-loaded, separated and purified by column chromatography, the eluent was petroleum ether: ethyl acetate = 20:1-10:1, and the product G-S278.3g was obtained with a yield of 77.61%, mass spectrum m / z, theoretical value 311.24; measured value M+H: 312.24.

[0116] (3) Synthesis of intermediate G-S3: G-S2 (78.3 g, 251.58 mmol, 1.0 equivalent), acetic acid 500 mL, and trifluoromethanesulfonic acid (3.78 g, 25.16 mmol, 0.1 equivalent) were added to a single-mouth bottle with a magnetic rotor in sequence, and the temperature was raised to 80 degrees Celsius for 8 hours. After the reaction was completed, most of the acetic acid was concentrated under reduced pressure, and dichloromethane was added for extraction. The aqueous layer was extracted three times with dichloromethane, and the organic phases were combined, washed once with brine, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure. The crude product was dissolved in dichloromethane, mixed with silica gel, and dry-loaded. The product was separated and purified by column chromatography with the eluent being petroleum ether: dichloromethane = 10:1-5:1 to obtain 60.5 g of product G-S3 with a yield of 82.01%. Mass spectrum m / z, theoretical value 293.22; measured value M+H: 294.22.

[0117] (4) Synthesis of intermediate G-S4: G-S3 (60.5 g, 206.33 mmol, 1.0 equiv), 4-tert-butylaniline (40.03 g, 268.23 mmol, 1.3 equiv), toluene 500 mL, sodium tert-butoxide (29.74 g, 309.49 mmol, 1.5 equiv), Pd2(dba)3 (3.77 g, 4.13 mmol, 0 .02 equivalent), tri-tert-butylphosphine 10% toluene solution (41.67g, 20.6mmoL, 0.1 equivalent), nitrogen replacement three times, heating to 108 degrees Celsius, reaction for 2h, after the reaction, cooling to below 80 degrees Celsius, adding 200mL of water and stirring for 0.5h, standing for stratification, discarding the aqueous phase, washing the organic phase with brine once, drying over anhydrous sodium sulfate, filtering, and distilling under reduced pressure to remove the solvent, the obtained crude product was refluxed with 4 times the mass of n-heptane to obtain product G-S4 59.86g, yield 80.25%. Mass spectrum m / z, theoretical value 361.54; measured value M+H: 362.54.

[0118] Example 8: Preparation of Intermediate H

[0119] The synthetic route of intermediate H is as follows:

[0120]

[0121] (1) Synthesis of intermediate H-S1: 2-bromophenol (50.00 g,

[0122] 289.01mmoL, 1 equivalent), 4-bromo-2-iodothiophene (100.20g, 346.81mmoL, 1.2 equivalent), cuprous iodide (11.01g,

[0123] 57.80mmoL, 20moL%), DMF 800mL stirred at room temperature, potassium carbonate (79.88g, 578.01mmoL, 2 equivalents), nitrogen replacement three times, heated to 100℃ for reaction, reaction for 18h, reaction completed. Stop heating, cool to room temperature, wash the reaction solution with water, add dichloromethane for extraction, extract the water layer with dichloromethane three times, combine the organic phases, wash the organic phases with brine once, dry with anhydrous sodium sulfate, filter, remove the solvent by vacuum distillation, dissolve the obtained crude product with dichloromethane, add silica gel and mix with the sample,

[0124] The product was loaded by dry method and separated and purified by column chromatography. The eluent was petroleum ether: dichloromethane = 10:1-5:1. 72 g of product H-S1 was obtained with a yield of 74.58%. The mass spectrum m / z was 334.03 in theoretical value and 335.03 in measured value M+H.

[0125] (2) Synthesis of intermediate H-S2: H-S1 (72 g,

[0126] 215.66mmoL, 1.0 equivalent), DMF 500mL, potassium carbonate (59.58g, 431.10mmoL, 2 equivalents), Pd2(dba)3

[0127] (3.95g, 4.31mmoL, 0.02 equivalent), tricyclohexylphosphine (6.04g, 21.56mmoL, 0.1 equivalent), nitrogen replacement three times, heating to 130 degrees Celsius, reaction for 5h, after the reaction, cooling to below 80 degrees Celsius, adding 500mL of water and stirring, adding dichloromethane for extraction, the water layer was extracted three times with dichloromethane, the organic phases were combined, the organic phases were washed once with brine, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by vacuum distillation, the obtained crude product was dissolved in dichloromethane, silica gel was added to the sample, dry sample was loaded, column chromatography was separated and purified, the eluent was petroleum ether: dichloromethane = 20:1-15:1, and the product H-S2 43.5g was obtained, the yield was 79.73%. Mass spectrum m / z, theoretical value 253.12; measured value M+H: 254.12.

[0128] (3) Synthesis of intermediate H-S3: H-S2 (43.5 g, 171.88 mmol, 1.0 equiv), 4-tert-butylaniline (33.34 g, 223.42 mmol, 1.3 equiv), 500 mL of toluene, sodium tert-butoxide (24.77 g, 257.79 mmol, 1.5 equiv), Pd2(dba)3 (3.14 g, 3.43 mmol, 0 .02 equivalent), tri-tert-butylphosphine 10% toluene solution (34.7g, 17.18mmoL, 0.1 equivalent), nitrogen replacement three times, heating to 108 degrees Celsius, reaction for 2h, after the reaction, cooling to below 80 degrees Celsius, adding 200mL of water and stirring for 0.5h, standing for stratification, discarding the aqueous phase, washing the organic phase with brine once, drying over anhydrous sodium sulfate, filtering, and distilling under reduced pressure to remove the solvent, the obtained crude product was refluxed with 4 times the mass of n-heptane to obtain 48.7g of product H-S3, with a yield of 88.16%. Mass spectrum m / z, theoretical value 321.44; measured value M+H: 322.44.

[0129] Example 9: Preparation of Intermediate I

[0130] The synthetic route of intermediate I is as follows:

[0131]

[0132] (1) Synthesis of intermediate I-S1: 2-bromothiophenol (65.00 g, 343 mmol, 1 equivalent), 4-bromo-2-iodothiophene (119.2 g, 412.54 mmol, 1.2 equivalent), cuprous iodide (13.09 g, 68.76 mmol, 20 mmol%), 800 mL of DMF were added in sequence at room temperature, and potassium carbonate (95.03 g, 687.57 mmol, 2 equivalent) was added to a single-mouth bottle with a magnetic rotor. The mixture was stirred at room temperature and the atmosphere was replaced with nitrogen three times. The temperature was raised to 100 °C for 18 h. The reaction was completed. The heating was stopped, and after cooling to room temperature, the reaction solution was washed with water, extracted with dichloromethane, the aqueous layer was extracted three times with dichloromethane, the organic phases were combined, the organic phases were washed once with brine, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure. The obtained crude product was dissolved in dichloromethane and mixed with silica gel, and the sample was loaded by dry method. The product was separated and purified by column chromatography, and the eluent was petroleum ether: dichloromethane = 10:1-5:1 to obtain 83.5 g of product I-S1 with a yield of 69.38%, mass spectrum m / z, theoretical value 350.09; measured value M+H: 351.9.

[0133] (2) Synthesis of intermediate I-S2: I-S1 (83.5 g, 238.51 mmol, 1.0 equivalent), DMF 500mL, potassium carbonate (65.93g, 477.02mmoL, 2 equivalents), Pd2(dba)3 (4.36g, 4.77mmoL, 0.02 equivalents), tricyclohexylphosphine (6.67g, 23.85mmoL, 0.1 equivalents), nitrogen replacement three times, heating to 130 degrees Celsius, reacting for 5h, after the reaction, cooling to below 80 degrees Celsius, adding 500mL of water and stirring, adding dichloromethane for extraction, the aqueous layer was extracted three times with dichloromethane, the organic phases were combined, the organic phases were washed once with brine, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure. The obtained crude product was dissolved in dichloromethane and mixed with silica gel, dry loaded, separated and purified by column chromatography, the eluent was petroleum ether: dichloromethane = 20:1-15:1, and the product I-S2 53.8g was obtained, and the yield was 83.8%. Mass spectrum m / z, theoretical value 269.18; measured value M+H: 254.12.

[0134] (3) Synthesis of intermediate I-S3: I-S2 (53.8 g, 199.87 mmol, 1.0 equivalent), 4-tert-butylaniline (38.77 g, 259.83 mmol, 1.3 equivalent), toluene 500 mL, sodium tert-butoxide (28.81 g, 299.8 mmol, 1.5 equivalent), Pd2(dba)3 (3.65 g, 3.99 mmol, 0. 02 equivalent), tri-tert-butylphosphine 10% toluene solution (40.37g, 19.98mmoL, 0.1 equivalent), nitrogen replacement three times, heating to 108 degrees Celsius, reaction for 2h, after the reaction, cooling to below 80 degrees Celsius, adding 200mL of water and stirring for 0.5h, standing for stratification, discarding the aqueous phase, washing the organic phase with brine once, drying over anhydrous sodium sulfate, filtering, and distilling under reduced pressure to remove the solvent, the obtained crude product was refluxed with 4 times the mass of n-heptane to obtain product I-S3 52.2g, yield 77.38%. Mass spectrum m / z, theoretical value 337.5; measured value M+H: 338.7.

[0135] Example 10: Preparation of Intermediate J

[0136] The synthetic route of intermediate J is as follows:

[0137]

[0138] (1) Synthesis of intermediate J-S1: 2-bromo-5-isopropylphenol (65.00 g, 302.2 mmoL, 1 equivalent), 4-bromo-2-iodothiophene (104.78 g, 362.64 mmoL, 1.2 equivalent), cuprous iodide (11.51 g, 60.44 mmoL, 20 mol%), 800 mL of DMF were added in sequence at room temperature, and potassium carbonate (83.53 g, 604.41 mmoL, 2 equivalents) was added to a single-mouth bottle equipped with a magnetic rotor. The mixture was stirred at room temperature and the atmosphere was replaced with nitrogen three times. The temperature was raised to 100 °C for 18 h. The reaction was completed. The heating was stopped, and after cooling to room temperature, the reaction solution was washed with water, extracted with dichloromethane, the aqueous layer was extracted three times with dichloromethane, the organic phases were combined, the organic phases were washed once with brine, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure. The obtained crude product was dissolved in dichloromethane and mixed with silica gel, and the sample was loaded by dry method. The product was separated and purified by column chromatography, and the eluent was petroleum ether: dichloromethane = 10:1-5:1 to obtain 88.6 g of product J-S1 with a yield of 77.95%. The mass spectrum m / z was 376.11 in theoretical value; the measured value M+H was 377.11.

[0139] (2) Synthesis of intermediate J-S2: J-S1 (88.6 g, 235.57 mmol, 1.0 equivalent), DMF 500mL, potassium carbonate (65.11g, 471.14mmoL, 2 equivalents), Pd2(dba)3 (4.31g, 4.71mmoL, 0.02 equivalents), tricyclohexylphosphine (6.59g, 23.55mmoL, 0.1 equivalents), nitrogen replacement three times, heating to 130 degrees Celsius, reacting for 5h, after the reaction, cooling to below 80 degrees Celsius, adding 500mL of water and stirring, adding dichloromethane for extraction, the aqueous layer was extracted three times with dichloromethane, the organic phases were combined, the organic phases were washed once with brine, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure. The obtained crude product was dissolved in dichloromethane and mixed with silica gel, dry loaded, separated and purified by column chromatography, the eluent was petroleum ether: dichloromethane = 20:1-15:1, and the product J-S2 58.7g was obtained with a yield of 84.41%. Mass spectrum m / z, theoretical value 295.19; measured value M+H: 296.19.

[0140] (3) Synthesis of intermediate J-S3: J-S2 (58.7 g, 198.85 mmoL, 1.0 equivalent), 4-tert-butylaniline (38.58 g, 258.51 mmoL, 1.3 equivalent), toluene 500 mL, sodium tert-butoxide (28.67 g, 298.28 mmoL, 1.5 equivalent), Pd2(dba)3 (3.62 g, 3.96 mmoL, 0 .02 equivalent), tri-tert-butylphosphine 10% toluene solution (39.99g, 19.8mmoL, 0.1 equivalent), nitrogen replacement three times, heating to 108 degrees Celsius, reacting for 2h, cooling to below 80 degrees Celsius, adding 200mL of water and stirring for 0.5h, standing for stratification, discarding the aqueous phase, washing the organic phase with brine once, drying over anhydrous sodium sulfate, filtering, and distilling under reduced pressure to remove the solvent, the obtained crude product was refluxed and slurried with 4 times the mass of n-heptane to obtain product J-S3 58.7g, yield 81.21%. Mass spectrum m / z, theoretical value 363.52; measured value M+H: 364.52.

[0141] Example 11: Preparation of Intermediate K

[0142] The synthetic route of intermediate K is as follows:

[0143]

[0144] (1) Synthesis of intermediate K-S1: To a single-necked bottle with a magnetic rotor, methyl 3-amino-2-bromobenzoate (100 g, 434.67 mmol, 1 equivalent) and 800 mL of PE were added in sequence, cooled to 0-5 °C and stirred, and NIS (92.9 g, 412.94 mmol, 0.95 equivalent) was added in 10 batches. After addition, the reaction was allowed to proceed for 2 h. The reaction solution was washed with water, and washed twice with sodium bisulfite aqueous solution (10%), and then washed once with brine, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure. The obtained crude product was dissolved in dichloromethane and mixed with silica gel, and the sample was loaded by dry method. The product was separated and purified by column chromatography with the eluent being petroleum ether: dichloromethane = 40:1-20:1 to obtain 126.20 g of product K-S1 with a yield of 81.56%. The mass spectrum m / z was 355.96 in theoretical value and 356.96 in measured value M+H.

[0145] (2) Synthesis of intermediate K-S2: K-S1 (126.20 g, 354.54 mmol, 1 equivalent) and PE 800 mL were added in sequence into a single-necked bottle with a magnetic rotor, cooled to 0-5 °C and stirred, and NCS (44.98 g, 336.81 mmol, 0.95 equivalent) was added in 5 batches. After addition, the reaction was allowed to proceed for 2 h. The reaction solution was washed with water, and washed twice with sodium bisulfite aqueous solution (10%), and then washed once with brine, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure. The crude product was dissolved in dichloromethane and mixed with silica gel. The sample was loaded by dry method and separated and purified by column chromatography. The eluent was petroleum ether: dichloromethane = 40:1-20:1 to obtain product K-S2108.7g with a yield of 78.53%. The mass spectrum m / z was theoretical value 390.40; the measured value M+H: 391.40.

[0146] (3) Synthesis of intermediate K-S3: K-S2 (108.7 g, 278.43 mmoL, 1 equivalent) and concentrated hydrochloric acid (92.5 mL, 1.11 mmoL, 4 equivalents) were added to a single-mouth bottle with a magnetic rotor in sequence. The temperature was cooled to 0 to -5 degrees Celsius in an ice-water bath. A 25% aqueous solution of sodium nitrite (76.84 g, 278.43 mmoL, 1 equivalent) was added dropwise. The mixture was stirred for half an hour. The mixture was then added dropwise to the stirring solution of cuprous chloride (5.51 g, 55.69 mmoL). L, 0.2 equivalent) + concentrated hydrochloric acid (92.5mL, 1.11mmoL, 4 equivalents) at 50 degrees Celsius, after the reaction, dichloromethane was added for extraction, the aqueous layer was extracted three times with dichloromethane, the organic phases were combined, the organic phases were washed once with brine, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure. The obtained crude product was dissolved in dichloromethane and mixed with silica gel, and the sample was loaded by dry method, separated and purified by column chromatography, the eluent was petroleum ether: dichloromethane = 15:1-5:1, and the product K-S4 93.7g was obtained, the yield was 82.11%, mass spectrum m / z, theoretical value 409.83; measured value M+H: 410.83.

[0147] (4) Synthesis of intermediate K-S4: K-S3 (93.70 g, 228.63 mmol, 1.20 equivalent), 4-isopropylphenylboronic acid (31.25 g, 190.53 mmol, 1 equivalent), DMF were added to a single-mouth bottle with a magnetic rotor. 800mL, 100mL of water, stirred at room temperature, potassium carbonate (26.33g, 190.53mmoL, 1 equivalent), nitrogen replacement three times, tetrakistriphenylphosphine palladium (4.4g, 3.81mmoL, 0.02 equivalent), heated to 100℃ for reaction, reacted for 12h, after the reaction, stopped heating, added dichloromethane for extraction, the aqueous layer was extracted three times with dichloromethane, the organic phases were combined, the organic phases were washed once with brine, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure. The crude product was dissolved in dichloromethane and mixed with silica gel, dry loaded, separated and purified by column chromatography, the eluent was petroleum ether: dichloromethane = 15:1-5:1, and the product K-S4 66.5g was obtained with a yield of 86.8%, mass spectrum m / z, theoretical value 402.11; measured value M+H: 403.11.

[0148] (5) Synthesis of intermediate K-S5: K-S4 (66.5 g, 165.38 mmol, 1.0 equivalent) and 400 mL of THF were added to a three-necked flask equipped with a magnetic rotor, cooled to 0-5°C, and 2 M methylmagnesium bromide was added dropwise. THF solution (248.1mL, 496.14mmoL, 3.0 equivalents) was maintained at this temperature for 3 hours, then naturally warmed to room temperature, reacted overnight, quenched with dilute hydrochloric acid aqueous solution, adjusted to weak acidity, extracted with ethyl acetate, the aqueous layer was extracted three times with ethyl acetate, the organic phases were combined, the organic phases were washed once with brine, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure. The obtained crude product was dissolved in dichloromethane and mixed with silica gel, dry-loaded, separated and purified by column chromatography, the eluent was petroleum ether: dichloromethane = 15:1-10:1, and the product K-S553.7g was obtained with a yield of 80.74%, mass spectrum m / z, theoretical value 402.15; measured value M+H: 403.15.

[0149] (6) Synthesis of intermediate K-S6: K-S5 (53.7 g, 133.53 mmol, 1.0 equivalent), acetic acid 500 mL, and trifluoromethanesulfonic acid (2 g, 13.351 mmol, 0.1 equivalent) were added to a single-mouth bottle with a magnetic rotor in sequence, and the temperature was raised to 80 °C. The reaction was carried out for 8 h. After the reaction was completed, most of the acetic acid was concentrated under reduced pressure and extracted with dichloromethane. The aqueous layer was extracted three times with dichloromethane. The organic phases were combined, washed once with brine, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by distillation under reduced pressure. The crude product was dissolved in dichloromethane, mixed with silica gel, and dry-loaded. The product was separated and purified by column chromatography with the eluent being petroleum ether: dichloromethane = 15:1-5:1. 42.8 g of product K-S6 was obtained with a yield of 83.44%. Mass spectrum m / z, theoretical value 384.14; measured value M+H: 385.14.

[0150] Example 12: Preparation of Intermediate L

[0151] The synthetic route of intermediate L is as follows:

[0152]

[0153] Synthesis of intermediate L-S1: 4-isopropylaniline (75 g, 554.71 mmoL, 1.3 equivalents), 4-isopropylbromobenzene (84.95 g, 426.7 mmoL, 1.0 equivalents), 500 mL of toluene, sodium tert-butoxide (61.51 g, 640.05 mmoL, 1.5 equivalents), Pd2(dba)3 (7.8 g, 8.53 mmoL, 0.02 equivalents) were added to a single-mouth bottle with a magnetic rotor. , 10% toluene solution of tri-tert-butylphosphine (86.19g, 42.67mmoL, 0.1 equivalent), nitrogen replacement three times, heating to 108 degrees Celsius, reaction for 2h, after the reaction, cooling to below 80 degrees Celsius, adding 200mL of water and stirring for 0.5h, standing for stratification, discarding the aqueous phase, washing the organic phase with dilute hydrochloric acid aqueous solution (5%) twice, drying over anhydrous sodium sulfate, filtering, and distilling under reduced pressure to remove the solvent to obtain the product L-S1105.2g, yield 97.3%. Mass spectrum m / z, theoretical value 253.38; measured value M+H: 254.38.

[0154] Example 13: Preparation of Intermediate M

[0155] The synthetic route of intermediate M is as follows:

[0156]

[0157] Synthesis of intermediate M-S1: Refer to the synthesis steps of L-S1 in Example 12, the yield of the final product is 97.52%. Mass spectrum m / z, theoretical value 281.44; measured value M+H: 282.44.

[0158] Example 14: Preparation of Compound 16

[0159] The synthetic route is as follows:

[0160]

[0161] (1) Synthesis of 16-S1: B-S3 (50 g, 134.38 mmoL, 1.0 equiv.), M-S1 (39.71 g, 141.10 mmoL, 1.05 equiv.), 500 mL of toluene, sodium tert-butoxide (19.37 g, 201.57 mmoL, 1.5 equiv.), Pd2(dba)3 (2.45 g, 2.68 mmoL, 0.02 Equivalent), S-Phos (5.52g, 13.44mmoL, 0.1 equivalent), nitrogen replacement three times, heating to 108 degrees Celsius, reacting for 2h, cooling to below 80 degrees Celsius, adding 200mL of water and stirring for 0.5h, standing for stratification, washing the organic phase with brine once, drying over anhydrous sodium sulfate, filtering, and removing the solvent by vacuum distillation. The obtained crude product was recrystallized twice with 2 times the mass of toluene and 1 times the mass of n-heptane to obtain 63.4g of product 16-S1 with a yield of 82.40%. Mass spectrum m / z, theoretical value 572.61; measured value M+H: 572.61.

[0162] (2) Synthesis of 16-S2: 16-S1 (63.4 g, 110.72 mmol, 1.0 eq.), A-S4 (47.45 g, 121.79 mmol, 1.1 eq.), 500 mL of xylene, sodium tert-butoxide (15.96 g, 166.08 mmol, 1.5 eq.), Pd2(dba)3 (2.02 g, 2.21 mmol, 1.0 eq.) were added to a single-mouth bottle equipped with a magnetic rotor. , 0.02 equivalent), S-Phos (4.54g, 11.07mmoL, 0.1 equivalent), nitrogen replacement three times, heating to 138 degrees Celsius, reaction for 2h, after the reaction, cooling to below 80 degrees Celsius, adding 200mL of water and stirring for 0.5h, standing for stratification, the organic phase was washed once with brine, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by vacuum distillation. The crude product was recrystallized twice with 2 times the mass of toluene to obtain 86.03g of product 16-S2, with a yield of 83.93%. Mass spectrum m / z, theoretical value 925.74; measured value M+H: 926.74.

[0163] (3) Synthesis of 16-S3: Under nitrogen protection, 16-S2 (86.03 g, 92.93 mmoL, 1.0 equivalent) and 2580 mL of tert-butylbenzene were added to a single-mouth bottle with a magnetic rotor in sequence. The temperature was lowered to -40 degrees Celsius, and 1.5 M tert-butyl lithium (123.9 mL, 185.86 mmoL, 2.0 equivalent) was added. The reaction was kept warm for 2 hours. After completion, the temperature was raised to 80 degrees Celsius, and the reaction was continued for another 2 hours. The temperature was lowered to -30 degrees Celsius, and BBr3 (46.56 g, 185.8 mmoL, 2 equivalent) was added dropwise. After the addition was completed, the temperature was raised to 80 degrees Celsius, and the reaction was continued for 2 hours. Then, DIEA (36.03 g, 278.79 mmoL, 3.0 equivalent) was added dropwise. After the addition was completed, the mixture was refluxed overnight. After the reaction was completed, the heating was stopped, the mixture was cooled to room temperature, and an appropriate amount of distilled water was added. The solvent was removed under reduced pressure, and the solid was dissolved in dichloromethane and passed through a short silica gel column to obtain 18.6 g of product 16-S3 with a yield of 22.26%. Mass spectrum m / z, theoretical value 899.08; measured value M+H: 900.08.

[0164] Example 15: Preparation of Compound 21

[0165] The synthetic route of compound 21 is as follows:

[0166]

[0167] (1) Synthesis of 21-S1: Referring to the synthesis method of compound 16-S1 in Example 14, the yield of the final product was 85.32%. Mass spectrum m / z, theoretical value 582.58; measured value M+H: 583.58.

[0168] (2) Synthesis of 21-S2: Referring to the synthesis method of compound 16-S2 in Example 14, the yield of the final product was 86.76%. Mass spectrum m / z, theoretical value 827.56; measured value M+H: 828.56.

[0169] (3) Synthesis of 21-S3: Referring to the synthesis method of compound 16-S3 in Example 14, the yield of the final product was 25.33%. Mass spectrum m / z, theoretical value 800.90; measured value M+H: 801.90.

[0170] Example 16: Preparation of Compound 29

[0171] The synthetic route of compound 29 is as follows:

[0172]

[0173] (1) Synthesis of 29-S1: Referring to the synthesis method of compound 16-S1 in Example 14, the yield of the final product was 83.65%. Mass spectrum m / z, theoretical value 572.61; measured value M+H: 573.61.

[0174] (2) Synthesis of 29-S2: Referring to the synthesis method of compound 16-S2 in Example 14, the yield of the final product was 82.83%. Mass spectrum m / z, theoretical value 939.77; measured value M+H: 940.77.

[0175] (3) Synthesis of 29-S3: Referring to the synthesis method of compound 16-S3 in Example 14, the yield of the final product was 28.53%. Mass spectrum m / z, theoretical value 913.11; measured value M+H: 914.11.

[0176] Example 17: Preparation of Compound 36

[0177] The synthetic route of compound 36 is as follows:

[0178]

[0179] (1) Synthesis of 36-S1: Referring to the synthesis method of compound 16-S1 in Example 14, the yield of the final product was 79.62%. Mass spectrum m / z, theoretical value 516.50; measured value M+H: 517.50.

[0180] (2) Synthesis of 36-S2: Referring to the synthesis method of compound 16-S2 in Example 14, the yield of the final product was 88.03%. Mass spectrum m / z, theoretical value 827.56; measured value M+H: 828.56.

[0181] (3) Synthesis of 36-S3: Referring to the synthesis method of compound 16-S3 in Example 14, the yield of the final product was 28.82%. Mass spectrum m / z, theoretical value 800.90; measured value M+H: 801.90.

[0182] Example 18: Preparation of Compound 161

[0183] The synthetic route of compound 161 is as follows:

[0184]

[0185] (1) Synthesis of 161-S1: Referring to the synthesis method of compound 16-S1 in Example 14, the yield of the final product was 83.52%. Mass spectrum m / z, theoretical value 532.57; measured value M+H: 533.57.

[0186] (2) Synthesis of 161-S2: Referring to the synthesis method of compound 16-S2 in Example 14, the yield of the final product was 87.68%. Mass spectrum m / z, theoretical value 843.62; measured value M+H: 844.62.

[0187] (3) Synthesis of 161-S3: Referring to the synthesis method of compound 16-S3 in Example 14, the yield of the final product was 19.86%. Mass spectrum m / z, theoretical value 816.96; measured value M+H: 817.96.

[0188] Example 19: Preparation of Compound 181

[0189] The synthetic route of compound 181 is as follows:

[0190]

[0191] (1) Synthesis of 181-S1: Referring to the synthesis method of compound 16-S1 in Example 14, the yield of the final product was 84.67%. Mass spectrum m / z, theoretical value 598.65; measured value M+H: 599.65.

[0192] (2) Synthesis of 181-S2: Referring to the synthesis method of compound 16-S2 in Example 14, the yield of the final product was 79.88%. Mass spectrum m / z, theoretical value 843.62; measured value M+H: 844.62.

[0193] (3) Synthesis of 181-S3: Referring to the synthesis method of compound 16-S3 in Example 14, the yield of the final product was 23.52%. Mass spectrum m / z, theoretical value 816.96; measured value M+H: 817.96.

[0194] Example 20: Preparation of Compound 201

[0195] The synthetic route of compound 201 is as follows:

[0196]

[0197] (1) Synthesis of 201-S1: Referring to the synthesis method of compound 16-S1 in Example 14, the yield of the final product was 78.68%. Mass spectrum m / z, theoretical value 532.57; measured value M+H: 533.57.

[0198] (2) Synthesis of 201-S2: Referring to the synthesis method of compound 16-S2 in Example 14, the yield of the final product was 84.62%. Mass spectrum m / z, theoretical value 857.65; measured value M+H: 858.65.

[0199] (3) Synthesis of 201-S3: Referring to the synthesis method of compound 16-S3 in Example 14, the yield of the final product was 26.85%. Mass spectrum m / z, theoretical value 830.99; measured value M+H: 831.99.

[0200] Example 21: Preparation of Compound 221

[0201] The synthetic route of compound 221 is as follows:

[0202]

[0203] (1) Synthesis of 221-S1: Referring to the synthesis method of compound 16-S1 in Example 14, the yield of the final product was 86.94%. Mass spectrum m / z, theoretical value 612.67; measured value M+H: 613.67.

[0204] (2) Synthesis of 221-S2: Referring to the synthesis method of compound 16-S2 in Example 14, the yield of the final product was 81.87%. Mass spectrum m / z, theoretical value 857.65; measured value M+H: 858.65.

[0205] (3) Synthesis of 221-S3: Referring to the synthesis method of compound 16-S3 in Example 14, the yield of the final product was 29.67%. Mass spectrum m / z, theoretical value 930.99; measured value M+H: 831.99.

[0206] Example 22: Preparation of Compound 241

[0207] The synthetic route of compound 241 is as follows:

[0208]

[0209] (1) Synthesis of 241-S1: Referring to the synthesis method of compound 16-S1 in Example 14, the yield of the final product was 78.89%. Mass spectrum m / z, theoretical value 516.50; measured value M+H: 517.50.

[0210] (2) Synthesis of 241-S2: Referring to the synthesis method of compound 16-S2 in Example 14, the yield of the final product was 82.65%. Mass spectrum m / z, theoretical value 801.48; measured value M+H: 802.48.

[0211] (3) Synthesis of 241-S3: Referring to the synthesis method of compound 16-S3 in Example 14, the yield of the final product was 32.58%. Mass spectrum m / z, theoretical value 774.82; measured value M+H: 775.82.

[0212] Example 23: Preparation of Compound 481

[0213] The synthetic route of compound 481 is as follows:

[0214]

[0215] (1) Synthesis of 481-S1: Referring to the synthesis method of compound 16-S1 in Example 14, the yield of the final product was 82.63%. Mass spectrum m / z, theoretical value 516.50; measured value M+H: 517.50.

[0216] (2) Synthesis of 481-S2: Referring to the synthesis method of compound 16-S2 in Example 14, the yield of the final product was 88.45%. Mass spectrum m / z, theoretical value 817.54; measured value M+H: 818.54.

[0217] (3) Synthesis of 481-S3: Referring to the synthesis method of compound 16-S3 in Example 14, the yield of the final product was 35.29%. Mass spectrum m / z, theoretical value 790.88; measured value M+H: 791.88.

[0218] Example 24: Preparation of Compound 501

[0219] The synthetic route of compound 501 is as follows:

[0220]

[0221] (1) Synthesis of 501-S1: Referring to the synthesis method of compound 16-S1 in Example 14, the yield of the final product was 76.89%. Mass spectrum m / z, theoretical value 572.57; measured value M+H: 573.57.

[0222] (2) Synthesis of 501-S2: Referring to the synthesis method of compound 16-S2 in Example 14, the yield of the final product was 88.97%. Mass spectrum m / z, theoretical value 817.54; measured value M+H: 818.54.

[0223] (3) Synthesis of 501-S3: Referring to the synthesis method of compound 16-S3 in Example 14, the yield of the final product was 36.68%. Mass spectrum m / z, theoretical value 790.88; measured value M+H: 791.88.

[0224] Example 25: Preparation of Compound 693

[0225] The synthetic route of compound 693 is as follows:

[0226]

[0227] (1) Synthesis of 693-S1: Referring to the synthesis method of compound 16-S1 in Example 14, the yield of the final product was 86.62%. Mass spectrum m / z, theoretical value 488.45; measured value M+H: 489.45.

[0228] (2) Synthesis of 693-S2: Referring to the synthesis method of compound 16-S2 in Example 14, the yield of the final product was 90.52%. Mass spectrum m / z, theoretical value 801.48; measured value M+H: 802.48.

[0229] (3) Synthesis of 693-S3: Referring to the synthesis method of compound 16-S3 in Example 14, the yield of the final product was 28.53%. Mass spectrum m / z, theoretical value 732.74; measured value M+H: 733.74.

[0230] Device Example Preparation: Example 26 to Example 37

[0231] As a device embodiment, the present invention is based on Figure 1 The organic electroluminescent device is prepared as shown in FIG. Figure 1 The structure shown is only used as one example to explain the organic electroluminescent device prepared by the present invention, and should not be used as a specific limitation on the device structure. Figure 1 As shown, the organic electroluminescent diode (bottom-emitting OLED device) of the present invention comprises a substrate 110, an anode 120, a hole injection layer 130, a hole transport layer 140, a light-emitting layer 150, a hole blocking layer 160, an electron transport layer 170, an electron injection layer 180 and a cathode 190. The layers of the organic electroluminescent diode of the present invention can be formed by vacuum evaporation, sputtering, ion plating and the like, or by wet film forming methods such as spin coating, printing, and the like, and the solvent used is not particularly limited.

[0232] Embodiment 26

[0233] On the surface of ITO glass with a light-emitting area of ​​2 mm×2 mm or on the anode, HT-1 and P-3 are co-evaporated or HT-1 is evaporated to form a 10 nm hole injection layer (HIL) (wherein the volume ratio of HT-1 to P-3 is 95:5), a 90 nm hole transport layer (HTL), and then HT-8 is evaporated on the hole transport layer to form an electron blocking layer (EBL) with a thickness of 10 nm. Subsequently, a host material known in the art (such as BH-1) and a boron nitrogen compound (Compound 16 prepared in Example 14) (guest material) of the present invention are co-evaporated on the electron blocking layer to form a 35 nm light-emitting layer (EmL) (wherein the volume ratio of the boron nitrogen compound to the host compound is 3:97), and finally ET-13 and LiQ are co-evaporated to form a 35 nm electron transport layer (ETL) (wherein the volume ratio of ET-13 to LiQ is 1:1), and then 70 nm of cathode Al is evaporated, thereby manufacturing an organic electroluminescent diode.

[0234] Referring to the method provided in the above device Example 26, the prepared boron nitrogen compound 21, compound 29, compound 36, compound 161, compound 181, compound 201, compound 221, compound 241, compound 481, compound 501, and compound 693 were selected as implementation objects to replace compound 16, and they were directly co-evaporated with the main compound in a volume ratio of 3:97 to form a light-emitting layer to prepare organic electroluminescent diodes, which were respectively recorded as Examples 27 to 37.

[0235] Manufacturing of Comparative Examples 1 to 2

[0236] Comparative Examples 1 to 2 are similar to the device embodiment, except that BN-1 and BN-2 are used as guest materials of the light-emitting layer in Comparative Examples 1 to 2 to replace the boron nitrogen compound of the present invention. The chemical structures of the compounds BN-1 and BN-2 in the comparative examples are as follows:

[0237]

[0238] The organic electroluminescent diodes in Examples 26 to 37 and Comparative Examples 1 to 2 were characterized by standard methods known in the art. The electronic luminescence properties of the obtained devices are shown in Table 1.

[0239] Table 1.

[0240]

[0241]

[0242] As can be seen from Table 1, the compounds prepared in Examples 26 to 37 of the present invention exhibit good luminescent properties when applied to devices, and the luminescent efficiency and life of the prepared organic electroluminescent devices are significantly improved, and the driving voltage is significantly reduced, indicating that the boron nitrogen compounds of the present invention have certain application value.

[0243] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A boron-nitrogen compound, characterized in that: The boron nitrogen compound has a structure as shown in formula (I) or formula (II): Wherein, X1 and X2 are each independently selected from O or S; * indicates the position to be fused; R1 and R4 are each independently selected from hydrogen, deuterium, and C1-C18 alkyl; R2, R3, R5, R6 and R7 are each independently selected from C1-C18 alkyl.

2. The boron nitrogen compound according to claim 1, characterized in that R1, R2, R3, R4, R5, R6 and R7 are each independently selected from C1-C10 alkyl groups.

3. The boron nitrogen compound according to claim 1, characterized in that R1 and R4 are each independently selected from H, methyl, isopropyl or tert-butyl, and R2, R3, R5, R6 and R7 are each independently selected from methyl, isopropyl or tert-butyl.

4. A boron-nitrogen compound, characterized in that: The boron nitrogen compound is selected from the following:

5. Use of the boron nitrogen compound according to any one of claims 1 to 4 in the preparation of an organic electroluminescent device. 6 . An organic electroluminescent diode comprising a cathode layer, an anode layer and an organic functional layer, wherein the organic functional layer comprises the boron nitrogen compound according to claim 1 .

7. The organic light emitting diode according to claim 6, characterized in that: The organic functional layer includes a hole injection layer, a hole transport layer, a light-emitting layer, a hole blocking layer, an electron injection layer and an electron transport layer. The light-emitting layer includes the boron nitrogen compound described in any one of claims 1 to 4, and the light-emitting layer also includes a main compound; wherein the volume ratio of the boron nitrogen compound to the main compound is 1:1 to 1:

99.

8. A display device comprising the organic electroluminescent diode according to claim 6.

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