A hole transport material and an organic electroluminescent device comprising the same

Abstract

The application discloses a kind of hole transport material and organic electroluminescent device comprising the material, it is related to organic electroluminescent material field, its structural formula is as shown in following: the organic electroluminescent device prepared by using the hole transport material described in the application is compared with control example, voltage is greatly reduced, luminous efficiency is significantly improved.

Description

Technical Field

[0001] This invention relates to the field of organic electroluminescent materials, and more specifically to a hole transport material and an organic electroluminescent device containing the material. Background Technology

[0002] Organic light-emitting devices (OLEDs), also known as organic light-emitting diodes, are a type of all-solid-state flat-panel display technology developed in the 1980s. Organic electroluminescence refers to the phenomenon where organic semiconductor materials emit light under an electric field through carrier injection, transport, recombination to form excitons, and exciton decay. Displays made based on this light-emitting principle are called OLEDs.

[0003] In OLEDs, the hole transport layer plays a crucial role in improving hole transport efficiency within the device and blocking electrons within the emissive layer, thereby maximizing carrier recombination. The hole transport layer can reduce the energy barrier during hole injection, increase hole injection efficiency, and improve device brightness and lifetime. For good hole transport materials, in addition to requiring high hole mobility, the following conditions must be met: (1) the ability to form a defect-free, uniform, amorphous thin film; (2) excellent thermal stability, maintaining an amorphous morphology even under long-term operation. Although the aging mechanism of OLEDs is not yet fully understood, studies have shown that changes in the physical morphology of the organic layer are one of the influencing factors, such as melting and crystallization of the organic layer caused by heat generated during device operation; (3) having a suitable highest molecular occupied orbital (HOMO) energy level to ensure effective hole injection and transport between various interfaces; and preventing excessive Joule heating during device operation that could lead to material recrystallization. This crystallization would disrupt the uniformity of the thin film and also disrupt the good interfacial contact between the hole transport layer and the anode and organic layer, thus reducing the device's lifetime.

[0004] Currently, finding high-performance hole transport materials has become a research hotspot for engineers in the OLED field. Summary of the Invention

[0005] Objective of the invention: To address the above-mentioned technical problems, the present invention provides a hole transport material and an organic electroluminescent device containing the material.

[0006] To achieve the above-mentioned objectives, the technical solution adopted by this invention is as follows:

[0007] A hole transport material, the structural formula of which is shown below:

[0008]

[0009] Where a is a fused substituted or unsubstituted benzene ring;

[0010] R1, R2, R3, and R4 are each independently a substituted or unsubstituted C6-C30 aromatic group, a substituted or unsubstituted C5-C30 heteroaromatic group, or a substituted or unsubstituted C6-C30 aromatic amine group.

[0011] R5 is any one of hydrogen, deuterium, substituted or unsubstituted C1-C5 alkyl, substituted or unsubstituted C2-C5 alkenyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C3-C6 heterocycloalkyl, substituted or unsubstituted C6-C30 aromatic group, or substituted or unsubstituted C5-C30 heteroaromatic group.

[0012] W represents O or S;

[0013] m and n are each independently 0 or 1.

[0014] Furthermore, R1, R2, R3, and R4 are each independently phenyl, tolyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthrene, fluorenyl, oxofluorenyl, 9,9-dimethylfluorenyl, 9,9'-spirodifluorenyl, 9,9-diphenylfluorenyl, dibenzothiophene, carbazolyl, benzocarbazolyl, N-phenylcarbazolyl, o-diphenyl, trideuterylmethylbiphenyl, methylbiphenyl, and triphenylamino.

[0015] Furthermore, R5 is selected from any one of hydrogen, deuterium, methyl, ethyl, n-propyl, isopropyl, tert-butyl, and phenyl.

[0016] Furthermore, the hole transport material is any one of the following structural compounds:

[0017]

[0018]

[0019]

[0020]

[0021]

[0022]

[0023]

[0024]

[0025] Furthermore, the preparation method of the above-mentioned hole transport material includes the following steps:

[0026] (1)

[0027] Compound A and dichloromethane were slowly added to concentrated sulfuric acid. After the addition was complete, N-bromosuccinimide was added in several portions while stirring at room temperature. After the addition was complete, the reaction was stirred at room temperature for 10-15 hours. Ethanol was added to the reaction solution, and a solid was precipitated. The solid was filtered to obtain a filter cake. The filter cake was heated with toluene for 2-5 hours, cooled to room temperature, and then filtered to obtain compound B.

[0028] (2)

[0029] Under inert gas protection, compound C and anhydrous THF were added to a reaction flask, the temperature was lowered to -60 to -90°C, n-butyllithium was added dropwise, and after reacting for 20-40 min, compound B and anhydrous THF were mixed and added dropwise. The reaction was continued at -60 to -90°C for 1-3 h, ammonium chloride solution was added to quench the reaction, and the temperature was slowly restored to room temperature. Dichloromethane and water were added for extraction and separation. After washing with water and drying, the crude product of compound D was obtained by concentration under reduced pressure. After purification by column chromatography, pure product of compound D was obtained.

[0030] (3)

[0031] Compound D was added to isopropanol, followed by the addition of hydrochloric acid. The mixture was heated to an azeotropic reaction for 4-6 hours, and then the isopropanol was removed by vacuum distillation. The mixture was then filtered to obtain compound E.

[0032] (4)

[0033] Under inert gas protection, compound E, with the general structural formula […], was […]. Compound F, sodium tert-butoxide, Pd2(dba)3, tri-tert-butylphosphine, and toluene were added to a reaction flask. After the addition was complete, the mixture was heated to reflux and reacted for 4-6 hours. After the reaction was completed, the mixture was cooled to room temperature, water was added, and the mixture was stirred for 10-20 minutes. The mixture was then filtered to obtain a filtrate. The filtrate was separated to obtain an organic phase. The organic phase was dried, evaporated to dryness, and purified by column chromatography to obtain the high-purity final product G.

[0034] The application of the aforementioned hole transport materials in the fabrication of organic electroluminescent devices.

[0035] An organic electroluminescent device includes a cathode, an anode, a light-emitting layer, and a hole transport layer, wherein the hole transport layer contains the aforementioned hole transport material.

[0036] A lighting device comprising the aforementioned organic electroluminescent device.

[0037] An electronic display device comprising the aforementioned organic electroluminescent device.

[0038] The beneficial effects of this invention are:

[0039] The hole transport material designed in this invention has the following core structure:

[0040] This structure ensures that the materials possess a very large conjugated system, expanding the nonlocalized range of electrons within the molecules and enhancing electron mobility, thereby increasing the hole migration capability of the molecules. Simultaneously, the addition of electron-donating groups such as R5 and aromatic amine branches increases the electron cloud density and spatial conformation of the molecules, further increasing the hole transfer rate between molecules and improving the hole transport capability of the molecules.

[0041] Higher electron cloud density and spatial conformation can effectively improve the HOMO energy level of material molecules, thereby reducing the interfacial barrier between the hole injection layer and the hole transport layer, and between the hole transport layer and the light-emitting layer. It can also greatly improve the hole injection efficiency and rate, reduce hole waste, and thus significantly reduce the device driving voltage, reduce energy consumption, and improve the device luminous efficiency and lifetime.

[0042] Meanwhile, this structure belongs to a large rigid group, which itself has very high Td (0.5%) and Tg, that is, it has very good thermal stability, chemical stability and light stability. This can greatly expand the range of materials and improve the stability and lifespan of devices. Especially when W is an oxygen atom, devices using this type of material have better lifespan. Attached Figure Description

[0043] Figure 1 This is a graph showing the relationship between the luminous intensity of the electroluminescent device and the luminous time in Example 5 of the present invention.

[0044] Depend on Figure 1 It can be seen that the lifetime (T97%) of the electroluminescent device in Application Example 5 of the present invention is 313H. Detailed Implementation

[0045] Unless otherwise specified in the examples, the procedures should be performed under standard conditions or conditions recommended by the manufacturer. Reagents or instruments whose manufacturers are not specified are all commercially available products.

[0046] Example 1:

[0047]

[0048] The method for synthesizing hole transport material 1 is as follows:

[0049] (1)

[0050] Compound A (1 eq, 180.06 g / mol, 0.056 mol, 10.0 g), dichloromethane (42 eq, 2.355 mol, 84.93 g / mol, 200.0 g), and concentrated sulfuric acid (0.05 eq, 98 g / mol, 0.27 g, 0.0028 mol) were added to a three-necked flask. After the addition was complete, N-bromosuccinimide (1.2 eq, 177.98 g / mol) was added in several portions with stirring at room temperature. 11.96 g (0.0672 mol) was added, and the mixture was stirred at room temperature for 12 hours. After the reaction was completed, the reaction was stopped by HPLC monitoring. Ethanol (193.8 eq, 10.853 mol, 46.07 g / mol, 500 g) was added to the reaction solution, and a solid precipitated. The solid was filtered to obtain a filter cake, which was then heated in toluene for 3 hours, cooled to room temperature, and filtered to obtain compound B (6.55 g, yield 45.5%). MS (EI): 257 (M + );

[0051] (2)

[0052] Compound C (1.1 eq, 278.03 g / mol, 0.025 mol, 7.03 g) and anhydrous THF (42.4 eq, 72.11 g / mol, 0.975 mol, 70.3 g) were added to a reaction flask under nitrogen protection. The mixture was cooled to -78°C with liquid nitrogen, and n-butyllithium (1.1 eq, 64.05 g / mol, 0.025 mol, 1.62 g) was added dropwise. After reacting for 30 min, compound B (1 eq, 257.97 g / mol, 0.02 g) was added. 3 mol (6.0 g) and anhydrous THF (36.2 eq, 72.11 g / mol, 0.832 mol, 60 g) were mixed and added dropwise. The reaction was continued at -78℃ for 2 h, then quenched with ammonium chloride solution. After slowly restoring to room temperature, dichloromethane and water were added for extraction and separation. The dichloromethane phase was separated, washed with water several times, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain crude compound 4. After purification by column chromatography, pure compound D (3.26 g, yield 30.9%) was obtained. MS (EI): 458 (M + );

[0053] (3)

[0054] Compound D (1 eq, 458.09 g / mol, 0.007 mol, 3.0 g) was added to isopropanol (71.2 eq, 60.06 g / mol, 0.499 mol, 30.0 g, 10 times the mass of compound D), followed by dropwise addition of hydrochloric acid (117.4 eq, 36.5 g / mol, 0.822 mol, 30.0 g, 10 times the mass of compound D). The mixture was heated to an azeotropic reaction for 5 h, and then the isopropanol was removed by vacuum distillation. The mixture was filtered to give compound E (3.02 g, yield 98.1%). MS (EI): 440 (M + );

[0055] (4)

[0056] Under nitrogen protection, compounds E (1 eq, 440.08 g / mol, 0.007 mol, 3.0 g), F (1.1 eq, 361.18 g / mol, 0.008 mol, 2.78 g), sodium tert-butoxide (1.1 eq, 96.1 g / mol, 0.008 mol, 0.769 g), Pd₂(dba)₃ (0.05 eq, 915 g / mol, 0.00035 mol, 0.32 g), and tri-tert-butylphosphine (0.05 eq, ... 202.32 g / mol, 0.00035 mol, 0.071 g, and toluene (30.0 g, 10 times the mass of compound E) were added to the reaction flask. After the addition was complete, the mixture was heated to reflux and reacted for 5 h. After the reaction was completed, it was cooled to room temperature, and 100 ml of water was added. The mixture was stirred for 15 min and then filtered to obtain the filtrate. The filtrate was separated to obtain the organic phase. The organic phase was dried with anhydrous magnesium sulfate, evaporated to dryness, and purified by column chromatography to obtain high-purity compound 1 (2.98 g, yield 59.3%). MS (EI): 721 (M + ).

[0057] Example 2:

[0058]

[0059] The method for synthesizing hole transport material 2 is as follows:

[0060] (1)

[0061] Compound A (1 eq, 180.06 g / mol, 0.056 mol, 10.0 g), dichloromethane (42 eq, 2.355 mol, 84.93 g / mol, 200.0 g), and concentrated sulfuric acid (0.05 eq, 98 g / mol, 0.27 g, 0.0028 mol) were added to a three-necked flask. After the addition was complete, N-bromosuccinimide (1.2 eq, 177.98 g / mol) was added in several portions with stirring at room temperature. 11.96 g (0.0672 mol) was added, and the mixture was stirred at room temperature for 12 hours. After the reaction was completed, the reaction was stopped by HPLC monitoring. Ethanol (193.8 eq, 10.853 mol, 46.07 g / mol, 500 g) was added to the reaction solution, and a solid precipitated. The solid was filtered to obtain a filter cake, which was then heated in toluene for 3 hours, cooled to room temperature, and filtered to obtain compound B (6.89 g, yield 47.9%). MS (EI): 257 (M + );

[0062] (2)

[0063] Compound C (1.1 eq, 278.03 g / mol, 0.025 mol, 7.03 g) and anhydrous THF (42.4 eq, 72.11 g / mol, 0.975 mol, 70.3 g) were added to a reaction flask under nitrogen protection. The mixture was cooled to -78°C with liquid nitrogen, and n-butyllithium (1.1 eq, 64.05 g / mol, 0.025 mol, 1.62 g) was added dropwise. After reacting for 30 min, compound B (1 eq, 257.97 g / mol, 0.02 g) was added. 3 mol (6.0 g) and anhydrous THF (36.2 eq, 72.11 g / mol, 0.832 mol, 60 g) were mixed and added dropwise. The reaction was continued at -78℃ for 2 h, then quenched with ammonium chloride solution. After slowly restoring to room temperature, dichloromethane and water were added for extraction and separation. The dichloromethane phase was separated, washed with water several times, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain crude compound 4. After purification by column chromatography, pure compound D (3.42 g, yield 32.5%) was obtained. MS (EI): 458 (M + );

[0064] (3)

[0065] Compound D (1 eq, 458.09 g / mol, 0.007 mol, 3.0 g) was added to isopropanol (71.2 eq, 60.06 g / mol, 0.499 mol, 30.0 g, 10 times the mass of compound D), followed by dropwise addition of hydrochloric acid (117.4 eq, 36.5 g / mol, 0.822 mol, 30.0 g, 10 times the mass of compound D). The mixture was heated to an azeotropic reaction for 5 h, and then the isopropanol was removed by vacuum distillation. The mixture was filtered to give compound E (3.02 g, yield 98.1%). MS (EI): 440 (M + );

[0066] (4)

[0067] Under nitrogen protection, compounds E (1 eq, 440.08 g / mol, 0.007 mol, 3.0 g), F (1.1 eq, 361.18 g / mol, 0.008 mol, 2.78 g), sodium tert-butoxide (1.1 eq, 96.1 g / mol, 0.008 mol, 0.769 g), Pd2(dba)3 (0.05 eq, 915 g / mol, 0.00035 mol, 0.32 g), and tri-tert-butylphosphine (0.05 eq, 20 g / mol, 3.0 g / mol, 440.08 g / mol, 0.007 mol, 3.0 g) were added. 2.32 g / mol, 0.00035 mol, 0.071 g, and toluene (30.0 g, 10 times the mass of compound E) were added to the reaction flask. After the addition was complete, the mixture was heated to reflux and reacted for 5 h. After the reaction was completed, the mixture was cooled to room temperature, and 100 ml of water was added. The mixture was stirred for 15 min and then filtered to obtain the filtrate. The filtrate was separated to obtain the organic phase. The organic phase was dried with anhydrous magnesium sulfate, evaporated to dryness, and purified by column chromatography to obtain high-purity hole transport material 2 (3.29 g, yield 65.3%). MS (EI): 721 (M + ).

[0068] Example 3:

[0069]

[0070] The method for synthesizing hole transport material 3 is as follows:

[0071] (1)

[0072] Compound A (1 eq, 180.06 g / mol, 0.056 mol, 10.0 g), dichloromethane (42 eq, 2.355 mol, 84.93 g / mol, 200.0 g), and concentrated sulfuric acid (0.05 eq, 98 g / mol, 0.27 g, 0.0028 mol) were added to a three-necked flask. After the addition was complete, N-bromosuccinimide (1.2 eq, 177.98 g / mol) was added in several portions with stirring at room temperature. 11.96 g (0.0672 mol) was added, and the mixture was stirred at room temperature for 12 hours. After the reaction was completed, the reaction was stopped by HPLC monitoring. Ethanol (193.8 eq, 10.853 mol, 46.07 g / mol, 500 g) was added to the reaction solution, and a solid precipitated. The solid was filtered to obtain a filter cake, which was then heated in toluene for 3 hours, cooled to room temperature, and filtered to obtain compound B (6.63 g, yield 46.1%). MS (EI): 257 (M + );

[0073] (2)

[0074] Compound C (1.1 eq, 278.03 g / mol, 0.025 mol, 7.03 g) and anhydrous THF (42.4 eq, 72.11 g / mol, 0.975 mol, 70.3 g) were added to a reaction flask under nitrogen protection. The mixture was cooled to -78°C with liquid nitrogen, and n-butyllithium (1.1 eq, 64.05 g / mol, 0.025 mol, 1.62 g) was added dropwise. After reacting for 30 min, compound B (1 eq, 257.97 g / mol, 0.02 g) was added. 3 mol (6.0 g) and anhydrous THF (36.2 eq, 72.11 g / mol, 0.832 mol, 60 g) were mixed and added dropwise. The reaction was continued at -78℃ for 2 h, then quenched with ammonium chloride solution. After slowly restoring to room temperature, dichloromethane and water were added for extraction and separation. The dichloromethane phase was separated, washed with water several times, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain crude compound 4. After purification by column chromatography, compound D (3.53 g, yield 33.5%) was obtained. MS (EI): 458 (M + );

[0075] (3)

[0076] Compound D (1 eq, 458.09 g / mol, 0.007 mol, 3.0 g) was added to isopropanol (71.2 eq, 60.06 g / mol, 0.499 mol, 30.0 g, 10 times the mass of compound D), followed by dropwise addition of hydrochloric acid (117.4 eq, 36.5 g / mol, 0.822 mol, 30.0 g, 10 times the mass of compound D). The mixture was heated to an azeotropic reaction for 5 h, and then the isopropanol was removed by vacuum distillation. The mixture was filtered to give compound E (3.03 g, yield 98.3%). MS (EI): 440 (M + );

[0077] (4)

[0078] Under nitrogen protection, compounds E (1 eq, 440.08 g / mol, 0.007 mol, 3.0 g), F (1.1 eq, 361.18 g / mol, 0.008 mol, 2.78 g), sodium tert-butoxide (1.1 eq, 96.1 g / mol, 0.008 mol, 0.769 g), Pd2(dba)3 (0.05 eq, 915 g / mol, 0.00035 mol, 0.32 g), and tri-tert-butylphosphine (0.05 eq, 20 g / mol, 3.0 g / mol, 440.08 g / mol, 0.007 mol, 3.0 g) were added. 2.32 g / mol, 0.00035 mol, 0.071 g, and toluene (30.0 g, 10 times the mass of compound E) were added to the reaction flask. After the addition was complete, the mixture was heated to reflux and reacted for 5 h. After the reaction was completed, it was cooled to room temperature, and 100 ml of water was added. The mixture was stirred for 15 min and then filtered to obtain the filtrate. The filtrate was separated to obtain the organic phase. The organic phase was dried with anhydrous magnesium sulfate, evaporated to dryness, and purified by column chromatography to obtain high-purity hole transport material 3 (3.12 g, yield 61.9%). MS (EI): 721 (M + ).

[0079] Example 4:

[0080] The method for synthesizing hole transport material 4 is as follows:

[0081]

[0082] Steps 1-3 are basically the same as in Example 1; the remaining steps are as follows:

[0083] (4)

[0084] Under nitrogen protection, compounds E (1 eq, 440.08 g / mol, 0.007 mol, 3.0 g), F (1.1 eq, 321.15 g / mol, 0.008 mol, 2.57 g), sodium tert-butoxide (1.1 eq, 96.1 g / mol, 0.008 mol, 0.769 g), Pd₂(dba)₃ (0.05 eq, 915 g / mol, 0.00035 mol, 0.32 g), and tri-tert-butylphosphine (0.05 eq, ... 202.32 g / mol, 0.00035 mol, 0.071 g, and toluene (30.0 g, 10 times the mass of compound E) were added to the reaction flask. After the addition was complete, the mixture was heated to reflux and reacted for 5 h. After the reaction was completed, it was cooled to room temperature, and 100 ml of water was added. The mixture was stirred for 15 min and then filtered to obtain the filtrate. The filtrate was separated to obtain the organic phase. The organic phase was dried with anhydrous magnesium sulfate, evaporated to dryness, and purified by column chromatography to obtain high-purity compound 4 (3.05 g, yield 63.9%). MS (EI): 681 (M + ).

[0085] Example 5:

[0086]

[0087] The method for synthesizing hole transport material 5 is as follows: Step 1 is basically the same as in Example 1, and the remaining steps are as follows:

[0088] (2)

[0089] Compound C (1.1 eq, 314.03 g / mol, 0.021 mol, 6.6 g) and anhydrous THF (42.4 eq, 72.11 g / mol, 0.89 mol, 64.2 g) were added to a reaction flask under nitrogen protection. The mixture was cooled to -78°C with liquid nitrogen, and n-butyllithium (1.1 eq, 64.05 g / mol, 0.023 mol, 1.47 g) was added dropwise. After reacting for 30 min, compound B (1 eq, 257.97 g / mol, 0.021 mol, 6.6 g) was added. The mixture of dichloromethane (5.4 g) and anhydrous THF (36.2 eq, 72.11 g / mol, 0.76 mol, 54.8 g) was added dropwise, and the reaction was continued at -78℃ for 2 h. The reaction was then quenched with ammonium chloride solution, and after slowly restoring to room temperature, dichloromethane and water were added for extraction and separation. The dichloromethane phase was separated, washed repeatedly with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain crude compound 4. After purification by column chromatography, pure compound D (3.36 g, yield 32.4%) was obtained. MS (EI): 494 (M + );

[0090] (3)

[0091] Compound D (1 eq, 494 g / mol, 0.006 mol, 3.0 g) was added to isopropanol (10 times the mass of compound D), followed by dropwise addition of hydrochloric acid (10 times the mass of compound D). The mixture was heated to an azeotropic reaction for 5 h, and then the isopropanol was removed by vacuum distillation. The mixture was filtered to give compound E (2.86 g, yield 98.2%), MS (EI): 476 (M). + );

[0092] (4)

[0093] Under nitrogen protection, compounds E (1 eq, 476 g / mol, 5.25 mmol, 2.5 g), F (1.1 eq, 361.18 g / mol, 5.78 mmol, 2.09 g), sodium tert-butoxide (1.1 eq, 96.1 g / mol, 5.78 mmol, 0.56 g), Pd2(dba)3 (0.05 eq, 915 g / mol, 0.26 mmol, 0.24 g), and tri-tert-butylphosphine (0.05 eq, 202 g / mol) were subjected to nitrogen treatment. 0.32 g / mol, 0.26 mmol, 0.053 g), and toluene (25 g, 10 times the mass of compound E) were added to the reaction flask. After the addition was complete, the mixture was heated to reflux and reacted for 5 h. After the reaction was completed, the mixture was cooled to room temperature, and 100 ml of water was added. The mixture was stirred for 15 min and then filtered to obtain the filtrate. The filtrate was separated to obtain the organic phase. The organic phase was dried with anhydrous magnesium sulfate, evaporated to dryness, and purified by column chromatography to obtain high-purity hole transport material 5 (2.55 g, yield 64.2%). MS (EI): 757 (M + ).

[0094] Example 6:

[0095]

[0096] The method for synthesizing hole transport material 6 is as follows:

[0097] (1)

[0098] Compound A (1 eq, 180.06 g / mol, 0.056 mol, 10.0 g), dichloromethane (42 eq, 2.355 mol, 84.93 g / mol, 200.0 g), and concentrated sulfuric acid (0.05 eq, 98 g / mol, 0.27 g, 0.0028 mol) were added to a three-necked flask. After the addition was complete, N-bromosuccinimide (1.2 eq, 177.98 g / mol) was added in several portions with stirring at room temperature. 11.96 g (0.0672 mol) was added, and the mixture was stirred at room temperature for 12 hours. After the reaction was completed, the reaction was stopped by HPLC monitoring. Ethanol (193.8 eq, 10.853 mol, 46.07 g / mol, 500 g) was added to the reaction solution, and a solid precipitated. The solid was filtered to obtain a filter cake, which was then heated in toluene for 3 hours, cooled to room temperature, and filtered to obtain compound B (6.59 g, yield 45.8%). MS (EI): 257 (M + );

[0099] (2)

[0100] Compound C (1.1 eq, 328.05 g / mol, 0.025 mol, 8.2 g) and anhydrous THF (42.4 eq, 72.11 g / mol, 0.975 mol, 70.3 g) were added to a reaction flask under nitrogen protection. The mixture was cooled to -78°C with liquid nitrogen, and n-butyllithium (1.1 eq, 64.05 g / mol, 0.025 mol, 1.62 g) was added dropwise. After reacting for 30 min, compound B (1 eq, 257.97 g / mol, 0.023 g) was added. The mixture of dichloromethane (6.0 g) and anhydrous THF (36.2 eq, 72.11 g / mol, 0.832 mol, 60 g) was added dropwise, and the reaction was continued at -78℃ for 2 h. The reaction was then quenched with ammonium chloride solution, and after slowly restoring to room temperature, dichloromethane and water were added for extraction and separation. The dichloromethane phase was separated, washed repeatedly with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain crude compound 4. After purification by column chromatography, compound D (3.83 g, yield 32.8%) was obtained. MS (EI): 508 (M + );

[0101] (3)

[0102] Compound D (1 eq, 508.10 g / mol, 0.006 mol, 3.0 g) was added to isopropanol (71.2 eq, 60.06 g / mol, 0.499 mol, 30.0 g, 10 times the mass of compound D), followed by dropwise addition of hydrochloric acid (117.4 eq, 36.5 g / mol, 0.822 mol, 30.0 g, 10 times the mass of compound D). The mixture was heated to an azeotropic reaction for 5 h, and then the isopropanol was removed by vacuum distillation. The mixture was filtered to give compound E (2.85 g, yield 96.9%), MS (EI): 490 (M + );

[0103] (4)

[0104] Under nitrogen protection, compounds E (1 eq, 490.09 g / mol, 0.004 mol, 2.0 g), F (1.1 eq, 361.18 g / mol, 0.005 mol, 1.81 g), sodium tert-butoxide (1.1 eq, 96.1 g / mol, 0.005 mol, 0.481 g), Pd2(dba)3 (0.05 eq, 915 g / mol, 0.0002 mol, 0.18 g), and tri-tert-butylphosphine (0.05 eq, 20 g / mol, 490.09 g / mol, 0.004 mol, 2.0 g) were subjected to nitrogen treatment. 2.32 g / mol, 0.0002 mol, 0.405 g), and toluene (20.0 g, 10 times the mass of compound E) were added to the reaction flask. After the addition was complete, the mixture was heated to reflux and reacted for 5 h. After the reaction was completed, it was cooled to room temperature, and 100 ml of water was added. The mixture was stirred for 15 min and then filtered to obtain the filtrate. The filtrate was separated to obtain the organic phase. The organic phase was dried with anhydrous magnesium sulfate, evaporated to dryness, and purified by column chromatography to obtain high-purity hole transport material 6 (1.99 g, yield 64.4%). MS (EI): 771 (M + ).

[0105] Example 7:

[0106]

[0107] The method for synthesizing hole transport material 7 is as follows:

[0108] (1)

[0109] Compound A (1 eq, 180.06 g / mol, 0.056 mol, 10.0 g), dichloromethane (42 eq, 2.355 mol, 84.93 g / mol, 200.0 g), and concentrated sulfuric acid (0.05 eq, 98 g / mol, 0.27 g, 0.0028 mol) were added to a three-necked flask. After the addition was complete, N-bromosuccinimide (1.2 eq, 177.98 g / mol) was added in several portions with stirring at room temperature. 11.96 g (0.0672 mol) was added, and the mixture was stirred at room temperature for 12 hours. After the reaction was completed, the reaction was stopped by HPLC monitoring. Ethanol (193.8 eq, 10.853 mol, 46.07 g / mol, 500 g) was added to the reaction solution, and a solid precipitated. The solid was filtered to obtain a filter cake, which was then heated in toluene for 3 hours, cooled to room temperature, and filtered to obtain compound B (6.55 g, yield 45.5%). MS (EI): 257 (M + );

[0110] (2)

[0111] Compound C (1.1 eq, 328.05 g / mol, 0.025 mol, 8.2 g) and anhydrous THF (42.4 eq, 72.11 g / mol, 0.975 mol, 70.3 g) were added to a reaction flask under nitrogen protection. The mixture was cooled to -78°C with liquid nitrogen, and n-butyllithium (1.1 eq, 64.05 g / mol, 0.025 mol, 1.62 g) was added dropwise. After reacting for 30 min, compound B (1 eq, 257.97 g / mol, 0.02 g) was added. 3 mol (6.0 g) and anhydrous THF (36.2 eq, 72.11 g / mol, 0.832 mol, 60 g) were mixed and added dropwise. The reaction was continued at -78℃ for 2 h, then quenched with ammonium chloride solution. After slowly restoring to room temperature, dichloromethane and water were added for extraction and separation. The dichloromethane phase was separated, washed with water several times, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain crude compound 4. After purification by column chromatography, pure compound D (4.1 g, yield 32.3%) was obtained. MS (EI): 508 (M + (3)

[0112] Compound D (1 eq, 508.10 g / mol, 0.006 mol, 3.0 g) was added to isopropanol (71.2 eq, 60.06 g / mol, 0.499 mol, 30.0 g, 10 times the mass of compound D), followed by dropwise addition of hydrochloric acid (117.4 eq, 36.5 g / mol, 0.822 mol, 30.0 g, 10 times the mass of compound D). The mixture was heated to an azeotropic reaction for 5 h, and then the isopropanol was removed by vacuum distillation. The mixture was filtered to give compound E (2.84 g, yield 96.7%). MS (EI): 490 (M + );

[0113] (4)

[0114] Under nitrogen protection, compounds E (1 eq, 490.09 g / mol, 0.004 mol, 2.0 g), F (1.1 eq, 361.18 g / mol, 0.005 mol, 1.81 g), sodium tert-butoxide (1.1 eq, 96.1 g / mol, 0.005 mol, 0.481 g), Pd2(dba)3 (0.05 eq, 915 g / mol, 0.0002 mol, 0.18 g), and tri-tert-butylphosphine (0.05 eq, 20 g / mol, 490.09 g / mol, 0.004 mol, 2.0 g) were subjected to nitrogen treatment. 2.32 g / mol, 0.0002 mol, 0.405 g), and toluene (20.0 g, 10 times the mass of compound E) were added to the reaction flask. After the addition was complete, the mixture was heated to reflux and reacted for 5 h. After the reaction was completed, the mixture was cooled to room temperature, and 100 ml of water was added. The mixture was stirred for 15 min and then filtered to obtain the filtrate. The filtrate was separated to obtain the organic phase. The organic phase was dried with anhydrous magnesium sulfate, evaporated to dryness, and purified by column chromatography to obtain high-purity hole transport material 7 (1.98 g, yield 64.2%). MS (EI): 771 (M + ).

[0115] Example 8:

[0116]

[0117] The method for synthesizing hole transport material 8 is as follows:

[0118] (1)

[0119] Compound A (1 eq, 180.06 g / mol, 0.056 mol, 10.0 g), dichloromethane (42 eq, 2.355 mol, 84.93 g / mol, 200.0 g), and concentrated sulfuric acid (0.05 eq, 98 g / mol, 0.27 g, 0.0028 mol) were added to a three-necked flask. After the addition was complete, N-bromosuccinimide (1.2 eq, 177.98 g / mol) was added in several portions with stirring at room temperature. 11.96 g (0.0672 mol) was added, and the mixture was stirred at room temperature for 12 hours. After the reaction was completed, the reaction was stopped by HPLC monitoring. Ethanol (193.8 eq, 10.853 mol, 46.07 g / mol, 500 g) was added to the reaction solution, and a solid precipitated. The solid was filtered to obtain a filter cake, which was then heated in toluene for 3 hours, cooled to room temperature, and filtered to obtain compound B (6.43 g, yield 44.7%). MS (EI): 257 (M + );

[0120] (2)

[0121] Compound C (1.1 eq, 328.05 g / mol, 0.025 mol, 8.2 g) and anhydrous THF (42.4 eq, 72.11 g / mol, 0.975 mol, 70.3 g) were added to a reaction flask under nitrogen protection. The mixture was cooled to -78°C with liquid nitrogen, and n-butyllithium (1.1 eq, 64.05 g / mol, 0.025 mol, 1.62 g) was added dropwise. After reacting for 30 min, compound B (1 eq, 257.97 g / mol, 0.023 g) was added. The mixture of dichloromethane (6.0 g) and anhydrous THF (36.2 eq, 72.11 g / mol, 0.832 mol, 60 g) was added dropwise, and the reaction was continued at -78℃ for 2 h. The reaction was then quenched with ammonium chloride solution, and after slowly restoring to room temperature, dichloromethane and water were added for extraction and separation. The dichloromethane phase was separated, washed repeatedly with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain crude compound 4. After purification by column chromatography, compound D (4.48 g, yield 35.3%) was obtained. MS (EI): 508 (M + );

[0122] (3)

[0123] Compound D (1 eq, 508.10 g / mol, 0.006 mol, 3.0 g) was added to isopropanol (71.2 eq, 60.06 g / mol, 0.499 mol, 30.0 g, 10 times the mass of compound D), followed by dropwise addition of hydrochloric acid (117.4 eq, 36.5 g / mol, 0.822 mol, 30.0 g, 10 times the mass of compound D). The mixture was heated to an azeotropic reaction for 5 h, and then the isopropanol was removed by vacuum distillation. The mixture was filtered to give compound E (2.81 g, yield 95.7%). MS (EI): 490 (M + );

[0124] (4)

[0125] Under nitrogen protection, compounds E (1 eq, 490.09 g / mol, 0.004 mol, 2.0 g), F (1.1 eq, 361.18 g / mol, 0.005 mol, 1.81 g), sodium tert-butoxide (1.1 eq, 96.1 g / mol, 0.005 mol, 0.481 g), Pd₂(dba)₃ (0.05 eq, 915 g / mol, 0.0002 mol, 0.18 g), and tri-tert-butylphosphine (0.05 eq, ... 202.32 g / mol, 0.0002 mol, 0.405 g), and toluene (20.0 g, 10 times the mass of compound E) were added to the reaction flask. After the addition was complete, the mixture was heated to reflux and reacted for 5 h. After the reaction was completed, it was cooled to room temperature, and 100 ml of water was added. The mixture was stirred for 15 min and then filtered to obtain the filtrate. The filtrate was separated to obtain the organic phase. The organic phase was dried with anhydrous magnesium sulfate, evaporated to dryness, and purified by column chromatography to obtain high-purity compound 8 (1.99 g, yield 68.2%). MS (EI): 731 (M + ).

[0126] Example 9:

[0127]

[0128] The method for synthesizing hole transport material 9 is as follows:

[0129] (1)

[0130] Compound A (1 eq, 347.13 g / mol, 0.029 mol, 10.0 g), dichloromethane (42 eq, 2.355 mol, 84.93 g / mol, 200.0 g), and concentrated sulfuric acid (0.05 eq, 98 g / mol, 0.14 g, 0.0014 mol) were added to a three-necked flask. After the addition was complete, N-bromosuccinimide (1.2 eq, 177.98 g / mol) was added in portions at room temperature with stirring. 6.19 g (0.0348 mol) was added to the reaction solution. After the addition was complete, the mixture was stirred at room temperature for 12 hours. After the reaction was completed according to HPLC monitoring, the reaction was stopped. Ethanol (193.8 eq, 10.853 mol, 46.07 g / mol, 500 g) was added to the reaction solution, and a solid precipitated. The solid was filtered to obtain a filter cake. The filter cake was heated in toluene for 3 hours, cooled to room temperature, and then filtered to obtain compound B (6.29 g, yield 51.1%). MS (EI): 425 (M + );

[0131] (2)

[0132] Compound C (1.1 eq, 278.03 g / mol, 0.015 mol, 4.17 g) and anhydrous THF (42.4 eq, 72.11 g / mol, 0.594 mol, 42.8 g) were added to a reaction flask under nitrogen protection. The mixture was cooled to -78°C with liquid nitrogen, and n-butyllithium (1.1 eq, 64.05 g / mol, 0.015 mol, 0.96 g) was added dropwise. After reacting for 30 min, compound B (1 eq, 425.04 g / mol, 0.01 g) was added. 4 mol (6.0 g) and anhydrous THF (59.5 eq, 72.11 g / mol, 0.833 mol, 60 g) were mixed and added dropwise. The reaction was continued at -78℃ for 2 h, then quenched with ammonium chloride solution. After slowly restoring to room temperature, dichloromethane and water were added for extraction and separation. The dichloromethane phase was separated, washed with water several times, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain crude compound 4. After purification by column chromatography, compound D (3.07 g, yield 32.6%) was obtained. MS (EI): 625 (M + );

[0133] (3)

[0134] Compound D (1 eq, 625.16 g / mol, 0.005 mol, 3.0 g) was added to isopropanol (71.2 eq, 60.06 g / mol, 0.499 mol, 30.0 g, 10 times the mass of compound D), followed by dropwise addition of hydrochloric acid (117.4 eq, 36.5 g / mol, 0.822 mol, 30.0 g, 10 times the mass of compound D). The mixture was heated to an azeotropic reaction for 5 h, and then the isopropanol was removed by vacuum distillation. The mixture was filtered to give compound E (3.0 g, yield 98.9%), MS (EI): 607 (M + );

[0135] (4)

[0136] Under nitrogen protection, compounds E (1 eq, 607.15 g / mol, 0.005 mol, 3.0 g), F (1.1 eq, 169.09 g / mol, 0.006 mol, 1.01 g), sodium tert-butoxide (1.1 eq, 96.1 g / mol, 0.006 mol, 0.577 g), Pd2(dba)3 (0.05 eq, 915 g / mol, 0.00025 mol, 0.23 g), and tri-tert-butylphosphine (0.05 eq, 20 g / mol, 607.15 g / mol, 0.005 mol, 3.0 g) were subjected to nitrogen treatment. 2.32 g / mol, 0.00025 mol, 0.051 g, and toluene (30.0 g, 10 times the mass of compound E) were added to the reaction flask. After the addition was complete, the mixture was heated to reflux and reacted for 5 h. After the reaction was completed, it was cooled to room temperature, and 100 ml of water was added. The mixture was stirred for 15 min and then filtered to obtain the filtrate. The filtrate was separated to obtain the organic phase. The organic phase was dried with anhydrous magnesium sulfate, evaporated to dryness, and purified by column chromatography to obtain high-purity hole transport material 9 (2.27 g, yield 65.1%). MS (EI): 696 (M + ).

[0137] Example 10:

[0138]

[0139] The method for synthesizing hole transport material 10 is as follows: Step 1 is basically the same as in Example 9, and the remaining steps are as follows:

[0140] (2)

[0141] Compound C (1.1 eq, 221.97 g / mol, 0.015 mol, 3.33 g) and anhydrous THF (42.4 eq, 72.11 g / mol, 0.594 mol, 42.8 g) were added to a reaction flask under nitrogen protection. The mixture was cooled to -78°C with liquid nitrogen, and n-butyllithium (1.1 eq, 64.05 g / mol, 0.015 mol, 0.96 g) was added dropwise. After reacting for 30 min, compound B (1 eq, 425.04 g / mol, 0.01 g) was added. 4 mol (6.0 g) and anhydrous THF (59.5 eq, 72.11 g / mol, 0.833 mol, 60 g) were mixed and added dropwise. The reaction was continued at -78℃ for 2 h, then quenched with ammonium chloride solution. After slowly restoring to room temperature, dichloromethane and water were added for extraction and separation. The dichloromethane phase was separated, washed with water several times, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain crude compound 4. After purification by column chromatography, compound D (3.43 g, yield 40.2%) was obtained. MS (EI): 569 (M + );

[0142] (3)

[0143] Compound D (1 eq, 569.10 g / mol, 0.005 mol, 3.0 g) was added to isopropanol (71.2 eq, 60.06 g / mol, 0.499 mol, 30.0 g, 10 times the mass of compound D), followed by dropwise addition of hydrochloric acid (117.4 eq, 36.5 g / mol, 0.822 mol, 30.0 g, 10 times the mass of compound D). The mixture was heated to an azeotropic reaction for 5 h, and then the isopropanol was removed by vacuum distillation. The mixture was filtered to give compound E (2.68 g, yield 97.4%). MS (EI): 551 (M + );

[0144] (4)

[0145] Under nitrogen protection, compounds E (1 eq, 551.09 g / mol, 0.004 mol, 2.0 g), F (1.1 eq, 169.09 g / mol, 0.005 mol, 0.85 g), sodium tert-butoxide (1.1 eq, 96.1 g / mol, 0.005 mol, 0.481 g), Pd2(dba)3 (0.05 eq, 915 g / mol, 0.0002 mol, 0.183 g), and tri-tert-butylphosphine (0.05 eq, 20 g / mol, 551.09 g / mol, 0.004 mol, 2.0 g) were prepared. 2.32 g / mol, 0.0002 mol, 0.041 g), and toluene (20.0 g, 10 times the mass of compound E) were added to the reaction flask. After the addition was complete, the mixture was heated to reflux and reacted for 5 h. After the reaction was completed, the mixture was cooled to room temperature, and 100 ml of water was added. The mixture was stirred for 15 min and then filtered to obtain the filtrate. The filtrate was separated to obtain the organic phase. The organic phase was dried with anhydrous magnesium sulfate, evaporated to dryness, and purified by column chromatography to obtain high-purity hole transport material 10 (1.63 g, yield 63.7%). MS (EI): 640 (M + ).

[0146] Example 11:

[0147]

[0148] The method for synthesizing hole transport material 11 is as follows: Step 1 is basically the same as in Example 9, and the remaining steps are as follows:

[0149] (2)

[0150] Compound C (1.1 eq, 328.05 g / mol, 0.015 mol, 4.92 g) and anhydrous THF (42.4 eq, 72.11 g / mol, 0.594 mol, 42.8 g) were added to a reaction flask under nitrogen protection. The mixture was cooled to -78°C with liquid nitrogen, and n-butyllithium (1.1 eq, 64.05 g / mol, 0.015 mol, 0.96 g) was added dropwise. After reacting for 30 min, compound B (1 eq, 425.04 g / mol, 0.01 g) was added. 4 mol (6.0 g) and anhydrous THF (59.5 eq, 72.11 g / mol, 0.833 mol, 60 g) were mixed and added dropwise. The reaction was continued at -78℃ for 2 h, then quenched with ammonium chloride solution. After slowly restoring to room temperature, dichloromethane and water were added for extraction and separation. The dichloromethane phase was separated, washed with water several times, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain crude compound 4. After purification by column chromatography, pure compound D (3.83 g, yield 37.9%) was obtained. MS (EI): 675 (M + );

[0151] (3)

[0152] Compound D (1 eq, 675.18 g / mol, 0.004 mol, 3.0 g) was added to isopropanol (71.2 eq, 60.06 g / mol, 0.499 mol, 30.0 g, 10 times the mass of compound D), followed by dropwise addition of hydrochloric acid (117.4 eq, 36.5 g / mol, 0.822 mol, 30.0 g, 10 times the mass of compound D). The mixture was heated to an azeotropic reaction for 5 h, and then the isopropanol was removed by vacuum distillation. The mixture was filtered to give compound E (2.55 g, yield 97.2%), MS (EI): 657 (M + );

[0153] (4)

[0154] Under nitrogen protection, compounds E (1 eq, 657.17 g / mol, 0.003 mol, 2.0 g), F (1.1 eq, 169.09 g / mol, 0.004 mol, 0.68 g), sodium tert-butoxide (1.1 eq, 96.1 g / mol, 0.004 mol, 0.384 g), Pd2(dba)3 (0.05 eq, 915 g / mol, 0.0002 mol, 0.183 g), and tri-tert-butylphosphine (0.05 eq, 20 g / mol, 657.17 g / mol, 0.003 mol, 2.0 g) were added. 2.32 g / mol, 0.0002 mol, 0.041 g), and toluene (20.0 g, 10 times the mass of compound E) were added to the reaction flask. After the addition was complete, the mixture was heated to reflux and reacted for 5 h. After the reaction was completed, the mixture was cooled to room temperature, and 100 ml of water was added. The mixture was stirred for 15 min and then filtered to obtain the filtrate. The filtrate was separated to obtain the organic phase. The organic phase was dried with anhydrous magnesium sulfate, evaporated to dryness, and purified by column chromatography to obtain high-purity hole transport material 11 (1.46 g, yield 65.2%). MS (EI): 746 (M + ).

[0155] Example 12:

[0156]

[0157] The method for synthesizing hole transport material 12 is as follows:

[0158] (1)

[0159] Compound A (1 eq, 347.13 g / mol, 0.029 mol, 10.0 g), dichloromethane (42 eq, 2.355 mol, 84.93 g / mol, 200.0 g), and concentrated sulfuric acid (0.05 eq, 98 g / mol, 0.14 g, 0.0014 mol) were added to a three-necked flask. After the addition was complete, N-bromosuccinimide (1.2 eq, 177.98 g / mol) was added in portions at room temperature with stirring. 6.19 g (0.0348 mol) was added to the reaction solution. After the addition was complete, the mixture was stirred at room temperature for 12 hours. After the reaction was completed according to HPLC monitoring, the reaction was stopped. Ethanol (193.8 eq, 10.853 mol, 46.07 g / mol, 500 g) was added to the reaction solution, and a solid precipitated. The solid was filtered to obtain a filter cake. The filter cake was heated in toluene for 3 hours, cooled to room temperature, and then filtered to obtain compound B (6.42 g, yield 52.1%). MS (EI): 425 (M + );

[0160] (2)

[0161] Compound C (1.1 eq, 328.05 g / mol, 0.015 mol, 4.92 g) and anhydrous THF (42.4 eq, 72.11 g / mol, 0.594 mol, 42.8 g) were added to a reaction flask under nitrogen protection. The mixture was cooled to -78°C with liquid nitrogen, and n-butyllithium (1.1 eq, 64.05 g / mol, 0.015 mol, 0.96 g) was added dropwise. After reacting for 30 min, compound B (1 eq, 425.04 g / mol, 0.01 g) was added. 4 mol (6.0 g) and anhydrous THF (59.5 eq, 72.11 g / mol, 0.833 mol, 60 g) were mixed and added dropwise. The reaction was continued at -78℃ for 2 h, then quenched with ammonium chloride solution. After slowly restoring to room temperature, dichloromethane and water were added for extraction and separation. The dichloromethane phase was separated, washed with water several times, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain crude compound 4. After purification by column chromatography, compound D (3.49 g, yield 36.9%) was obtained. MS (EI): 675 (M + );

[0162] (3)

[0163] Compound D (1 eq, 675.18 g / mol, 0.004 mol, 3.0 g) was added to isopropanol (71.2 eq, 60.06 g / mol, 0.499 mol, 30.0 g, 10 times the mass of compound D), followed by dropwise addition of hydrochloric acid (117.4 eq, 36.5 g / mol, 0.822 mol, 30.0 g, 10 times the mass of compound D). The mixture was heated to an azeotropic reaction for 5 h, and then the isopropanol was removed by vacuum distillation. The mixture was filtered to give compound E (2.54 g, yield 96.8%), MS (EI): 657 (M). + );

[0164] (4)

[0165] Under nitrogen protection, compounds E (1 eq, 657.17 g / mol, 0.003 mol, 2.0 g), F (1.1 eq, 169.09 g / mol, 0.004 mol, 0.68 g), sodium tert-butoxide (1.1 eq, 96.1 g / mol, 0.004 mol, 0.384 g), Pd2(dba)3 (0.05 eq, 915 g / mol, 0.0002 mol, 0.183 g), and tri-tert-butylphosphine (0.05 eq, ... 202.32 g / mol, 0.0002 mol, 0.041 g), and toluene (20.0 g, 10 times the mass of compound E) were added to the reaction flask. After the addition was complete, the mixture was heated to reflux and reacted for 5 h. After the reaction was completed, it was cooled to room temperature, and 100 ml of water was added. The mixture was stirred for 15 min and then filtered to obtain the filtrate. The filtrate was separated to obtain the organic phase. The organic phase was dried with anhydrous magnesium sulfate, evaporated to dryness, and purified by column chromatography to obtain high-purity compound 12 (1.52 g, yield 67.8%). MS (EI): 746 (M + ).

[0166] Example 13:

[0167]

[0168] The method for synthesizing hole transport material 37 is as follows:

[0169] (1)

[0170] Compound A (1 eq, 499.19 g / mol, 0.020 mol, 10.0 g), dichloromethane (117.8 eq, 2.355 mol, 84.93 g / mol, 200.0 g), and concentrated sulfuric acid (0.05 eq, 98 g / mol, 0.098 g, 0.001 mol) were added slowly to a three-necked flask. After the addition was complete, N-bromosuccinimide (1.2 eq, 177.98 g / mol) was added in several portions with stirring at room temperature. 4.27 g, 0.024 mol), after the addition of the reactants, the mixture was stirred at room temperature for 12 hours. After the reaction was complete as monitored by HPLC, the reaction was stopped, and ethanol (542.7 eq, 10.853 mol, 46.07 g / mol, 500 g) was added to the reaction solution. A solid precipitated, and the solid was filtered to obtain a filter cake. The filter cake was heated in toluene for 3 hours, cooled to room temperature, and then filtered to obtain compound B (6.13 g, yield 52.1%). MS (EI): 588 (M + );

[0171] (2)

[0172] Compound C (1.1 eq, 278.03 g / mol, 0.012 mol, 3.36 g) and anhydrous THF (42.4 eq, 72.11 g / mol, 0.509 mol, 36.7 g) were added to a reaction flask under nitrogen protection. The mixture was cooled to -78°C with liquid nitrogen, and n-butyllithium (1.1 eq, 64.05 g / mol, 0.012 mol, 0.769 g) was added dropwise. After reacting for 30 min, compound B (1 eq, 577.1 g / mol, 0.011 mol, 3.36 g) was added. The mixture of dichloromethane (6.0 g) and anhydrous THF (36.2 eq, 72.11 g / mol, 0.434 mol, 31.32 g) was added dropwise, and the reaction was continued at -78℃ for 2 h. The reaction was then quenched with ammonium chloride solution, and after slowly restoring to room temperature, dichloromethane and water were added for extraction and separation. The dichloromethane phase was separated, washed repeatedly with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain crude compound 4. After purification by column chromatography, pure compound D (3.31 g, yield 38.8%) was obtained. MS (EI): 777 (M + );

[0173] (3)

[0174] Compound D (1 eq, 777.22 g / mol, 0.004 mol, 3.0 g) was added to isopropanol (124.8 eq, 60.06 g / mol, 0.499 mol, 30.0 g, 10 times the mass of compound D), followed by dropwise addition of hydrochloric acid (205.5 eq, 36.5 g / mol, 0.822 mol, 30.0 g, 10 times the mass of compound D). The mixture was heated to an azeotropic reaction for 5 h, and then the isopropanol was removed by vacuum distillation. The mixture was filtered to give compound E (3.0 g, yield 96.4%), MS (EI): 759 (M). + );

[0175] (4)

[0176] Under nitrogen protection, compounds E (1 eq, 759.21 g / mol, 0.004 mol, 3.0 g), F (1.1 eq, 361.18 g / mol, 0.005 mol, 1.81 g), sodium tert-butoxide (1.1 eq, 96.1 g / mol, 0.005 mol, 0.481 g), Pd2(dba)3 (0.05 eq, 915 g / mol, 0.0002 mol, 0.18 g), and tri-tert-butylphosphine (0.05 eq, 202 g / mol) were added. 0.32 g / mol, 0.0002 mol, 0.041 g), and toluene (30.0 g, 10 times the mass of compound E) were added to the reaction flask. After the addition was complete, the mixture was heated to reflux and reacted for 5 h. After the reaction was completed, the mixture was cooled to room temperature, and 100 ml of water was added. The mixture was stirred for 15 min and then filtered to obtain the filtrate. The filtrate was separated to obtain the organic phase. The organic phase was dried with anhydrous magnesium sulfate, evaporated to dryness, and purified by column chromatography to obtain high-purity hole transport material 37 (2.72 g, yield 65.5%). MS (EI): 1040 (M + ).

[0177] Example 14:

[0178]

[0179] The method for synthesizing hole transport material 41 is as follows: Step 1 is basically the same as in Example 13, and the remaining steps are as follows:

[0180] (2)

[0181] Compound C (1.1 eq, 314.03 g / mol, 0.012 mol, 3.76 g) and anhydrous THF (42.4 eq, 72.11 g / mol, 0.509 mol, 36.7 g) were added to a reaction flask under nitrogen protection. The mixture was cooled to -78°C with liquid nitrogen, and n-butyllithium (1.1 eq, 64.05 g / mol, 0.012 mol, 0.77 g) was added dropwise. After reacting for 30 min, compound B (1 eq, 577.10 g / mol, 0.01 g / mol, 3.76 g) was added. 1 mol (6.0 g) and anhydrous THF (69.3 eq, 72.11 g / mol, 0.832 mol, 60 g) were mixed and added dropwise. The reaction was continued at -78℃ for 2 h, then quenched with ammonium chloride solution. After slowly restoring to room temperature, dichloromethane and water were added for extraction and separation. The dichloromethane phase was separated, washed with water several times, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain crude compound 4. After purification by column chromatography, compound D (3.68 g, yield 37.7%) was obtained. MS (EI): 675 (M + );

[0182] (3)

[0183] Compound D (1 eq, 813.22 g / mol, 0.004 mol, 3.0 g) was added to isopropanol (124.7 eq, 60.06 g / mol, 0.499 mol, 30.0 g, 10 times the mass of compound D), followed by dropwise addition of hydrochloric acid (205.5 eq, 36.5 g / mol, 0.822 mol, 30.0 g, 10 times the mass of compound D). The mixture was heated to an azeotropic reaction for 5 h, and then the isopropanol was removed by vacuum distillation. The mixture was filtered to give compound E (3.01 g, yield 94.8%), MS (EI): 795 (M). + );

[0184] (4)

[0185] Under nitrogen protection, compounds E (1 eq, 795.21 g / mol, 0.004 mol, 3.0 g), F (1.1 eq, 361.18 g / mol, 0.005 mol, 1.81 g), sodium tert-butoxide (1.1 eq, 96.1 g / mol, 0.005 mol, 0.481 g), Pd2(dba)3 (0.05 eq, 915 g / mol, 0.0002 mol, 0.18 g), and tri-tert-butylphosphine (0.05 eq, 202 g / mol, 3.0 g / mol, 0.004 mol, 3.0 g) were mixed. 0.32 g / mol, 0.0002 mol, 0.405 g), and toluene (30.0 g, 10 times the mass of compound E) were added to the reaction flask. After the addition was complete, the mixture was heated to reflux and reacted for 5 h. After the reaction was completed, it was cooled to room temperature, and 100 ml of water was added. The mixture was stirred for 15 min and then filtered to obtain the filtrate. The filtrate was separated to obtain the organic phase. The organic phase was dried with anhydrous magnesium sulfate, evaporated to dryness, and purified by column chromatography to obtain high-purity hole transport material 41 (2.90 g, yield 67.4%). MS (EI): 1076 (M + ).

[0186] Example 15:

[0187]

[0188] The method for synthesizing hole transport material 83 is as follows:

[0189] (1)

[0190] Compound A (1 eq, 347.13 g / mol, 0.029 mol, 10.0 g), dichloromethane (42 eq, 2.355 mol, 84.93 g / mol, 200.0 g), and concentrated sulfuric acid (0.05 eq, 98 g / mol, 0.14 g, 0.0014 mol) were added to a three-necked flask. After the addition was complete, N-bromosuccinimide (1.2 eq, 177.98 g / mol) was added in portions at room temperature with stirring. 6.19 g (0.0348 mol) was added to the reaction solution. After the addition was complete, the mixture was stirred at room temperature for 12 hours. After the reaction was completed according to HPLC monitoring, the reaction was stopped. Ethanol (193.8 eq, 10.853 mol, 46.07 g / mol, 500 g) was added to the reaction solution, and a solid precipitated. The solid was filtered to obtain a filter cake. The filter cake was heated in toluene for 3 hours, cooled to room temperature, and then filtered to obtain compound B (6.29 g, yield 51.1%). MS (EI): 425 (M + );

[0191] (2)

[0192] Compound C (1.1 eq, 314.03 g / mol, 0.015 mol, 4.71 g) and anhydrous THF (42.4 eq, 72.11 g / mol, 0.636 mol, 45.8 g) were added to a reaction flask under nitrogen protection. The mixture was cooled to -78°C with liquid nitrogen, and n-butyllithium (1.1 eq, 64.05 g / mol, 0.015 mol, 0.96 g) was added dropwise. After reacting for 30 min, compound B (1 eq, 425.04 g / mol, 0.01 g) was added. 4 mol (6.0 g) and anhydrous THF (59.4 eq, 72.11 g / mol, 0.832 mol, 60 g) were mixed and added dropwise. The reaction was continued at -78℃ for 2 h, then quenched with ammonium chloride solution. After slowly restoring to room temperature, dichloromethane and water were added for extraction and separation. The dichloromethane phase was separated, washed with water several times, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain crude compound 4. After purification by column chromatography, pure compound D (3.68 g, yield 37.7%) was obtained. MS (EI): 661 (M + );

[0193] (3)

[0194] Compound D (1 eq, 661.16 g / mol, 0.005 mol, 3.0 g) was added to isopropanol (99.8 eq, 60.06 g / mol, 0.499 mol, 30.0 g, 10 times the mass of compound D), followed by dropwise addition of hydrochloric acid (164.4 eq, 36.5 g / mol, 0.822 mol, 30.0 g, 10 times the mass of compound D). The mixture was heated to an azeotropic reaction for 5 h, and then the isopropanol was removed by vacuum distillation. The mixture was filtered to give compound E (3.18 g, yield 98.8%). MS (EI): 643 (M + );

[0195] (4)

[0196] Under nitrogen protection, compounds E (1 eq, 643.15 g / mol, 0.005 mol, 3.0 g), F (1.1 eq, 361.18 g / mol, 0.006 mol, 2.17 g), sodium tert-butoxide (1.1 eq, 96.1 g / mol, 0.005 mol, 0.481 g), Pd2(dba)3 (0.05 eq, 915 g / mol, 0.0003 mol, 0.275 g), and tri-tert-butylphosphine (0.05 eq, 20 g / mol, 643.15 g / mol, 0.005 mol, 3.0 g) were added. 2.32 g / mol, 0.0003 mol, 0.061 g, and toluene (30.0 g, 10 times the mass of compound E) were added to the reaction flask. After the addition was complete, the mixture was heated to reflux and reacted for 5 h. After the reaction was completed, it was cooled to room temperature, and 100 ml of water was added. The mixture was stirred for 15 min and then filtered to obtain the filtrate. The filtrate was separated to obtain the organic phase. The organic phase was dried with anhydrous magnesium sulfate, evaporated to dryness, and purified by column chromatography to obtain high-purity hole transport material 83 (3.05 g, yield 68.1%). MS (EI): 896 (M + ).

[0197] Example 16:

[0198]

[0199] The method for synthesizing hole transport material 102 is as follows:

[0200] (1)

[0201] Compound A (1 eq, 180.06 g / mol, 0.056 mol, 10.0 g), dichloromethane (42 eq, 2.355 mol, 84.93 g / mol, 200.0 g), and concentrated sulfuric acid (0.05 eq, 98 g / mol, 0.27 g, 0.0028 mol) were added to a three-necked flask. After the addition was complete, N-bromosuccinimide (1.2 eq, 177.98 g / mol) was added in several portions with stirring at room temperature. 11.96 g (0.0672 mol) was added, and the mixture was stirred at room temperature for 12 hours. After the reaction was completed, the reaction was stopped by HPLC monitoring. Ethanol (193.8 eq, 10.853 mol, 46.07 g / mol, 500 g) was added to the reaction solution, and a solid precipitated. The solid was filtered to obtain a filter cake, which was then heated in toluene for 3 hours, cooled to room temperature, and filtered to obtain compound B (6.79 g, yield 47.2%). MS (EI): 257 (M + );

[0202] (2)

[0203] Compound C (1.1 eq, 286.00 g / mol, 0.025 mol, 7.15 g) and anhydrous THF (42.4 eq, 72.11 g / mol, 0.975 mol, 70.3 g) were added to a reaction flask under nitrogen protection. The mixture was cooled to -78°C with liquid nitrogen, and n-butyllithium (1.1 eq, 64.05 g / mol, 0.025 mol, 1.62 g) was added dropwise. After reacting for 30 min, compound B (1 eq, 257.97 g / mol, 0.02 g) was added. 3 mol (6.0 g) and anhydrous THF (36.2 eq, 72.11 g / mol, 0.832 mol, 60 g) were mixed and added dropwise. The reaction was continued at -78℃ for 2 h, then quenched with ammonium chloride solution. After slowly restoring to room temperature, dichloromethane and water were added for extraction and separation. The dichloromethane phase was separated, washed with water several times, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain crude compound 4. After purification by column chromatography, pure compound D (3.90 g, yield 33.5%) was obtained. MS (EI): 466 (M + );

[0204] (3)

[0205] Compound D (1 eq, 466.06 g / mol, 0.006 mol, 3.0 g) was added to isopropanol (83.2 eq, 60.06 g / mol, 0.499 mol, 30.0 g, 10 times the mass of compound D), followed by dropwise addition of hydrochloric acid (137 eq, 36.5 g / mol, 0.822 mol, 30.0 g, 10 times the mass of compound D). The mixture was heated to an azeotropic reaction for 5 h, and then the isopropanol was removed by vacuum distillation. The mixture was filtered to give compound E (2.65 g, yield 98.5%), MS (EI): 448 (M + );

[0206] (4)

[0207] Under nitrogen protection, compounds E (1 eq, 448.05 g / mol, 0.005 mol, 2.0 g), F (1.1 eq, 335.13 g / mol, 0.006 mol, 2.01 g), sodium tert-butoxide (1.1 eq, 96.1 g / mol, 0.006 mol, 0.577 g), Pd2(dba)3 (0.05 eq, 915 g / mol, 0.00025 mol, 0.229 g), and tri-tert-butylphosphine (0.05 eq, 20 g / mol, 448.05 g / mol, 0.005 mol, 2.0 g) were subjected to nitrogen treatment. 2.32 g / mol, 0.00025 mol, 0.051 g, and toluene (20.0 g, 10 times the mass of compound E) were added to the reaction flask. After the addition was complete, the mixture was heated to reflux and reacted for 5 h. After the reaction was completed, it was cooled to room temperature, and 100 ml of water was added. The mixture was stirred for 15 min and then filtered to obtain the filtrate. The filtrate was separated to obtain the organic phase. The organic phase was dried with anhydrous magnesium sulfate, evaporated to dryness, and purified by column chromatography to obtain high-purity hole transport material 102 (2.32 g, yield 65.9%). MS (EI): 703 (M + ).

[0208] Example 17:

[0209]

[0210] The method for synthesizing hole transport material 122 is as follows: Steps 1-3 are basically the same as in Example 2, and the remaining steps are as follows:

[0211] (4)

[0212] Under nitrogen protection, compounds E (1 eq, 440.08 g / mol, 0.007 mol, 3.0 g), F (1.1 eq, 321.15 g / mol, 0.008 mol, 2.57 g), sodium tert-butoxide (1.1 eq, 96.1 g / mol, 0.008 mol, 0.769 g), Pd2(dba)3 (0.05 eq, 915 g / mol, 0.00035 mol, 0.32 g), and tri-tert-butylphosphine (0.05 eq, 202 g / mol) were added. 0.32 g / mol, 0.00035 mol, 0.071 g), and toluene (30.0 g, 10 times the mass of compound E) were added to the reaction flask. After the addition was complete, the mixture was heated to reflux and reacted for 5 h. After the reaction was completed, it was cooled to room temperature, and 100 ml of water was added. The mixture was stirred for 15 min and then filtered to obtain the filtrate. The filtrate was separated to obtain the organic phase. The organic phase was dried with anhydrous magnesium sulfate, evaporated to dryness, and purified by column chromatography to obtain high-purity hole transport material 122 (3.18 g, yield 66.8%). MS (EI): 681 (M + ).

[0213] Example 18:

[0214]

[0215] The method for synthesizing hole transport material 123 is as follows: Steps 1-3 are basically the same as in Example 3, and the remaining steps are as follows:

[0216] (4)

[0217] Under nitrogen protection, compounds E (1 eq, 440.08 g / mol, 0.007 mol, 3.0 g), F (1.1 eq, 378.22 g / mol, 0.008 mol, 3.03 g), sodium tert-butoxide (1.1 eq, 96.1 g / mol, 0.008 mol, 0.769 g), Pd2(dba)3 (0.05 eq, 915 g / mol, 0.00035 mol, 0.32 g), and tri-tert-butylphosphine (0.05 eq, 202 g / mol) were added. 0.32 g / mol, 0.00035 mol, 0.071 g), and toluene (30.0 g, 10 times the mass of compound E) were added to the reaction flask. After the addition was complete, the mixture was heated to reflux and reacted for 5 h. After the reaction was completed, it was cooled to room temperature, and 100 ml of water was added. The mixture was stirred for 15 min and then filtered to obtain the filtrate. The filtrate was separated to obtain the organic phase. The organic phase was dried with anhydrous magnesium sulfate, evaporated to dryness, and purified by column chromatography to obtain high-purity hole transport material 123 (3.12 g, yield 60.3%). MS (EI): 738 (M + ).

[0218] Example 19:

[0219]

[0220] The method for synthesizing hole transport material 134 is as follows: Steps 1-3 are basically the same as in Example 6, and the remaining steps are as follows:

[0221] (4)

[0222] Under nitrogen protection, compounds E (1 eq, 490.09 g / mol, 0.004 mol, 2.0 g), F (1.1 eq, 321.15 g / mol, 0.005 mol, 1.61 g), sodium tert-butoxide (1.1 eq, 96.1 g / mol, 0.005 mol, 0.481 g), Pd2(dba)3 (0.05 eq, 915 g / mol, 0.0002 mol, 0.18 g), and tri-tert-butylphosphine (0.05 eq, 202 g / mol) were added. 0.32 g / mol, 0.0002 mol, 0.405 g), and toluene (20.0 g, 10 times the mass of compound E) were added to the reaction flask. After the addition was complete, the mixture was heated to reflux and reacted for 5 h. After the reaction was completed, it was cooled to room temperature, and 100 ml of water was added. The mixture was stirred for 15 min and then filtered to obtain the filtrate. The filtrate was separated to obtain the organic phase. The organic phase was dried with anhydrous magnesium sulfate, evaporated to dryness, and purified by column chromatography to obtain high-purity hole transport material 134 (1.91 g, yield 65.3%). MS (EI): 731 (M + ).

[0223] Example 20:

[0224]

[0225] The method for synthesizing hole transport material 139 is as follows: Steps 1-3 are basically the same as in Example 7, and the remaining steps are as follows:

[0226] (4)

[0227] Under nitrogen protection, compounds E (1 eq, 490.09 g / mol, 0.004 mol, 2.0 g), F (1.1 eq, 375.20 g / mol, 0.005 mol, 1.88 g), sodium tert-butoxide (1.1 eq, 96.1 g / mol, 0.005 mol, 0.481 g), Pd2(dba)3 (0.05 eq, 915 g / mol, 0.0002 mol, 0.18 g), and tri-tert-butylphosphine (0.05 eq, 202 g / mol) were added. 0.32 g / mol, 0.0002 mol, 0.405 g), and toluene (20.0 g, 10 times the mass of compound E) were added to the reaction flask. After the addition was complete, the mixture was heated to reflux and reacted for 5 h. After the reaction was completed, it was cooled to room temperature, and 100 ml of water was added. The mixture was stirred for 15 min and then filtered to obtain the filtrate. The filtrate was separated to obtain the organic phase. The organic phase was dried with anhydrous magnesium sulfate, evaporated to dryness, and purified by column chromatography to obtain high-purity hole transport material 139 (1.99 g, yield 63.6%). MS (EI): 785 (M + ).

[0228] Example 21:

[0229]

[0230] The method for synthesizing hole transport material 149 is as follows: Steps 1-3 are basically the same as in Example 3, and the remaining steps are as follows:

[0231] (4)

[0232] Under nitrogen protection, compounds E (1 eq, 440.08 g / mol, 0.007 mol, 3.0 g), F (1.1 eq, 426.17 g / mol, 0.008 mol, 3.41 g), sodium tert-butoxide (1.1 eq, 96.1 g / mol, 0.008 mol, 0.769 g), Pd2(dba)3 (0.05 eq, 915 g / mol, 0.00035 mol, 0.32 g), and tri-tert-butylphosphine (0.05 eq, 202 g / mol) were added. 0.32 g / mol, 0.00035 mol, 0.071 g, and toluene (30.0 g, 10 times the mass of compound E) were added to the reaction flask. After the addition was complete, the mixture was heated to reflux and reacted for 5 h. After the reaction was completed, it was cooled to room temperature, and 100 ml of water was added. The mixture was stirred for 15 min and then filtered to obtain the filtrate. The filtrate was separated to obtain the organic phase. The organic phase was dried with anhydrous magnesium sulfate, evaporated to dryness, and purified by column chromatography to obtain high-purity hole transport material 149 (3.46 g, yield 62.8%). MS (EI): 788 (M + ).

[0233] Example 22:

[0234]

[0235] The method for synthesizing hole transport material 151 is as follows: Steps 1-3 are basically the same as in Example 7, and the remaining steps are as follows:

[0236] (4)

[0237] Under nitrogen protection, compounds E (1 eq, 490.09 g / mol, 0.004 mol, 2.0 g), F (1.1 eq, 426.17 g / mol, 0.005 mol, 2.13 g), sodium tert-butoxide (1.1 eq, 96.1 g / mol, 0.005 mol, 0.481 g), Pd2(dba)3 (0.05 eq, 915 g / mol, 0.0002 mol, 0.18 g), and tri-tert-butylphosphine (0.05 eq, 202 g / mol) were added. 0.32 g / mol, 0.0002 mol, 0.405 g), and toluene (20.0 g, 10 times the mass of compound E) were added to the reaction flask. After the addition was complete, the mixture was heated to reflux and reacted for 5 h. After the reaction was completed, it was cooled to room temperature, and 100 ml of water was added. The mixture was stirred for 15 min and then filtered to obtain the filtrate. The filtrate was separated to obtain the organic phase. The organic phase was dried with anhydrous magnesium sulfate, evaporated to dryness, and purified by column chromatography to obtain high-purity hole transport material 151 (2.07 g, yield 61.7%). MS (EI): 838 (M + ).

[0238] Performance testing:

[0239] Application Example 1:

[0240] ITO was used as the anode substrate material for the reflective layer, and its surface was sequentially treated with water, acetone, and N2 plasma. A hole injection layer (HIL) with a thickness of 10 nm was deposited on top of the ITO anode substrate. A hole transport layer (HTL) with a thickness of 120 nm was formed by evaporating hole transport material 1 from Example 1 of this invention on top of the hole injection layer (HIL). 9,10-Bis(2-naphthyl)anthraces (ADN) was used as the main blue light material, and BD-1 was used as the blue light dopant (BD-1 was used at 5% of the weight of ADN). A 20 nm thick light-emitting layer is formed by evaporating a hole transport layer (HTL) at different rates; an electron transport layer (ETL) with a thickness of 35 nm is obtained by evaporating a mixture of ETM and LiQ in a 1:1 ratio; an electron injection layer (EIL) with a thickness of 2 nm is formed by evaporating LiQ on top of the electron transport layer (ETL); then a cathode with a thickness of 15 nm is obtained by evaporating a mixture of magnesium (Mg) and silver (Ag) in a 9:1 ratio; a 65 nm thick DNTPD is deposited on the cathode sealing layer; in addition, the cathode surface is sealed with a UV-curable adhesive and a sealing film containing a desiccant to protect the organic electroluminescent device from the influence of atmospheric oxygen or moisture. Thus, an organic electroluminescent device is prepared.

[0241]

[0242]

[0243] Application Example 2-22

[0244] Using hole transport materials 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 37, 41, 83, 102, 122, 123, 134, 139, 149, and 151 from Examples 2-22 of the present invention as hole transport layer (HTL) materials, and with the other parts being the same as in Application Example 1, organic electroluminescent devices of Application Examples 2-22 were fabricated accordingly.

[0245] Compare with Examples 1, 2, 3, and 4

[0246] The difference from Application Example 1 is that compounds 151 and 118 from HTL-1, HTL-2, and prior art CN 102448926 are used instead of the compounds of the present invention as the hole transport layer; otherwise, they are the same as in Application Example 1.

[0247] The organic electroluminescent device manufactured in the above application example and the organic electroluminescent device manufactured in the comparative example have the characteristic of operating at a current density of 10 mA / cm². 2 The results were measured under the specified conditions and are shown in Table 1.

[0248] Table 1:

[0249]

[0250]

[0251] As shown in Table 1 above, the experimental comparison data reveals that the organic electroluminescent device prepared using the hole transport material described in this invention exhibits a significantly lower voltage and a significantly higher luminous efficiency compared to the control example. This demonstrates that the compound of this invention can greatly reduce the driving voltage of the device, thereby significantly reducing power consumption and significantly improving luminous efficiency. Furthermore, by reducing the driving voltage, the lifetime of the organic electroluminescent device is significantly improved.

Claims

1. A hole transport material, characterized in that, Its structural formula is shown below: ； Where a is a fused substituted or unsubstituted benzene ring; R1, R2, R3, and R4 are each independently phenyl, biphenyl, naphthyl, fluorenyl, oxofluorenyl, 9,9-dimethylfluorenyl, carbazolyl, o-diphenylphenyl, trideuterylmethylbiphenyl, methylbiphenyl, and triphenylamino. R5 is tert-butyl; W represents O or S; m is 0, and n is 0 or 1.

2. The hole transport material as described in claim 1, characterized in that, The hole transport material is any one of the following compounds with the following structural formulas: 。 3. The hole transport material as described in claim 1, characterized in that, Its preparation method includes the following steps: （1） ； Compound A and dichloromethane were slowly added to concentrated sulfuric acid. After the addition was complete, N-bromosuccinimide was added in several portions while stirring at room temperature. After the addition was complete, the reaction was stirred at room temperature for 10-15 hours. Ethanol was added to the reaction solution, and a solid was precipitated. The solid was filtered to obtain a filter cake. The filter cake was heated with toluene for 2-5 hours, cooled to room temperature, and then filtered to obtain compound B. （2） ； Under inert gas protection, compound C and anhydrous THF were added to a reaction flask, the temperature was lowered to -60 to -90°C, n-butyllithium was added dropwise, and after reacting for 20-40 min, compound B and anhydrous THF were mixed and added dropwise. The reaction was continued at -60 to -90°C for 1-3 h, ammonium chloride solution was added to quench the reaction, and the temperature was slowly restored to room temperature. Dichloromethane and water were added for extraction and separation. After washing with water and drying, the crude product of compound D was obtained by concentration under reduced pressure. After purification by column chromatography, pure product of compound D was obtained. （3） ； Compound D was added to isopropanol, followed by the addition of hydrochloric acid. The mixture was heated to an azeotropic reaction for 4-6 hours, and then the isopropanol was removed by vacuum distillation. The mixture was then filtered to obtain compound E. （4） ； Under inert gas protection, compound E, with the general structural formula […], was […]. Compound F, sodium tert-butoxide, Pd2(dba)3, tri-tert-butylphosphine, and toluene were added to a reaction flask. After the addition was complete, the mixture was heated to reflux and reacted for 4-6 hours. After the reaction was completed, the mixture was cooled to room temperature, water was added, and the mixture was stirred for 10-20 minutes. The mixture was then filtered to obtain a filtrate. The filtrate was separated to obtain an organic phase. The organic phase was dried, evaporated to dryness, and purified by column chromatography to obtain the high-purity final product G.

4. The use of the hole transport material as described in any one of claims 1-2 in the fabrication of organic electroluminescent devices.

5. An organic electroluminescent device, characterized in that, It includes a cathode, an anode, a light-emitting layer, and a hole transport layer, wherein the hole transport layer contains a hole transport material as described in any one of claims 1-2.

6. A lighting device, characterized in that, It contains the organic electroluminescent device as described in claim 5.

7. An electronic display device, characterized in that, It contains the organic electroluminescent device as described in claim 5.

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