A method for preparing a diarylcarbazole material

Abstract

This invention discloses a method for preparing a diarylcarbazole material, relating to the field of organic light-emitting device technology. The method includes: obtaining intermediate A through a nitration reaction of 4-bromo-2-chloro-1-fluorobenzene; obtaining coupling intermediate B through a Suzuki coupling reaction of intermediate A and 1-naphthoboric acid; preparing intermediate C through a nitro cyclization reaction of intermediate B; coupling intermediate C with iodobenzene or iodobenzene derivative D to form intermediate E; preparing pinacol borate intermediate F using intermediate E; obtaining intermediate H through a Suzuki coupling reaction of intermediate F and o-bromoaniline or o-bromoaniline derivative G; cyclizing intermediate H under alkaline conditions to obtain intermediate I; and coupling intermediate I with a haloaryl derivative J to obtain the diarylcarbazole material. The preparation route provided by this invention has high reaction selectivity, produces a single product, has no obvious reaction defects, and avoids the problems of isomers in cyclization reactions and polybromination in bromination reactions.

Description

Technical Field

[0001] This invention relates to the field of organic light-emitting device technology, and specifically to a method for preparing a material based on diarylcarbazole. Background Technology

[0002] Organic light-emitting diodes (OLEDs) have many advantages, such as high resolution, wide viewing angle, full-color display, flexibility, and ultra-thin and lightweight design. They are widely used in information display, solid-state lighting, sensing and other fields, and have a huge market prospect.

[0003] Luminescent materials are the core of OLED technology. They are generally constructed using a host-guest doping process, where the host material transports charges and generates excitons, while the guest molecules capture these excitons to emit light. With the widespread application of OLED technology, higher demands are being placed on the luminescent performance and strength of materials, such as in large-screen televisions and automotive displays. These applications require materials with higher luminescent efficiency and stability, capable of withstanding harsh environments such as sunlight and vibrations. However, current luminescent materials still suffer from insufficient luminescent efficiency, inadequate stability, and low glass transition temperature (Tg). Therefore, there is an urgent need to develop luminescent materials with higher luminescent efficiency and stability.

[0004] Diarylcarbazole materials are an important class of nitrogen-containing heterocyclic compounds. They are modified by introducing aryl groups onto the carbazole group, which enhances the rigidity of the conjugated fused ring structure, facilitates hole transport, and has a high triplet energy level and good electron donation capability. They are ideal materials for the development of host materials. Their devices have the characteristics of low power consumption, long driving lifetime and high luminous efficiency. They have obvious structural advantages and great research value.

[0005] There are three existing methods for preparing diarylcarbazole materials.

[0006] Method 1:

[0007]

[0008] Problems: (1) The ring-closing reaction from L4 to L5 has two ring-closing positions, which will produce 5-20% of ring-closing isomers. The reaction selectivity is poor, resulting in waste of materials; (2) The synthesis of L1, L3, L4, L5 and L6 all require expensive catalysts. Among them, L4 to L5 requires 4% mol palladium acetate to achieve the ideal effect, which greatly increases the synthesis cost. See WO2015099486A1 for details.

[0009] Method 2:

[0010]

[0011] Problems encountered: The M3→M4 nitro ring-closing reaction involves two ring-closing sites, generating approximately 30% of the ring-closing isomers. Furthermore, the target product M4 is more soluble than the isomers, making purification exceptionally difficult (see WO2018021737A1 for details). A similar method to convert M2 into boric acid also presents the same problems, making purification challenging (see CN202110915767.7 for details).

[0012] Method 3:

[0013]

[0014] Problems: (1) During the N2→N3 bromination reaction, polybrominated impurities are easily generated in the naphthalene ring, which is not conducive to subsequent purification; (2) Since the N5→N6 ring-closing reaction is selective, in order to avoid isomerization, only para-substituted aniline can be selected, which greatly limits the expansion of diarylcarbazole materials. See CN116535408A for details.

[0015] In summary, existing technologies all face the problem of isomer formation when synthesizing diarylcarbazole materials: the isomers generated in Method 1 (from L4 to L5) and Method 2 (from M3 to M4) need to be purified and removed, resulting in material waste; in Method 3 (from N5 to N6), the research scope of derivatives is limited in order to avoid the formation of isomers. At the same time, the above three methods use a large amount of expensive palladium catalysts, resulting in high costs and hindering industrial production. Summary of the Invention

[0016] To address the shortcomings of the aforementioned background technology, the main technical problem solved by this invention is the generation of isomers and polybromination in the existing processes for preparing diarylcarbazole materials. This invention provides a method for preparing diarylcarbazole materials. The preparation route provided by this invention exhibits high reaction selectivity, yields a single product, has no obvious reaction defects, and avoids the problems of isomer formation in cyclization reactions and polybromination in bromination reactions. Excluding the final step of derivative purification, the yield is 70-75%, and the yields of other intermediates are all above 80%. In key steps, this method outperforms known routes with cyclization reaction yields of 50-70%.

[0017] The first objective of this invention is to provide a method for preparing a diarylcarbazole material, comprising the following steps: obtaining intermediate A by nitration of 4-bromo-2-chloro-1-fluorobenzene; obtaining coupling intermediate B by Suzuki coupling reaction of intermediate A and 1-naphthoboric acid; preparing intermediate C by nitro cyclization reaction of intermediate B; synthesizing intermediate E from intermediate C using iodobenzene or iodobenzene derivative D; preparing pinacol borate intermediate F from intermediate E; obtaining intermediate H by Suzuki coupling reaction of intermediate F and o-bromoaniline or o-bromoaniline derivative G; cyclizing intermediate H under alkaline conditions to obtain intermediate I; and coupling intermediate I with haloaryl derivative J to obtain diarylcarbazole material K.

[0018] The synthesis route is as follows:

[0019]

[0020] R1 to R3 are independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted alkyl of C1 to C30, substituted or unsubstituted alkenyl of C2 to C30, substituted or unsubstituted alkynyl of C2 to C30, substituted or unsubstituted cycloalkyl of C3 to C30, substituted or unsubstituted alkoxy of C1 to C30, substituted or unsubstituted silyl of C1 to C30, substituted or unsubstituted aryl of C6 to C60, substituted or unsubstituted heteroaryl of C3 to C30, or a ring A that shares one side with an adjacent phenyl group to form a fused ring.

[0021] The ring A is selected from benzene rings, 3- to 7-membered saturated or partially unsaturated carbon rings, 3- to 7-membered saturated or partially unsaturated heterocycles, C6-C60 fused-ring aryl groups, or C3-C30 fused-ring heteroaryl groups.

[0022] The second objective of this invention is to provide a material based on diarylcarbazole.

[0023] The third objective of this invention is to provide an application of diarylcarbazole-based materials in organic light-emitting devices.

[0024] Compared with the prior art, the beneficial effects of the present invention are:

[0025] This invention provides a method for preparing diarylcarbazole materials. This method has high reaction selectivity, produces a single product, has no obvious reaction defects, and does not have the problems of cyclization reaction isomers and polybromination reaction. Except for the purification of the derivative in the last step, the yield is 70-75%, and the yield of the remaining intermediates is all above 80%. In the key steps, it is superior to the known route with a cyclization reaction yield of 50-70%.

[0026] The preparation route provided by this invention prepares intermediate H from intermediate F using the most widely used Suzuki coupling method. The brominated derivative of the raw material is easy to obtain, which enriches the range of modification fragments and greatly expands the development field of diarylcarbazole materials.

[0027] The preparation route provided by this invention prepares intermediate I from intermediate H by using fluorobenzene and aniline for cyclization under potassium tert-butoxide alkaline conditions. No catalyst is required, and the raw materials are inexpensive and readily available. Compared with the chlorine cyclization used in route one and the bromine cyclization used in route three, which both require 2-4% palladium acetate catalysis (palladium acetate unit price: 240 yuan / g), this method greatly saves production costs and has significant advantages. Attached Figure Description

[0028] Figure 1 The above is the H-NMR spectrum of synthesis example K-3 of the present invention;

[0029] Figure 2 This is a structural diagram of the organic electroluminescent device in the device embodiment of the present invention;

[0030] Wherein, 1-substrate; 2-anode; 3-hole injection layer; 4-hole transport layer; 5-light-emitting layer; 6-electron transport layer; 7-electron injection layer; 8-cathode. Detailed Implementation

[0031] To enable those skilled in the art to better understand and implement the technical solutions of the present invention, the present invention will be further described below in conjunction with specific embodiments and accompanying drawings. However, the embodiments described are not intended to limit the present invention.

[0032] The purpose of this invention is to provide a diarylcarbazole material and to address the problems of isomerization and polybromination in the preparation process of diarylcarbazole materials, thereby providing a new preparation method and expanding the research scope of diarylcarbazole materials.

[0033] The first aspect of this invention provides a method for preparing a diarylcarbazole-based material, comprising the following steps:

[0034] Intermediate A was obtained by nitration of 4-bromo-2-chloro-1-fluorobenzene;

[0035] Coupling intermediate B was obtained by using intermediate A and 1-naphthoboronic acid via a Suzuki coupling reaction;

[0036] Intermediate C was prepared from intermediate B via a nitro cyclization reaction.

[0037] Intermediate C is synthesized into intermediate E using iodobenzene or iodobenzene derivative D;

[0038] Pinaryl borate intermediate F was prepared using intermediate E;

[0039] Intermediate F and o-bromoaniline or o-bromoaniline derivative G are coupled via a Suzuki reaction to obtain intermediate H;

[0040] Intermediate H was cyclized under alkaline conditions to obtain intermediate I;

[0041] The intermediate I and the haloaryl derivative J were coupled to obtain the diarylcarbazole material K.

[0042] The synthesis route is as follows:

[0043]

[0044] R1 to R3 are independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted alkyl of C1 to C30, substituted or unsubstituted alkenyl of C2 to C30, substituted or unsubstituted alkynyl of C2 to C30, substituted or unsubstituted cycloalkyl of C3 to C30, substituted or unsubstituted alkoxy of C1 to C30, substituted or unsubstituted silyl of C1 to C30, substituted or unsubstituted aryl of C6 to C60, substituted or unsubstituted heteroaryl of C3 to C30, or a ring A that shares one side with an adjacent phenyl group to form a fused ring.

[0045] The ring A is selected from benzene rings, 3- to 7-membered saturated or partially unsaturated carbon rings, 3- to 7-membered saturated or partially unsaturated heterocycles, C6-C60 fused-ring aryl groups, or C3-C30 fused-ring heteroaryl groups.

[0046] The first step of this invention uses 4-bromo-2-chloro-1-fluorobenzene as the starting material for a nitration reaction. Due to the directing effect of the bromine atom and the para-occupation of the fluorine atom, the electrophilic reaction can only occur at the ortho position of the bromine atom, resulting in a single product. The second step involves coupling to the 1-position of the naphthalene ring. The formation of a five-membered ring structure is more stable, thus enabling high selectivity for the nitro ring-closing position in the third step. The fourth step introduces a phenyl group to avoid the influence of the carbazole structure on subsequent reactions. The fifth step uses a palladium-catalyzed reaction to prepare a borate ester from the brominated product. The sixth step selects an o-bromoarylamine for the coupling reaction, ensuring that the ring-closing reaction in the seventh step has a unique structure, avoiding the formation of isomers due to two ring-closing positions. At the same time, because the chlorine atom is locked in advance at the starting material stage, the problem of polybromination in the later bromination is avoided.

[0047] The iodobenzene or iodobenzene derivative D comprises the following structure:

[0048]

[0049] The o-bromoaniline or o-bromoaniline derivative G comprises one of the following structures:

[0050]

[0051] The haloaryl derivative J comprises one of the following structures:

[0052]

[0053] Intermediate A is prepared according to the following steps: Dichloromethane, concentrated sulfuric acid and 4-bromo-2-chloro-1-fluorobenzene are added sequentially to a reactor, stirring is started, nitrogen gas is introduced, 68% concentrated nitric acid is added dropwise at 0°C, the temperature is raised to reflux for 1-2 hours, the temperature is lowered to 25±5°C, the lower acid layer is separated, the organic phase is washed with water, washed with sodium bicarbonate solution, washed with water again and concentrated, then n-hexane is added, the temperature is raised to reflux and stirred for 1-2 hours, the temperature is lowered to 0±5°C, crystallization is carried out for 1-2 hours, filtered and dried to obtain intermediate A;

[0054] Intermediate B is prepared according to the following steps: Intermediate A, 1-naphthoboric acid, potassium carbonate, toluene, ethanol, and pure water are added to a reactor, stirring is started, nitrogen gas is introduced, tetra(triphenylphosphine)palladium is added, the temperature is raised to 75±5℃ and reacted for 3-6 hours, the temperature is lowered to 35±5℃, the aqueous layer is separated and washed with water, the temperature is maintained at 60±5℃ and passed through a silica gel column, concentrated at normal pressure, ethanol is added and the temperature is raised to reflux and stirred for 1-2 hours, the temperature is lowered to 25±5℃, filtered, and dried to obtain intermediate B;

[0055] Intermediate C is prepared according to the following steps: Intermediate B, triphenylphosphine, and o-dichlorobenzene are added to a reactor, stirring is started, nitrogen gas is introduced, the temperature is raised to 160±10℃ and reacted for 8-12 hours, the temperature is lowered to 90±5℃, o-dichlorobenzene is removed by vacuum distillation, the temperature is lowered to 70±5℃, ethanol is added, the mixture is refluxed and stirred for 1-2 hours, the temperature is lowered to 25±5℃, filtered, the filter cake is refluxed and stirred with n-hexane for 1-2 hours, the temperature is lowered to 25±5℃, filtered, and dried to obtain intermediate C.

[0056] Intermediate E is prepared according to the following steps: Intermediate C, iodobenzene derivative D, cuprous iodide, 1,10-phenanthroline, potassium carbonate, and dioxane are added to a reactor. Stirring is started, nitrogen gas is introduced, and the mixture is heated to reflux and kept at that temperature for 8-12 hours. The temperature is then lowered to 50±5℃, filtered, and the filter cake is washed with dioxane. The dioxane is concentrated and evaporated. Toluene and water are added for extraction and phase separation. The toluene phase is concentrated at atmospheric pressure, ethanol is added, and the mixture is heated to reflux and stirred for 1-2 hours. The temperature is then lowered to 25±5℃, filtered, and dried to obtain intermediate E.

[0057] Intermediate F is prepared according to the following steps: Intermediate E, pinacol diborate, tris(benzylacetone)dipalladium, X-Phos, potassium acetate, and dioxane are added to a reactor. Stirring is started, nitrogen gas is introduced, and the material is heated to reflux for 6-8 hours. The temperature is then lowered to 50±5℃, filtered, and the filter cake is washed with dioxane. The dioxane is concentrated and evaporated to remove the dioxane. Dichloromethane and water are added for phase separation. The dichloromethane phase is concentrated at atmospheric pressure, and n-hexane is added. The temperature is raised to reflux and slurryed for 1-2 hours, then lowered to 25±5℃, filtered, and dried to obtain intermediate F.

[0058] The intermediate H is prepared according to the following steps: intermediate F, o-bromoaniline or o-bromoaniline derivative G, potassium carbonate, toluene and pure water are added to a reactor, stirring is started, and palladium dichloride of bistriphenylphosphine is added under nitrogen protection. The mixture is heated to reflux for 2-4 hours, cooled to 50±5℃, allowed to stand to separate the aqueous layer, the organic phase is washed with water, kept at 60±5℃ and passed through a silica gel column and the silica gel is washed off, the organic layers are combined, toluene is removed by evaporation under normal pressure, ethanol is added and refluxed for 1-2 hours, the mixture is cooled to 25±5℃, filtered, and off-white intermediate H is obtained.

[0059] Intermediate I is prepared according to the following steps: Intermediate H, potassium tert-butoxide, and dimethyl sulfoxide are added to a reactor, stirring is started, nitrogen gas is introduced, the material is heated to 90±5℃ and kept at this temperature for 2-4 hours, then cooled to 25±5℃, water is added to separate the material, stirring is carried out for 0.5-1 hours, and the mixture is filtered. The filter cake is washed with water. The filter cake is transferred to a reactor, chlorobenzene is added, and the mixture is heated to distill the water to dissolve the material. The mixture is kept at 120±5℃ and passed through a silica gel column. The mixture is concentrated at normal pressure, cooled to 25±5℃, and kept at this temperature for 1-2 hours to crystallize. The mixture is then filtered to obtain intermediate I.

[0060] The diarylcarbazole material K is prepared according to the following steps: intermediate I, haloaryl derivative J, sodium tert-butoxide and toluene are added to a reactor, stirring is started, nitrogen gas is introduced, and when the material is heated to 60±5℃, 10% tri-tert-butylphosphine toluene solution and tris(benzylideneacetone)dipalladium are added, and the temperature is raised to reflux for 1-2 hours. After the reaction is completed, the temperature is lowered to 50±5℃, water is added to quench the reaction, water is separated, the organic phase is washed once with water, and the solution is kept at 80±5℃ and passed through a silica gel column and the silica gel is washed. The filtrates are combined, concentrated and toluene is evaporated, the temperature is lowered to 70±5℃, ethanol is added, the temperature is lowered to 25±5℃, and the solution is filtered to obtain an off-white solid. The solution is then recrystallized 2-3 times with toluene / ethyl acetate to obtain the off-white solid diarylcarbazole material K.

[0061] The Pd catalyst is palladium acetate, tris(dibenzylideneacetone)palladium, tetratriphenylphosphine palladium, [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloride dichloromethane complex, or bis(triphenylphosphine)palladium dichloride.

[0062] A second aspect of the present invention provides a diarylcarbazole-based material, the general structural formula of which is shown in formula (K) below:

[0063]

[0064] In formula (K), R1 to R3 are independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted alkyl groups of C1 to C30, substituted or unsubstituted alkenyl groups of C2 to C30, substituted or unsubstituted alkynyl groups of C2 to C30, substituted or unsubstituted cycloalkyl groups of C3 to C30, substituted or unsubstituted alkoxy groups of C1 to C30, substituted or unsubstituted silyl groups of C1 to C30, substituted or unsubstituted aryl groups of C6 to C60, substituted or unsubstituted heteroaryl groups of C3 to C30, or ring A that shares one side with an adjacent phenyl group to form a fused ring; the substituents include substituted C1-C60 groups. The substituents in the alkyl, substituted C3-C60 cycloalkyl, substituted C1-C60 heteroalkyl, substituted C6-C60 aryl, substituted C3-C60 heteroaryl, substituted C6-C30 arylene, substituted C6-C30 heteroarylene, substituted C6-C60 aromatic amino, and substituted C3-C60 heteroaryl groups are selected from one or a combination of at least two of the following: deuterium, halogen, cyano, C1-C12 alkyl, C3-C60 cycloalkyl, C6-C60 aryl, C3-C60 heteroaryl, C6-C60 aromatic amino, and C3-C60 heteroaryl groups.

[0065] The ring A is selected from benzene rings, 3- to 7-membered saturated or partially unsaturated carbon rings, 3- to 7-membered saturated or partially unsaturated heterocycles, C6-C60 fused-ring aryl groups, or C3-C30 fused-ring heteroaryl groups.

[0066] The diarylcarbazole-based material includes any one of the following compounds:

[0067]

[0068]

[0069] A third aspect of the present invention provides an application of diarylcarbazole-based materials in organic light-emitting materials.

[0070] It should be noted that, unless otherwise specified, the experimental methods used in this invention are all conventional methods; and the reagents and materials used, unless otherwise specified, are all commercially available.

[0071] Example 1

[0072] This embodiment provides a method for preparing a diarylcarbazole material, as shown in K-1:

[0073]

[0074] The synthetic route for the diarylcarbazole material shown in K-1 is as follows:

[0075]

[0076] Synthesis A: 300 mL of dichloromethane, 120 g of concentrated sulfuric acid, and 60 g (0.286 mol, 1 eq) of 4-bromo-2-chloro-1-fluorobenzene were added sequentially to a 1 L reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, nitrogen gas was introduced, and 26.5 g (0.286 mol, 1 eq) of 68% concentrated nitric acid was added dropwise at 0 °C. The reaction was exothermic; the temperature was controlled below 15 °C during the dropwise addition. After the addition was complete, the temperature was raised to reflux, and the reaction continued for 2 h, monitoring the reaction of the starting material 4-bromo-2-chloro-1-fluorobenzene until complete. After HPLC verification, the mixture was allowed to stand and separate into layers. The lower sulfuric acid layer was removed. The dichloromethane phase was washed once each with 100 mL of water, 100 mL of saturated sodium bicarbonate aqueous solution, and 100 mL of water. Dichloromethane was concentrated and evaporated, then 90 mL of n-hexane was added, the mixture was heated to reflux and stirred for 1 hour, then cooled to 0°C to crystallize for 2 hours, filtered, washed with an appropriate amount of n-hexane, and dried to obtain 60.8 g of yellow-green solid with a purity of 98.4% and a yield of 83.5%.

[0077] Synthesis B: Add 300 mL of toluene, 150 mL of pure water, potassium carbonate (66 g, 0.477 mol, 2.0 eq), 1-naphthoboric acid (49.2 g, 0.286 mol, 1.2 eq), intermediate A (60.8 g, 0.239 mol, 1.0 eq), and 50 mL of ethanol to a 1 L reaction flask equipped with a stirrer, thermometer, and reflux condenser to rinse the flask walls. Start the stirrer and add tetrakis(triphenylphosphine)palladium (2.8 g, 0.0024 mol, 0.01 eq) under continuous N2 protection. Then, heat to reflux for 3 h. Monitor the reaction of intermediate A by HPLC until complete. After the HPLC results are satisfactory, allow the mixture to stand to separate the aqueous layer. Wash the organic phase once with 200 mL of water, maintain the temperature at 60 °C, and pass it through a 5 cm thick silica gel column. Elute the silica gel with an appropriate amount of toluene. The organic layers were combined, and toluene was removed by evaporation under normal pressure until a yellow-green solid precipitated. Then, 150 mL of ethanol was added and the mixture was refluxed and stirred for 1 hour. After cooling to room temperature, the mixture was filtered to obtain 64.7 g of yellow-green solid with a purity of 99.2% and a yield of 90%.

[0078] Synthesis C: Intermediate B (64.7 g, 0.215 mol, 1.0 eq), triphenylphosphine (169 g, 0.644 mol, 3.0 eq), and 500 mL of o-dichlorobenzene were added to a 1 L reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, and nitrogen gas was continuously introduced. The mixture was heated to reflux and reacted for 12 h. HPLC monitoring showed that intermediate B was essentially complete. After passing HPLC, the mixture was cooled to 90 °C, and o-dichlorobenzene was removed by vacuum distillation. The mixture was then cooled to 70 °C, and 500 mL of ethanol was added. The mixture was refluxed and stirred for 1 h. The mixture was then cooled to room temperature, filtered, and the filter cake was further refluxed with 300 mL of n-hexane for 1 h. The mixture was then cooled to room temperature, filtered, and dried to obtain 47.5 g of a light brown solid with a purity of 97.6% and a yield of 82%.

[0079] Synthesis of E-1: Intermediate C (47.5 g, 0.176 mol, 1.0 eq), iodobenzene D-1 (54 g, 0.264 mol, 1.5 eq), cuprous iodide (3.4 g, 0.0176 mol, 0.1 eq), 1,10-phenanthroline (3.2 g, 0.0176 mol, 0.1 eq), potassium carbonate (48.6 g, 0.352 mol, 2.0 eq), and 450 mL of dioxane were added to a 1 L reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, nitrogen gas was continuously introduced, the material was heated to reflux, and the reaction was maintained at this temperature for 9 h. The reaction of intermediate C was monitored by HPLC to ensure complete reaction. The mixture was cooled to 50°C, filtered, and the filter cake was washed with 100 mL of dioxane. The dioxane was then concentrated and evaporated to remove it. 400 mL of toluene and 200 mL of water were added for extraction and phase separation. The toluene phase was concentrated at atmospheric pressure, and 300 mL of ethanol was added. The mixture was heated to reflux and stirred for 1 hour, then cooled to 25°C, filtered, and dried to obtain 51.2 g of off-white solid with a purity of 98.4% and a yield of 84%.

[0080] Synthesis of F-1: Intermediate E-1 (51.2 g, 0.148 mol, 1.0 eq), pinacol diboronate (41.4 g, 0.163 mol, 1.1 eq), tris(benzylacetone)dipalladium (1.4 g, 0.0015 mol, 0.01 eq), X-Phos (2.1 g, 0.0044 mol, 0.03 eq), potassium acetate (28.4 g, 0.296 mol, 2.0 eq), and 450 mL of dioxane were added to a 1 L reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, nitrogen gas was introduced, and the mixture was heated to reflux and kept at this temperature for 6 h. The reaction of intermediate E-1 was monitored by HPLC until it was complete. The mixture was cooled to 50°C, filtered, and the filter cake was washed with 100 mL of dioxane. The dioxane was then concentrated and evaporated to remove it. 400 mL of dichloromethane and 200 mL of water were added for extraction and phase separation. The organic phase of dichloromethane was concentrated at atmospheric pressure, and 300 mL of n-hexane was added. The mixture was heated to reflux and stirred for 1 hour. The mixture was then cooled to 25°C, filtered, and dried to obtain 55.1 g of an off-white solid with an HPLC purity of 98.8% and a yield of 85.1%.

[0081] Synthesis of H-1: Intermediate F-1 (55.1 g, 0.126 mol, 1.0 eq), o-bromoaniline G-1 (22.8 g, 0.132 mol, 1.05 eq), potassium carbonate (34.8 g, 0.252 mol, 2.0 eq), 400 mL toluene, and 150 mL pure water were added to a 1 L reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, and under continuous nitrogen protection, palladium dichloride bis(triphenylphosphine) dichloride (0.9 g, 0.0013 mol, 0.01 eq) was added. The mixture was then heated to reflux for 3 h, and the reaction of intermediate F-1 was monitored by HPLC to ensure complete reaction. After passing the HPLC test, the mixture was cooled to 50 °C, allowed to stand to separate the aqueous layer, and the organic phase was washed once with 100 mL of water. The mixture was then held at 60 °C and passed through a 5 cm thick silica gel column, with the silica gel washed with an appropriate amount of toluene. The organic layers were combined, toluene was removed by evaporation under normal pressure, 150 mL of ethanol was added and the mixture was refluxed and stirred for 1 hour. The mixture was then cooled to 25 °C and filtered to obtain 43.6 g of off-white solid with a purity of 98.2% and a yield of 86%.

[0082] Synthesis of I-1: Intermediate H-1 (43.6 g, 0.108 mol, 1.0 eq), potassium tert-butoxide (24.3 g, 0.216 mol, 2.0 eq), and 100 mL of dimethyl sulfoxide were added to a 500 mL reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, and nitrogen gas was introduced. The mixture was heated to 90 °C and maintained at this temperature for 3 h. HPLC monitoring was used to ensure the complete reaction of intermediate H-1. After passing HPLC tests, the mixture was cooled to room temperature, 250 mL of water was added, and the mixture was stirred for 0.5 h. The mixture was then filtered, and the filter cake was thoroughly washed with water. The filter cake was transferred to a flask, and 300 mL of chlorobenzene was added. The mixture was heated to 130 °C and passed through a 5 cm thick silica gel column. The solution was then concentrated to 100 mL, cooled to 25 °C, and allowed to crystallize for 1 h. The mixture was then filtered to obtain 33.5 g of a white solid with a purity of 99.4% and a yield of 81%.

[0083] Synthesis of K-1: Intermediate I-1 (33.5 g, 0.088 mol, 1.0 eq), bromobenzene J-1 (20.7 g, 0.132 mol, 1.5 eq), sodium tert-butoxide (12.6 g, 0.132 mol, 1.5 eq), and 500 mL of toluene were added to a 1 L reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, nitrogen gas was introduced, and when the material temperature reached 60 °C, 10% tri-tert-butylphosphine toluene solution (7.1 g, 0.0035 mol, 0.04 eq) and tris(benzylideneacetone) dipalladium (0.8 g, 0.0009 mol, 0.01 eq) were added, and the mixture was then heated to reflux for 2 h. HPLC was used to monitor the complete reaction of intermediate I-1. After the reaction was completed, the temperature was lowered to 50°C, and 100 mL of water was added to quench the reaction. The water was separated, and the organic phase was washed with water again. The mixture was kept at 80°C and passed through a 5 cm silica gel column, with the silica gel being washed off. The filtrates were combined, concentrated, and toluene was removed by evaporation. The temperature was lowered to 80°C, and 160 mL of ethanol was added. The temperature was lowered to 25°C, and the mixture was filtered to obtain a white wet solid. The solid was then recrystallized twice from toluene and ethyl acetate to obtain 30 g of white solid with a purity of 99.93% and a yield of 75%.

[0084] Example 2

[0085] This embodiment provides a method for preparing a diarylcarbazole material, as shown in K-2:

[0086]

[0087] The K-2 preparation steps of the diarylcarbazole material shown are different from the preparation steps of the diarylcarbazole material shown in K-1 provided in Example 1, except that:

[0088] Replace compound J-1 in step 8 of Example 1 with the compound represented by formula J-2. The synthetic route for K-2 is as follows:

[0089]

[0090] Synthesis of K-2: Intermediate I-1 (33.5 g, 0.088 mol, 1.0 eq), p-bromobiphenyl J-2 (22.6 g, 0.097 mol, 1.1 eq), sodium tert-butoxide (12.6 g, 0.132 mol, 1.5 eq), and 500 mL of toluene were added to a 1 L reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, nitrogen gas was introduced, and when the material temperature reached 60 °C, 10% tri-tert-butylphosphine toluene solution (7.1 g, 0.0035 mol, 0.04 eq) and tris(benzylideneacetone) dipalladium (0.8 g, 0.0009 mol, 0.01 eq) were added, and the mixture was then heated to reflux for 2 h. Samples were taken for HPLC monitoring to ensure the complete reaction of intermediate I-1. After the reaction was completed, the temperature was lowered to 50°C, and 100 mL of water was added to quench the reaction. The water was separated, and the organic phase was washed with water again. The mixture was kept at 80°C and passed through a 5 cm silica gel column, with the silica gel being washed off. The filtrates were combined, concentrated, and toluene was removed by evaporation. The temperature was lowered to 80°C, and 160 mL of ethanol was added. The temperature was lowered to 25°C, and the mixture was filtered to obtain an off-white solid. After recrystallization twice with toluene and ethyl acetate, 33.8 g of off-white solid was obtained with a purity of 99.93% and a yield of 72%.

[0091] Example 3

[0092] This embodiment provides a method for preparing a diarylcarbazole material, as shown in K-3:

[0093]

[0094] The synthetic route for the diarylcarbazole material shown in K-3 is as follows:

[0095]

[0096] The only difference between the preparation steps of K-3 and the preparation steps of the diarylcarbazole material shown in Example 1 (K-1) is:

[0097] Replace compound J-1 in step 8 of Example 1 with the compound shown in formula J-3.

[0098] Synthesis of K-3: Intermediate I-1 (33.5 g, 0.088 mol, 1.0 eq), 4-bromophenyldibenzofuran J-3 (31.4 g, 0.097 mol, 1.1 eq), sodium tert-butoxide (12.6 g, 0.132 mol, 1.5 eq), and 500 mL of toluene were added to a 1 L reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, nitrogen gas was introduced, and when the material temperature reached 60 °C, 10% tri-tert-butylphosphine toluene solution (7.1 g, 0.0035 mol, 0.04 eq) and tris(benzylideneacetone) dipalladium (0.8 g, 0.0009 mol, 0.01 eq) were added, and the mixture was then heated to reflux for 2 h. HPLC was used to monitor the complete reaction of intermediate I-1. After the reaction was completed, the temperature was lowered to 50°C, and 100 mL of water was added to quench the reaction. The water was separated, and the organic phase was washed with water again. The mixture was kept at 80°C and passed through a 5 cm silica gel column, with the silica gel being washed off. The filtrates were combined, concentrated, and toluene was removed by evaporation. The temperature was lowered to 80°C, and 160 mL of ethanol was added. The temperature was lowered to 25°C, and the mixture was filtered to obtain an off-white solid. After recrystallization twice with toluene and ethyl acetate, 40.7 g of off-white solid was obtained with a purity of 99.91% and a yield of 74%.

[0099] See Figure 1 The image shows the H-NMR spectrum of K-3.

[0100] Example 4

[0101] This embodiment provides a method for preparing a diarylcarbazole material, as shown in K-4:

[0102]

[0103] The synthetic route for the diarylcarbazole material shown in K-4 is as follows:

[0104]

[0105] The only difference between the preparation steps of K-4 and the preparation steps of the diarylcarbazole material shown in K-1 provided in Example 1 is that:

[0106] Replace compound J-1 in step 8 of Example 1 with the compound shown in formula J-4.

[0107] Synthesis of K-4: Intermediate I-1 (33.5 g, 0.088 mol, 1.0 eq), 3-bromophenyldibenzofuran J-4 (31.4 g, 0.097 mol, 1.1 eq), sodium tert-butoxide (12.6 g, 0.132 mol, 1.5 eq), and 500 mL of toluene were added to a 1 L reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, nitrogen gas was introduced, and when the material temperature reached 60 °C, 10% tri-tert-butylphosphine toluene solution (7.1 g, 0.0035 mol, 0.04 eq) and tris(benzylideneacetone) dipalladium (0.8 g, 0.0009 mol, 0.01 eq) were added, and the mixture was then heated to reflux for 2 h. HPLC was used to monitor the complete reaction of intermediate I-1. After the reaction was completed, the temperature was lowered to 50°C, and 100 mL of water was added to quench the reaction. The water was separated, and the organic phase was washed with water again. The mixture was kept at 80°C and passed through a 5 cm silica gel column, with the silica gel being washed off. The filtrates were combined, concentrated, and toluene was removed by evaporation. The temperature was lowered to 80°C, and 160 mL of ethanol was added. The temperature was lowered to 25°C, and the mixture was filtered to obtain an off-white solid. After recrystallization twice with toluene and ethyl acetate, 39.6 g of off-white solid was obtained with a purity of 99.93% and a yield of 72%.

[0108] Example 5

[0109] This embodiment provides a method for preparing a diarylcarbazole material, as shown in K-5:

[0110]

[0111] The synthetic route for the diarylcarbazole material shown in K-5 is as follows:

[0112]

[0113] The only difference between the preparation steps of K-5 and the preparation steps of the diarylcarbazole material shown in K-1 provided in Example 1 is that:

[0114] Replace compound J-1 in step 8 of Example 1 with the compound shown in formula J-5.

[0115] Synthesis of K-5: Intermediate I-1 (33.5 g, 0.088 mol, 1.0 eq), p-bromobenznaphthalene J-5 (27.5 g, 0.097 mol, 1.1 eq), sodium tert-butoxide (12.6 g, 0.132 mol, 1.5 eq), and 500 mL of toluene were added to a 1 L reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, nitrogen gas was introduced, and when the material temperature reached 60 °C, 10% tri-tert-butylphosphine toluene solution (7.1 g, 0.0035 mol, 0.04 eq) and tris(benzylideneacetone) dipalladium (0.8 g, 0.0009 mol, 0.01 eq) were added, and the mixture was then heated to reflux for 2 h. HPLC was used to monitor the complete reaction of intermediate I-1. After the reaction was completed, the temperature was lowered to 50°C, and 100 mL of water was added to quench the reaction. The water was separated, and the organic phase was washed with water again. The mixture was kept at 80°C and passed through a 5 cm silica gel column, with the silica gel being washed off. The filtrates were combined, concentrated, and toluene was removed by evaporation. The temperature was lowered to 80°C, and 160 mL of ethanol was added. The temperature was lowered to 25°C, and the mixture was filtered to obtain an off-white solid. After recrystallization twice with toluene and ethyl acetate, 38.6 g of off-white solid with a purity of 99.90% and a yield of 75% was obtained.

[0116] Example 6

[0117] This embodiment provides a method for preparing a diarylcarbazole material, as shown in K-6:

[0118]

[0119] The synthetic route for the diarylcarbazole material shown in K-6 is as follows:

[0120]

[0121] Synthesis of E-6: Intermediate C (47.5 g, 0.176 mol, 1.0 eq), 2-iodonaphthalene D-6 (49 g, 0.194 mol, 1.1 eq), cuprous iodide (3.4 g, 0.0176 mol, 0.1 eq), 1,10-phenanthroline (3.2 g, 0.0176 mol, 0.1 eq), potassium carbonate (48.6 g, 0.352 mol, 2.0 eq), and 450 mL of dioxane were added to a 1 L reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, nitrogen gas was continuously introduced, and the mixture was heated to reflux and maintained at this temperature for 9 h. The reaction of intermediate C was monitored by HPLC until complete. The mixture was then cooled to 50°C, filtered, and the filter cake was washed with 100 mL of dioxane. The dioxane was then concentrated and evaporated to remove it. 400 mL of toluene and 200 mL of water were added for extraction and phase separation. The toluene phase was concentrated at atmospheric pressure, and 300 mL of ethanol was added. The mixture was heated to reflux and stirred for 1 hour, then cooled to 25°C, filtered, and dried to obtain 57.2 g of off-white solid with a purity of 98.1% and a yield of 82%.

[0122] Synthesis of F-6: Intermediate E-6 (57.2 g, 0.144 mol, 1.0 eq), pinacol diborate (40.2 g, 0.158 mol, 1.1 eq), tris(benzylacetone)dipalladium (1.4 g, 0.0015 mol, 0.01 eq), X-Phos (2.1 g, 0.0044 mol, 0.03 eq), potassium acetate (27.6 g, 0.288 mol, 2.0 eq), and 450 mL of dioxane were added to a 1 L reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, nitrogen gas was introduced, and the mixture was heated to reflux and maintained at this temperature for 6 h. The reaction of intermediate E-6 was monitored by HPLC until complete. The mixture was then cooled to 50°C, filtered, and the filter cake was washed with 100 mL of dioxane. The dioxane was then concentrated and evaporated to remove it. 400 mL of dichloromethane and 200 mL of water were added for extraction and phase separation. The organic phase of dichloromethane was concentrated at atmospheric pressure, and 300 mL of n-hexane was added. The mixture was heated to reflux and stirred for 1 hour. The mixture was then cooled to 25°C, filtered, and dried to obtain 58.8 g of an off-white solid with an HPLC purity of 98.2% and a yield of 84%.

[0123] Synthesis of H-6: Intermediate F-6 (58.8 g, 0.121 mol, 1.0 eq), o-bromoaniline G-1 (21.8 g, 0.127 mol, 1.05 eq), potassium carbonate (33.4 g, 0.242 mol, 2.0 eq), 400 mL toluene, and 150 mL pure water were added to a 1 L reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, and under continuous nitrogen protection, palladium dichloride bis(triphenylphosphine) (0.9 g, 0.0013 mol, 0.01 eq) was added. The mixture was then heated to reflux for 3 h. HPLC monitoring was used to ensure the complete reaction of intermediate F-6. After passing HPLC tests, the mixture was cooled to 50 °C, allowed to stand to separate the aqueous layer, and the organic phase was washed once with 100 mL of water. The mixture was then held at 60 °C and passed through a 5 cm thick silica gel column, with the silica gel washed with an appropriate amount of toluene. The organic layers were combined, toluene was removed by evaporation under normal pressure, 150 mL of ethanol was added and refluxed for 1 hour, the mixture was cooled to 25 °C and filtered to obtain 45.4 g of off-white solid with a purity of 98.6% and a yield of 83%.

[0124] Synthesis of I-6: Intermediate H-6 (45.4 g, 0.101 mol, 1.0 eq), potassium tert-butoxide (22.7 g, 0.202 mol, 2.0 eq), and 100 mL of dimethyl sulfoxide were added to a 500 mL reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, and nitrogen gas was introduced. The mixture was heated to 90 °C and maintained at this temperature for 3 h. HPLC monitoring was used to ensure the complete reaction of intermediate H-6. After passing HPLC tests, the mixture was cooled to room temperature, 250 mL of water was added, and the mixture was stirred for 0.5 h. The mixture was then filtered, and the filter cake was thoroughly washed with water. The filter cake was transferred to a flask, and 300 mL of chlorobenzene was added. The mixture was heated to 130 °C and passed through a 5 cm thick silica gel column. The solution was then concentrated to 100 mL, cooled to 25 °C, and allowed to crystallize for 1 h. The mixture was then filtered to obtain 35.3 g of a white solid with a purity of 99.0% and a yield of 81%.

[0125] Synthesis of K-6: Intermediate I-6 (35.3 g, 0.082 mol, 1.0 eq), bromobenznaphthalene J-5 (25.5 g, 0.091 mol, 1.1 eq), sodium tert-butoxide (11.8 g, 0.123 mol, 1.5 eq), and 500 mL of toluene were added to a 1 L reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, nitrogen gas was introduced, and the mixture was heated to 60 °C. Then, a 10% tri-tert-butylphosphine toluene solution (7.0 g, 0.0035 mol, 0.04 eq) and tris(benzylacetone)dipalladium (0.8 g, 0.0009 mol, 0.01 eq) were added, and the mixture was refluxed for 2 h. HPLC was used to monitor the complete reaction of intermediate I-6. After the reaction was completed, the temperature was lowered to 50°C, and 100 mL of water was added to quench the reaction. The water was separated, and the organic phase was washed with water again. The mixture was kept at 80°C and passed through a 5 cm silica gel column, with the silica gel being washed off. The filtrates were combined, concentrated, and toluene was removed by evaporation. The temperature was lowered to 80°C, and 160 mL of ethanol was added. The temperature was lowered to 25°C, and the mixture was filtered to obtain an off-white solid. The solid was then recrystallized twice from toluene and ethyl acetate to obtain 37.5 g of off-white solid with a purity of 99.92% and a yield of 72%.

[0126] Example 7

[0127] This embodiment provides a method for preparing a diarylcarbazole material, as shown in K-7:

[0128]

[0129] The synthetic route for the diarylcarbazole material shown in K-7 is as follows:

[0130]

[0131] Synthesis of E-7: Intermediate C (47.5 g, 0.176 mol, 1.0 eq), m-iodobiphenyl D-7 (54.2 g, 0.194 mol, 1.1 eq), cuprous iodide (3.4 g, 0.0176 mol, 0.1 eq), 1,10-phenanthroline (3.2 g, 0.0176 mol, 0.1 eq), potassium carbonate (48.6 g, 0.352 mol, 2.0 eq), and 450 mL of dioxane were added to a 1 L reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, nitrogen gas was continuously introduced, the material was heated to reflux, and the reaction was maintained at this temperature for 9 h. The reaction of intermediate C was monitored by HPLC to ensure complete reaction. The mixture was cooled to 50°C, filtered, and the filter cake was washed with 100 mL of dioxane. The dioxane was then concentrated and evaporated to remove it. 400 mL of toluene and 200 mL of water were added for extraction and phase separation. The toluene phase was concentrated at atmospheric pressure, and 300 mL of ethanol was added. The mixture was heated to reflux and stirred for 1 hour, then cooled to 25°C, filtered, and dried to obtain 60.2 g of off-white solid with a purity of 98.6% and a yield of 81%.

[0132] Synthesis of F-7: Intermediate E-7 (60.2 g, 0.143 mol, 1.0 eq), pinacol diborate (40.2 g, 0.158 mol, 1.1 eq), tris(benzylacetone)dipalladium (1.4 g, 0.0015 mol, 0.01 eq), X-Phos (2.1 g, 0.0044 mol, 0.03 eq), potassium acetate (27.6 g, 0.288 mol, 2.0 eq), and 450 mL of dioxane were added to a 1 L reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, nitrogen gas was introduced, and the material was heated to reflux and kept at this temperature for 6 h. The reaction of intermediate E-7 was monitored by HPLC to ensure complete reaction. The mixture was cooled to 50°C, filtered, and the filter cake was washed with 100 mL of dioxane. The dioxane was then concentrated and evaporated to remove it. 400 mL of dichloromethane and 200 mL of water were added for extraction and phase separation. The organic phase of dichloromethane was concentrated at atmospheric pressure, and 300 mL of n-hexane was added. The mixture was heated to reflux and stirred for 1 hour. The mixture was then cooled to 25°C, filtered, and dried to obtain 60.2 g of an off-white solid with an HPLC purity of 98.3% and a yield of 82%.

[0133] Synthesis of H-7: Intermediate F-7 (60.2 g, 0.117 mol, 1.0 eq), o-bromoaniline G-1 (21.1 g, 0.123 mol, 1.05 eq), potassium carbonate (32.3 g, 0.234 mol, 2.0 eq), 400 mL toluene, and 150 mL pure water were added to a 1 L reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, and under continuous nitrogen protection, palladium dichloride bis(triphenylphosphine) dichloride (0.9 g, 0.0013 mol, 0.01 eq) was added. The mixture was then heated to reflux for 3 h, and the reaction of intermediate F-7 was monitored by HPLC to ensure complete reaction. After passing the HPLC test, the mixture was cooled to 50 °C, allowed to stand to separate the aqueous layer, and the organic phase was washed once with 100 mL of water. The mixture was then held at 60 °C and passed through a 5 cm thick silica gel column, with the silica gel washed with an appropriate amount of toluene. The organic layers were combined, toluene was removed by evaporation under normal pressure, 150 mL of ethanol was added and the mixture was refluxed and stirred for 1 hour. The mixture was then cooled to 25 °C and filtered to obtain 44.2 g of off-white solid with a purity of 97.8% and a yield of 79%.

[0134] Synthesis of I-7: Intermediate H-7 (44.2 g, 0.092 mol, 1.0 eq), potassium tert-butoxide (20.7 g, 0.184 mol, 2.0 eq), and 100 mL of dimethyl sulfoxide were added to a 500 mL reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, nitrogen gas was introduced, and the mixture was heated to 90 °C and maintained at this temperature for 3 h. HPLC monitoring was used to ensure the complete reaction of intermediate H-7. After passing HPLC tests, the mixture was cooled to room temperature, 250 mL of water was added, and the mixture was stirred for 0.5 h. The mixture was then filtered, and the filter cake was thoroughly washed with water. The filter cake was transferred to a flask, and 300 mL of chlorobenzene was added. The mixture was heated to 130 °C and passed through a 5 cm thick silica gel column. The solution was then concentrated to 100 mL, cooled to 25 °C, and crystallized for 1 h. The mixture was filtered to obtain 32.9 g of an off-white solid with a purity of 99.0% and a yield of 78%.

[0135] Synthesis of K-7: Intermediate I-7 (32.9 g, 0.072 mol, 1.0 eq), p-bromobenznaphthalene J-5 (22.3 g, 0.079 mol, 1.1 eq), sodium tert-butoxide (10.4 g, 0.108 mol, 1.5 eq), and 500 mL of toluene were added to a 1 L reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, nitrogen gas was introduced, and the mixture was heated to 60 °C. Then, a 10% tri-tert-butylphosphine toluene solution (5.7 g, 0.003 mol, 0.04 eq) and tris(benzylacetone)dipalladium (0.66 g, 0.0007 mol, 0.01 eq) were added, and the mixture was refluxed for 2 h. HPLC was used to monitor the complete reaction of intermediate I-7. After the reaction was completed, the temperature was lowered to 50°C, and 100 mL of water was added to quench the reaction. The water was separated, and the organic phase was washed with water again. The mixture was kept at 80°C and passed through a 5 cm silica gel column, with the silica gel being washed off. The filtrates were combined, concentrated, and toluene was removed by evaporation. The temperature was lowered to 80°C, and 160 mL of ethanol was added. The temperature was lowered to 25°C, and the mixture was filtered to obtain an off-white solid. After recrystallization twice with toluene and ethyl acetate, 34.7 g of off-white solid was obtained with a purity of 99.91% and a yield of 73%.

[0136] Example 8

[0137] This embodiment provides a method for preparing a diarylcarbazole material, as shown in K-8:

[0138]

[0139] The synthetic route for the diarylcarbazole material shown in K-8 is as follows:

[0140]

[0141] Synthesis of E-8: Intermediate C (47.5 g, 0.176 mol, 1.0 eq), p-iodobiphenyl D-8 (54.2 g, 0.194 mol, 1.1 eq), cuprous iodide (3.4 g, 0.0176 mol, 0.1 eq), 1,10-phenanthroline (3.2 g, 0.0176 mol, 0.1 eq), potassium carbonate (48.6 g, 0.352 mol, 2.0 eq), and 450 mL of dioxane were added to a 1 L reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, nitrogen gas was continuously introduced, and the material was heated to reflux and the reaction was maintained at this temperature for 9 h. The reaction of intermediate C was monitored by HPLC to ensure complete reaction. The mixture was cooled to 50°C, filtered, and the filter cake was washed with 100 mL of dioxane. The dioxane was then concentrated and evaporated to remove it. 400 mL of toluene and 200 mL of water were added for extraction and phase separation. The toluene phase was concentrated at atmospheric pressure, and 300 mL of ethanol was added. The mixture was heated to reflux and stirred for 1 hour, then cooled to 25°C, filtered, and dried to obtain 60.7 g of off-white solid with a purity of 98.6% and a yield of 82%.

[0142] Synthesis of F-8: Intermediate E-8 (60.7 g, 0.144 mol, 1.0 eq), pinacol diboronate (40.2 g, 0.158 mol, 1.1 eq), tris(benzylacetone)dipalladium (1.4 g, 0.0015 mol, 0.01 eq), X-Phos (2.1 g, 0.0044 mol, 0.03 eq), potassium acetate (27.6 g, 0.288 mol, 2.0 eq), and 450 mL of dioxane were added to a 1 L reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, nitrogen gas was introduced, and the mixture was heated to reflux and kept at this temperature for 6 h. The reaction of intermediate E-8 was monitored by HPLC until it was complete. The mixture was cooled to 50°C, filtered, and the filter cake was washed with 100 mL of dioxane. The dioxane was then concentrated and evaporated to remove it. 400 mL of dichloromethane and 200 mL of water were added for extraction and phase separation. The organic phase of dichloromethane was concentrated at atmospheric pressure, and 300 mL of n-hexane was added. The mixture was heated to reflux and stirred for 1 hour. The mixture was then cooled to 25°C, filtered, and dried to obtain 59.3 g of an off-white solid with an HPLC purity of 97.8% and a yield of 80%.

[0143] Synthesis of H-8: Intermediate F-8 (59.3 g, 0.115 mol, 1.0 eq), o-bromoaniline G-1 (20.8 g, 0.121 mol, 1.05 eq), potassium carbonate (31.8 g, 0.231 mol, 2.0 eq), 400 mL toluene, and 150 mL pure water were added to a 1 L reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, and under continuous nitrogen protection, palladium dichloride bis(triphenylphosphine) dichloride (0.9 g, 0.0013 mol, 0.01 eq) was added. The mixture was then heated to reflux for 3 h, and the reaction of intermediate F-8 was monitored by HPLC to ensure complete reaction. After passing the HPLC test, the mixture was cooled to 50 °C, allowed to stand to separate the aqueous layer, and the organic phase was washed once with 100 mL of water. The mixture was then held at 60 °C and passed through a 5 cm thick silica gel column, with the silica gel washed with an appropriate amount of toluene. The organic layers were combined, toluene was removed by evaporation under normal pressure, and then 150 mL of ethanol was added and refluxed for 1 hour. The mixture was cooled to 25 °C and filtered to obtain 44.7 g of off-white solid with a purity of 98.2% and a yield of 81%.

[0144] Synthesis of I-8: Intermediate H-8 (44.7 g, 0.093 mol, 1.0 eq), potassium tert-butoxide (20.7 g, 0.184 mol, 2.0 eq), and 100 mL of dimethyl sulfoxide were added to a 500 mL reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, nitrogen gas was introduced, and the mixture was heated to 90 °C and maintained at this temperature for 3 h. HPLC monitoring was used to ensure the complete reaction of intermediate H-8. After passing HPLC tests, the mixture was cooled to room temperature, 250 mL of water was added, and the mixture was stirred for 0.5 h. The mixture was then filtered, and the filter cake was thoroughly washed with water. The filter cake was transferred to a flask, and 300 mL of chlorobenzene was added. The mixture was heated to 130 °C and passed through a 5 cm thick silica gel column. The solution was then concentrated to 100 mL, cooled to 25 °C, and crystallized for 1 h. The mixture was filtered to obtain 33.6 g of a white solid with a purity of 99.0% and a yield of 79%.

[0145] Synthesis of K-8: Intermediate I-8 (33.6 g, 0.073 mol, 1.0 eq), p-bromobenznaphthalene J-5 (22.3 g, 0.079 mol, 1.1 eq), sodium tert-butoxide (10.4 g, 0.108 mol, 1.5 eq), and 500 mL of toluene were added to a 1 L reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, nitrogen gas was introduced, and the mixture was heated to 60 °C. Then, a 10% tri-tert-butylphosphine toluene solution (5.9 g, 0.003 mol, 0.04 eq) and tris(benzylacetone)dipalladium (0.66 g, 0.0007 mol, 0.01 eq) were added, and the mixture was refluxed for 2 h. HPLC was used to monitor the complete reaction of intermediate I-8. After the reaction was completed, the temperature was lowered to 50°C, and 100 mL of water was added to quench the reaction. The water was separated, and the organic phase was washed with water again. The mixture was kept at 80°C and passed through a 5 cm silica gel column, with the silica gel being washed off. The filtrates were combined, concentrated, and toluene was removed by evaporation. The temperature was lowered to 80°C, and 160 mL of ethanol was added. The temperature was lowered to 25°C, and the mixture was filtered to obtain an off-white solid. The solid was then recrystallized twice from toluene and ethyl acetate to obtain 35.7 g of off-white solid with a purity of 99.93% and a yield of 75%.

[0146] Example 9

[0147] This embodiment provides a method for preparing a diarylcarbazole material, as shown in K-9:

[0148]

[0149] The synthetic route for the diarylcarbazole material shown in K-9 is as follows:

[0150]

[0151] Synthesis of H-9: Intermediate F-1 (55.1 g, 0.126 mol, 1.0 eq), 1-bromo-2-naphthylamine G-9 (29.4 g, 0.133 mol, 1.05 eq), potassium carbonate (34.8 g, 0.252 mol, 2.0 eq), 400 mL toluene, and 150 mL pure water were added to a 1 L reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, and under continuous nitrogen protection, palladium dichloride bis(triphenylphosphine) dichloride (0.9 g, 0.0013 mol, 0.01 eq) was added. The mixture was then heated to reflux for 3 h, and the reaction of intermediate F-1 was monitored by HPLC to ensure complete reaction. After passing the HPLC test, the mixture was cooled to 50 °C, allowed to stand to separate the aqueous layer, and the organic phase was washed once with 100 mL of water. The mixture was then held at 60 °C and passed through a 5 cm thick silica gel column, with the silica gel washed with an appropriate amount of toluene. The organic layers were combined, toluene was removed by evaporation under normal pressure, 150 mL of ethanol was added and the mixture was refluxed and stirred for 1 hour. The mixture was then cooled to 25 °C and filtered to obtain 47.3 g of off-white solid with a purity of 98.5% and a yield of 83%.

[0152] Synthesis of I-9: Intermediate H-9 (47.3 g, 0.105 mol, 1.0 eq), potassium tert-butoxide (23.7 g, 0.211 mol, 2.0 eq), and 100 mL of dimethyl sulfoxide were added to a 500 mL reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, nitrogen gas was introduced, and the mixture was heated to 90 °C and maintained at this temperature for 3 h. HPLC monitoring was used to ensure the complete reaction of intermediate H-9. After passing HPLC tests, the mixture was cooled to room temperature, 250 mL of water was added, and the mixture was stirred for 0.5 h. The mixture was then filtered, and the filter cake was thoroughly washed with water. The filter cake was transferred to a flask, and 300 mL of chlorobenzene was added. The mixture was heated to 130 °C and passed through a 5 cm thick silica gel column. The solution was then concentrated to 100 mL, cooled to 25 °C, and allowed to crystallize for 1 h. The mixture was then filtered to obtain 45.2 g of an off-white solid with a purity of 99.1% and a yield of 81%.

[0153] Synthesis of K-9: Intermediate I-9 (45.2 g, 0.085 mol, 1.0 eq), p-bromobenznaphthalene J-5 (26.5 g, 0.093 mol, 1.1 eq), sodium tert-butoxide (12.2 g, 0.128 mol, 1.5 eq), and 500 mL of toluene were added to a 1 L reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, nitrogen gas was introduced, and when the material temperature reached 60 °C, 10% tri-tert-butylphosphine toluene solution (7.1 g, 0.0035 mol, 0.04 eq) and tris(benzylideneacetone) dipalladium (0.8 g, 0.0009 mol, 0.01 eq) were added. The mixture was then heated to reflux for 2 h. HPLC was used to monitor the complete reaction of intermediate I-9. After the reaction was completed, the temperature was lowered to 50°C, and 100 mL of water was added to quench the reaction. The water was separated, and the organic phase was washed with water again. The mixture was kept at 80°C and passed through a 5 cm silica gel column, with the silica gel being washed off. The filtrates were combined, concentrated, and toluene was removed by evaporation. The temperature was lowered to 80°C, and 160 mL of ethanol was added. The temperature was lowered to 25°C, and the mixture was filtered to obtain an off-white solid. After recrystallization twice with toluene and ethyl acetate, 38.3 g of off-white solid was obtained with a purity of 99.90% and a yield of 71%.

[0154] Example 10

[0155] This embodiment provides a method for preparing a diarylcarbazole material, as shown in K-10:

[0156]

[0157] The synthetic route for the diarylcarbazole material shown in K-10 is as follows:

[0158]

[0159] Synthesis of H-10: Intermediate F-1 (55.1 g, 0.126 mol, 1.0 eq), 2-bromo-1-naphthylamine G-10 (29.4 g, 0.133 mol, 1.05 eq), potassium carbonate (34.8 g, 0.252 mol, 2.0 eq), 400 mL toluene, and 150 mL pure water were added to a 1 L reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, and under continuous nitrogen protection, palladium dichloride bis(triphenylphosphine) chloride (0.9 g, 0.0013 mol, 0.01 eq) was added. The mixture was then heated to reflux for 3 h, and the reaction of intermediate F-1 was monitored by HPLC to ensure complete reaction. After passing the HPLC test, the mixture was cooled to 50 °C, allowed to stand to separate the aqueous layer, and the organic phase was washed once with 100 mL of water. The mixture was then held at 60 °C and passed through a 5 cm thick silica gel column, with the silica gel washed with an appropriate amount of toluene. The organic layers were combined, toluene was removed by evaporation under normal pressure, 150 mL of ethanol was added and the mixture was refluxed and stirred for 1 hour. The mixture was then cooled to 25 °C and filtered to obtain 45.6 g of off-white solid with a purity of 98.6% and a yield of 80%.

[0160] Synthesis of I-10: Intermediate H-10 (45.6 g, 0.101 mol, 1.0 eq), potassium tert-butoxide (22.7 g, 0.202 mol, 2.0 eq), and 100 mL of dimethyl sulfoxide were added to a 500 mL reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, nitrogen gas was introduced, and the mixture was heated to 90 °C and maintained at this temperature for 3 h. HPLC monitoring was used to ensure the complete reaction of intermediate H-10. After HPLC confirmation, the mixture was cooled to room temperature, 250 mL of water was added, and the mixture was stirred for 0.5 h. The mixture was then filtered, and the filter cake was thoroughly washed with water. The filter cake was transferred to a flask, and 300 mL of chlorobenzene was added. The mixture was heated to 130 °C and passed through a 5 cm silica gel column. The solution was then concentrated to 100 mL, cooled to 25 °C, and crystallized for 1 h. The mixture was filtered to obtain 43.0 g of an off-white solid with a purity of 98.7% and a yield of 80%.

[0161] Synthesis of K-10: Intermediate I-10 (43.0 g, 0.081 mol, 1.0 eq), p-bromobenznaphthalene J-5 (26.5 g, 0.093 mol, 1.15 eq), sodium tert-butoxide (12.2 g, 0.128 mol, 1.6 eq), and 500 mL of toluene were added to a 1 L reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, nitrogen gas was introduced, and the mixture was heated to 60 °C. Then, a 10% tri-tert-butylphosphine toluene solution (7.0 g, 0.0032 mol, 0.04 eq) and tris(benzylacetone)dipalladium (0.8 g, 0.0009 mol, 0.01 eq) were added, and the mixture was refluxed for 2 h. HPLC was used to monitor the complete reaction of intermediate I-10. After the reaction was completed, the temperature was lowered to 50°C, and 100 mL of water was added to quench the reaction. The water was separated, and the organic phase was washed with water again. The mixture was kept at 80°C and passed through a 5 cm silica gel column, with the silica gel being washed off. The filtrates were combined, concentrated, and toluene was removed by evaporation. The temperature was lowered to 80°C, and 160 mL of ethanol was added. The temperature was lowered to 25°C, and the mixture was filtered to obtain an off-white solid. After recrystallization twice with toluene and ethyl acetate, 37.1 g of off-white solid was obtained with a purity of 99.93% and a yield of 72%.

[0162] Example 11

[0163] This embodiment provides a method for preparing a diarylcarbazole material, as shown in K-11:

[0164]

[0165] The synthetic route for the diarylcarbazole material shown in K-11 is as follows:

[0166]

[0167] Synthesis of H-11: Intermediate F-1 (55.1 g, 0.126 mol, 1.0 eq), 3-bromo-2-naphthylamine G-11 (29.4 g, 0.133 mol, 1.05 eq), potassium carbonate (34.8 g, 0.252 mol, 2.0 eq), 400 mL toluene, and 150 mL pure water were added to a 1 L reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, and under continuous nitrogen protection, palladium dichloride bis(triphenylphosphine) dichloride (0.9 g, 0.0013 mol, 0.01 eq) was added. The mixture was then heated to reflux for 3 h, and the reaction of intermediate F-1 was monitored by HPLC to ensure complete reaction. After passing the HPLC test, the mixture was cooled to 50 °C, allowed to stand to separate the aqueous layer, and the organic phase was washed once with 100 mL of water. The mixture was then held at 60 °C and passed through a 5 cm thick silica gel column, with the silica gel washed with an appropriate amount of toluene. The organic layers were combined, toluene was removed by evaporation under normal pressure, and then 150 mL of ethanol was added and refluxed for 1 hour. The mixture was cooled to 25 °C and filtered to obtain 47.3 g of off-white solid with a purity of 98.2% and a yield of 83%.

[0168] Synthesis of I-11: Intermediate H-11 (47.3 g, 0.105 mol, 1.0 eq), potassium tert-butoxide (23.7 g, 0.211 mol, 2.0 eq), and 100 mL of dimethyl sulfoxide were added to a 500 mL reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, nitrogen gas was introduced, and the mixture was heated to 90 °C and maintained at this temperature for 3 h. HPLC monitoring was used to ensure the complete reaction of intermediate H-11. After passing HPLC tests, the mixture was cooled to room temperature, 250 mL of water was added, and the mixture was stirred for 0.5 h. The mixture was then filtered, and the filter cake was thoroughly washed with water. The filter cake was transferred to a flask, and 300 mL of chlorobenzene was added. The mixture was heated to 130 °C and passed through a 5 cm silica gel column. The solution was then concentrated to 100 mL, cooled to 25 °C, and crystallized for 1 h. The mixture was filtered to obtain 44.6 g of a white solid with a purity of 98.9% and a yield of 80%.

[0169] Synthesis of K-11: Intermediate I-11 (44.6 g, 0.084 mol, 1.0 eq), p-bromobenznaphthalene J-5 (26.5 g, 0.093 mol, 1.1 eq), sodium tert-butoxide (12.2 g, 0.128 mol, 1.5 eq), and 500 mL of toluene were added to a 1 L reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, nitrogen gas was introduced, and when the material temperature reached 60 °C, 10% tri-tert-butylphosphine toluene solution (7.1 g, 0.0035 mol, 0.04 eq) and tris(benzylideneacetone) dipalladium (0.8 g, 0.0009 mol, 0.01 eq) were added, and the mixture was then heated to reflux for 2 h. HPLC was used to monitor the complete reaction of intermediate I-11. After the reaction was completed, the temperature was lowered to 50°C, and 100 mL of water was added to quench the reaction. The water was separated, and the organic phase was washed with water again. The mixture was kept at 80°C and passed through a 5 cm silica gel column, with the silica gel being washed off. The filtrates were combined, concentrated, and toluene was removed by evaporation. The temperature was lowered to 80°C, and 160 mL of ethanol was added. The temperature was lowered to 25°C, and the mixture was filtered to obtain an off-white solid. After recrystallization twice with toluene and ethyl acetate, 37.3 g of off-white solid was obtained with a purity of 99.91% and a yield of 70%.

[0170] Example 12

[0171] This embodiment provides a method for preparing a diarylcarbazole material, as shown in K-12:

[0172]

[0173] The synthetic route for the diarylcarbazole material shown in K-12 is as follows:

[0174]

[0175] Synthesis of H-12: Intermediate F-1 (55.1 g, 0.126 mol, 1.0 eq), 3-phenyl-2-bromo-1-aniline G-12 (33.0 g, 0.133 mol, 1.05 eq), potassium carbonate (34.8 g, 0.252 mol, 2.0 eq), 400 mL toluene, and 150 mL pure water were added to a 1 L reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, and under continuous nitrogen protection, palladium dichloride bis(triphenylphosphine) chloride (0.9 g, 0.0013 mol, 0.01 eq) was added. The mixture was then heated to reflux for 3 h, and the reaction of intermediate F-1 was monitored by HPLC to ensure complete reaction. After passing the HPLC test, the mixture was cooled to 50 °C, allowed to stand to separate the aqueous layer, and the organic phase was washed once with 100 mL of water. The mixture was then held at 60 °C and passed through a 5 cm thick silica gel column, with the silica gel washed with an appropriate amount of toluene. The organic layers were combined, toluene was removed by evaporation under normal pressure, 150 mL of ethanol was added and refluxed for 1 hour, the mixture was cooled to 25 °C and filtered to obtain 42.2 g of off-white solid with a purity of 97.5% and a yield of 70%.

[0176] Synthesis of I-12: Intermediate H-12 (42.2 g, 0.088 mol, 1.0 eq), potassium tert-butoxide (19.8 g, 0.176 mol, 2.0 eq), and 100 mL of dimethyl sulfoxide were added to a 500 mL reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, nitrogen gas was introduced, and the mixture was heated to 90 °C and maintained at this temperature for 3 h. HPLC monitoring was used to ensure the complete reaction of intermediate H-12. After passing HPLC tests, the mixture was cooled to room temperature, 250 mL of water was added, and the mixture was stirred for 0.5 h. The mixture was then filtered, and the filter cake was thoroughly washed with water. The filter cake was transferred to a flask, and 300 mL of chlorobenzene was added. The mixture was heated to 130 °C and passed through a 5 cm silica gel column. The solution was then concentrated to 100 mL, cooled to 25 °C, and crystallized for 1 h. The mixture was filtered to obtain 31.5 g of an off-white solid with a purity of 98.9% and a yield of 78%.

[0177] Synthesis of K-12: Intermediate I-12 (31.5 g, 0.069 mol, 1.0 eq), m-bromobenznaphthalene J-12 (21.5 g, 0.076 mol, 1.1 eq), sodium tert-butoxide (9.9 g, 0.104 mol, 1.5 eq), and 500 mL of toluene were added to a 1 L reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, nitrogen gas was introduced, and when the material temperature reached 60 °C, 10% tri-tert-butylphosphine toluene solution (5.6 g, 0.0028 mol, 0.04 eq) and tris(benzylideneacetone) dipalladium (0.63 g, 0.0007 mol, 0.01 eq) were added. The mixture was then heated to reflux for 2 h. HPLC was used to monitor the complete reaction of intermediate I-12. After the reaction was completed, the temperature was lowered to 50°C, and 100 mL of water was added to quench the reaction. The water was separated, and the organic phase was washed with water again. The mixture was kept at 80°C and passed through a 5 cm silica gel column, with the silica gel being washed off. The filtrates were combined, concentrated, and toluene was removed by evaporation. The temperature was lowered to 80°C, and 160 mL of ethanol was added. The temperature was lowered to 25°C, and the mixture was filtered to obtain an off-white solid. After recrystallization twice with toluene and ethyl acetate, 31.9 g of off-white solid with a purity of 99.92% and a yield of 70% was obtained.

[0178] Example 13

[0179] This embodiment provides a method for preparing a diarylcarbazole material, as shown in K-13:

[0180]

[0181] The synthetic route for the diarylcarbazole material shown in K-13 is as follows:

[0182]

[0183] Synthesis of H-13: Intermediate F-1 (55.1 g, 0.126 mol, 1.0 eq), 4-phenyl-2-bromo-1-aniline G-13 (33.0 g, 0.133 mol, 1.05 eq), potassium carbonate (34.8 g, 0.252 mol, 2.0 eq), 400 mL toluene, and 150 mL pure water were added to a 1 L reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, and under continuous nitrogen protection, palladium dichloride bis(triphenylphosphine) dichloride (0.9 g, 0.0013 mol, 0.01 eq) was added. The mixture was then heated to reflux for 3 h, and the reaction of intermediate F-1 was monitored by HPLC to ensure complete reaction. After passing the HPLC test, the mixture was cooled to 50 °C, allowed to stand to separate the aqueous layer, and the organic phase was washed once with 100 mL of water. The mixture was then held at 60 °C and passed through a 5 cm thick silica gel column, with the silica gel washed with an appropriate amount of toluene. The organic layers were combined, toluene was removed by evaporation under normal pressure, and then 150 mL of ethanol was added and refluxed for 1 hour. The mixture was cooled to 25 °C and filtered to obtain 50.6 g of off-white solid with a purity of 98.5% and a yield of 84%.

[0184] Synthesis of I-13: Intermediate H-13 (50.6 g, 0.106 mol, 1.0 eq), potassium tert-butoxide (23.9 g, 0.212 mol, 2.0 eq), and 100 mL of dimethyl sulfoxide were added to a 500 mL reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, nitrogen gas was introduced, and the mixture was heated to 90 °C and maintained at this temperature for 3 h. HPLC monitoring was used to ensure the complete reaction of intermediate H-13. After passing HPLC tests, the mixture was cooled to room temperature, 250 mL of water was added, and the mixture was stirred for 0.5 h. The mixture was then filtered, and the filter cake was thoroughly washed with water. The filter cake was transferred to a flask, and 300 mL of chlorobenzene was added. The mixture was heated to 130 °C and passed through a 5 cm silica gel column. The solution was then concentrated to 100 mL, cooled to 25 °C, and crystallized for 1 h. The mixture was filtered to obtain 39.4 g of an off-white solid with a purity of 98.2% and a yield of 81%.

[0185] Synthesis of K-13: Intermediate I-13 (39.4 g, 0.086 mol, 1.0 eq), m-bromobenznaphthalene J-12 (26.8 g, 0.095 mol, 1.1 eq), sodium tert-butoxide (12.4 g, 0.129 mol, 1.5 eq), and 500 mL of toluene were added to a 1 L reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, nitrogen gas was introduced, and when the material temperature reached 60 °C, 10% tri-tert-butylphosphine toluene solution (7.0 g, 0.0034 mol, 0.04 eq) and tris(benzylideneacetone) dipalladium (0.8 g, 0.0009 mol, 0.01 eq) were added, and the mixture was then heated to reflux for 2 h. HPLC was used to monitor the complete reaction of intermediate I-13. After the reaction was completed, the temperature was lowered to 50°C, and 100 mL of water was added to quench the reaction. The water was separated, and the organic phase was washed with water again. The mixture was kept at 80°C and passed through a 5 cm silica gel column, with the silica gel being washed off. The filtrates were combined, concentrated, and toluene was removed by evaporation. The temperature was lowered to 80°C, and 160 mL of ethanol was added. The temperature was lowered to 25°C, and the mixture was filtered to obtain an off-white solid. The solid was then recrystallized twice from toluene and ethyl acetate to obtain 41.5 g of off-white solid with a purity of 99.90% and a yield of 73%.

[0186] Example 14

[0187] This embodiment provides a method for preparing a diarylcarbazole material, as shown in K-14:

[0188]

[0189] The synthetic route for the diarylcarbazole material shown in K-14 is as follows:

[0190]

[0191] Synthesis of H-14: Intermediate F-1 (55.1 g, 0.126 mol, 1.0 eq), 5-phenyl-2-bromo-1-aniline G-14 (33.0 g, 0.133 mol, 1.05 eq), potassium carbonate (34.8 g, 0.252 mol, 2.0 eq), 400 mL toluene, and 150 mL pure water were added to a 1 L reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, and under continuous nitrogen protection, palladium dichloride bis(triphenylphosphine) dichloride (0.9 g, 0.0013 mol, 0.01 eq) was added. The mixture was then heated to reflux for 3 h, and the reaction of intermediate F-1 was monitored by HPLC to ensure complete reaction. After passing the HPLC test, the mixture was cooled to 50 °C, allowed to stand to separate the aqueous layer, and the organic phase was washed once with 100 mL of water. The mixture was then held at 60 °C and passed through a 5 cm thick silica gel column, with the silica gel washed with an appropriate amount of toluene. The organic layers were combined, toluene was removed by evaporation under normal pressure, and then 150 mL of ethanol was added and refluxed for 1 hour. The mixture was cooled to 25 °C and filtered to obtain 50.5 g of off-white solid with a purity of 98.2% and a yield of 83.9%.

[0192] Synthesis of I-14: Intermediate H-14 (50.5 g, 0.106 mol, 1.0 eq), potassium tert-butoxide (23.9 g, 0.212 mol, 2.0 eq), and 100 mL of dimethyl sulfoxide were added to a 500 mL reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, nitrogen gas was introduced, and the mixture was heated to 90 °C and maintained at this temperature for 3 h. HPLC monitoring was used to ensure the complete reaction of intermediate H-14. After passing HPLC tests, the mixture was cooled to room temperature, 250 mL of water was added, and the mixture was stirred for 0.5 h. The mixture was then filtered, and the filter cake was thoroughly washed with water. The filter cake was transferred to a flask, and 300 mL of chlorobenzene was added. The mixture was heated to 130 °C and passed through a 5 cm silica gel column. The solution was then concentrated to 100 mL, cooled to 25 °C, and crystallized for 1 h. The mixture was filtered to obtain 40.4 g of an off-white solid with a purity of 98.3% and a yield of 83%.

[0193] Synthesis of K-14: Intermediate I-14 (40.4 g, 0.088 mol, 1.0 eq), p-bromobenznaphthalene J-5 (27.4 g, 0.097 mol, 1.1 eq), sodium tert-butoxide (12.4 g, 0.129 mol, 1.5 eq), and 500 mL of toluene were added to a 1 L reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, nitrogen gas was introduced, and when the material temperature reached 60 °C, 10% tri-tert-butylphosphine toluene solution (7.0 g, 0.0034 mol, 0.04 eq) and tris(benzylideneacetone) dipalladium (0.8 g, 0.0009 mol, 0.01 eq) were added, and the mixture was then heated to reflux for 2 h. HPLC was used to monitor the complete reaction of intermediate I-14. After the reaction was completed, the temperature was lowered to 50°C, and 100 mL of water was added to quench the reaction. The water was separated, and the organic phase was washed with water again. The mixture was kept at 80°C and passed through a 5 cm silica gel column, with the silica gel being washed off. The filtrates were combined, concentrated, and toluene was removed by evaporation. The temperature was lowered to 80°C, and 160 mL of ethanol was added. The temperature was lowered to 25°C, and the mixture was filtered to obtain an off-white solid. After recrystallization twice with toluene and ethyl acetate, 43 g of off-white solid was obtained with a purity of 99.94% and a yield of 74%.

[0194] Example 15

[0195] This embodiment provides a method for preparing a diarylcarbazole material, as shown in K-15:

[0196]

[0197] The synthetic route for the diarylcarbazole material shown in K-15 is as follows:

[0198]

[0199] Synthesis of H-15: Intermediate F-6 (58.8 g, 0.121 mol, 1.0 eq), 1-bromo-2-naphthylamine G-9 (28.2 g, 0.127 mol, 1.05 eq), potassium carbonate (33.4 g, 0.242 mol, 2.0 eq), 400 mL toluene, and 150 mL pure water were added to a 1 L reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, and under continuous nitrogen protection, palladium dichloride bis(triphenylphosphine) dichloride (0.9 g, 0.0013 mol, 0.01 eq) was added. The mixture was then heated to reflux for 3 h, and the reaction of intermediate F-6 was monitored by HPLC to ensure complete reaction. After passing the HPLC test, the mixture was cooled to 50 °C, allowed to stand to separate the aqueous layer, and the organic phase was washed once with 100 mL of water. The mixture was then held at 60 °C and passed through a 5 cm thick silica gel column, with the silica gel washed with an appropriate amount of toluene. The organic layers were combined, toluene was removed by evaporation under normal pressure, 150 mL of ethanol was added and refluxed for 1 hour, the mixture was cooled to 25 °C and filtered to obtain 60.8 g of off-white solid with a purity of 98.1% and a yield of 83%.

[0200] Synthesis of I-15: Intermediate H-15 (60.8 g, 0.101 mol, 1.0 eq), potassium tert-butoxide (22.7 g, 0.202 mol, 2.0 eq), and 100 mL of dimethyl sulfoxide were added to a 500 mL reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, nitrogen gas was introduced, and the mixture was heated to 90 °C and maintained at this temperature for 3 h. HPLC monitoring was used to ensure the complete reaction of intermediate H-15. After passing HPLC tests, the mixture was cooled to room temperature, 250 mL of water was added, and the mixture was stirred for 0.5 h. The mixture was then filtered, and the filter cake was thoroughly washed with water. The filter cake was transferred to a flask, and 300 mL of chlorobenzene was added. The mixture was heated to 130 °C and passed through a 5 cm silica gel column. The solution was then concentrated to 100 mL, cooled to 25 °C, and crystallized for 1 h. The mixture was filtered to obtain 48.3 g of an off-white solid with a purity of 99.2% and a yield of 81%.

[0201] Synthesis of K-15: Intermediate I-15 (48.3 g, 0.082 mol, 1.0 eq), 3-bromophenyldibenzofuran J-4 (29.2 g, 0.090 mol, 1.1 eq), sodium tert-butoxide (11.8 g, 0.123 mol, 1.5 eq), and 500 mL of toluene were added to a 1 L reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, nitrogen gas was introduced, and the mixture was heated to 60 °C. Then, a 10% tri-tert-butylphosphine toluene solution (7.0 g, 0.0035 mol, 0.04 eq) and tris(benzylideneacetone)dipalladium (0.8 g, 0.0009 mol, 0.01 eq) were added, and the mixture was refluxed for 2 h. HPLC was used to monitor the complete reaction of intermediate I-15. After the reaction was completed, the temperature was lowered to 50°C, and 100 mL of water was added to quench the reaction. The water was separated, and the organic phase was washed with water again. The mixture was kept at 80°C and passed through a 5 cm silica gel column, with the silica gel being washed off. The filtrates were combined, concentrated, and toluene was removed by evaporation. The temperature was lowered to 80°C, and 160 mL of ethanol was added. The temperature was lowered to 25°C, and the mixture was filtered to obtain an off-white solid. After recrystallization twice with toluene and ethyl acetate, 41.6 g of off-white solid was obtained with a purity of 99.93% and a yield of 70%.

[0202] Example 16

[0203] This embodiment provides a method for preparing a diarylcarbazole material, as shown in K-16:

[0204]

[0205] The synthetic route for the diarylcarbazole material shown in K-16 is as follows:

[0206]

[0207] Synthesis of H-16: Intermediate F-6 (58.8 g, 0.121 mol, 1.0 eq), 5-phenyl-2-bromoaniline G-14 (31.5 g, 0.127 mol, 1.05 eq), potassium carbonate (33.4 g, 0.242 mol, 2.0 eq), 400 mL toluene, and 150 mL pure water were added to a 1 L reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, and under continuous nitrogen protection, palladium dichloride bis(triphenylphosphine) chloride (0.9 g, 0.0013 mol, 0.01 eq) was added. The mixture was then heated to reflux for 3 h, and the reaction of intermediate F-6 was monitored by HPLC to ensure complete reaction. After passing the HPLC test, the mixture was cooled to 50 °C, allowed to stand to separate the aqueous layer, and the organic phase was washed once with 100 mL of water. The mixture was then held at 60 °C and passed through a 5 cm thick silica gel column, with the silica gel washed with an appropriate amount of toluene. The organic layers were combined, toluene was removed by evaporation under normal pressure, and then 150 mL of ethanol was added and refluxed for 1 hour. The mixture was cooled to 25 °C and filtered to obtain 51.2 g of off-white solid with a purity of 98.1% and a yield of 80%.

[0208] Synthesis of I-16: Intermediate H-16 (51.2 g, 0.097 mol, 1.0 eq), potassium tert-butoxide (22.7 g, 0.202 mol, 2.1 eq), and 100 mL of dimethyl sulfoxide were added to a 500 mL reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, nitrogen gas was introduced, and the mixture was heated to 90 °C and maintained at this temperature for 3 h. HPLC monitoring was used to ensure the complete reaction of intermediate H-16. After HPLC confirmation, the mixture was cooled to room temperature, 250 mL of water was added, and the mixture was stirred for 0.5 h. The mixture was then filtered, and the filter cake was thoroughly washed with water. The filter cake was transferred to a flask, and 300 mL of chlorobenzene was added. The mixture was heated to 130 °C and passed through a 5 cm silica gel column. The solution was then concentrated to 100 mL, cooled to 25 °C, and crystallized for 1 h. Filtration yielded 41.4 g of an off-white solid with a purity of 98.6% and a yield of 84%.

[0209] Synthesis of K-16: Intermediate I-16 (41.4 g, 0.082 mol, 1.0 eq), 3-bromophenyldibenzofuran J-4 (29.2 g, 0.090 mol, 1.1 eq), sodium tert-butoxide (11.8 g, 0.123 mol, 1.5 eq), and 500 mL of toluene were added to a 1 L reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, nitrogen gas was introduced, and the mixture was heated to 60 °C. Then, a 10% tri-tert-butylphosphine toluene solution (7.0 g, 0.0035 mol, 0.04 eq) and tris(benzylideneacetone)dipalladium (0.8 g, 0.0009 mol, 0.01 eq) were added, and the mixture was refluxed for 2 h. HPLC was used to monitor the complete reaction of intermediate I-16. After the reaction was completed, the temperature was lowered to 50°C, and 100 mL of water was added to quench the reaction. The water was separated, and the organic phase was washed with water again. The mixture was kept at 80°C and passed through a 5 cm silica gel column, with the silica gel being washed off. The filtrates were combined, concentrated, and toluene was removed by evaporation. The temperature was lowered to 80°C, and 160 mL of ethanol was added. The temperature was lowered to 25°C, and the mixture was filtered to obtain an off-white solid. After recrystallization twice with toluene and ethyl acetate, 44.3 g of off-white solid was obtained with a purity of 99.91% and a yield of 72%.

[0210] Example 17

[0211] This embodiment provides a method for preparing a diarylcarbazole material, as shown in K-17:

[0212]

[0213] The synthetic route for the diarylcarbazole material shown in K-17 is as follows:

[0214]

[0215] Synthesis of H-17: Intermediate F-7 (60.2 g, 0.117 mol, 1.0 eq), 1-bromo-2-naphthylamine G-9 (27.3 g, 0.123 mol, 1.05 eq), potassium carbonate (32.3 g, 0.234 mol, 2.0 eq), 400 mL toluene, and 150 mL pure water were added to a 1 L reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, and under continuous nitrogen protection, palladium dichloride bis(triphenylphosphine) dichloride (0.9 g, 0.0013 mol, 0.01 eq) was added. The mixture was then heated to reflux for 3 h, and the reaction of intermediate F-7 was monitored by HPLC to ensure complete reaction. After passing the HPLC test, the mixture was cooled to 50 °C, allowed to stand to separate the aqueous layer, and the organic phase was washed once with 100 mL of water. The mixture was then held at 60 °C and passed through a 5 cm thick silica gel column, with the silica gel washed with an appropriate amount of toluene. The organic layers were combined, toluene was removed by evaporation at normal pressure, 150 mL of ethanol was added and the mixture was refluxed and stirred for 1 hour. The mixture was then cooled to 25 °C and filtered to obtain 48.2 g of off-white solid with a purity of 97.6% and a yield of 78%.

[0216] Synthesis of I-17: Intermediate H-17 (48.2 g, 0.091 mol, 1.0 eq), potassium tert-butoxide (20.7 g, 0.184 mol, 2.0 eq), and 100 mL of dimethyl sulfoxide were added to a 500 mL reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, nitrogen gas was introduced, and the mixture was heated to 90 °C and maintained at this temperature for 3 h. HPLC monitoring was used to ensure the complete reaction of intermediate H-17. After passing HPLC tests, the mixture was cooled to room temperature, 250 mL of water was added, and the mixture was stirred for 0.5 h. The mixture was then filtered, and the filter cake was thoroughly washed with water. The filter cake was transferred to a flask, and 300 mL of chlorobenzene was added. The mixture was heated to 130 °C and passed through a 5 cm silica gel column. The solution was then concentrated to 100 mL, cooled to 25 °C, and allowed to crystallize for 1 h. The mixture was filtered to obtain 36.1 g of an off-white solid with a purity of 97.3% and a yield of 78%.

[0217] Synthesis of K-17: Intermediate I-17 (36.1 g, 0.071 mol, 1.0 eq), 4-bromophenyldibenzofuran J-3 (25.2 g, 0.078 mol, 1.1 eq), sodium tert-butoxide (10.4 g, 0.108 mol, 1.5 eq), and 500 mL of toluene were added to a 1 L reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, nitrogen gas was introduced, and the mixture was heated to 60 °C. Then, a 10% tri-tert-butylphosphine toluene solution (5.7 g, 0.003 mol, 0.04 eq) and tris(benzylacetone)dipalladium (0.66 g, 0.0007 mol, 0.01 eq) were added, and the mixture was refluxed for 2 h. HPLC was used to monitor the complete reaction of intermediate I-17. After the reaction was completed, the temperature was lowered to 50°C, and 100 mL of water was added to quench the reaction. The water was separated, and the organic phase was washed with water again. The mixture was kept at 80°C and passed through a 5 cm silica gel column, with the silica gel being washed off. The filtrates were combined, concentrated, and toluene was evaporated. The temperature was lowered to 80°C, and 160 mL of ethanol was added. The temperature was lowered to 25°C, and the mixture was filtered to obtain an off-white solid. After recrystallization twice with toluene and ethyl acetate, 38.9 g of off-white solid was obtained with a purity of 99.90% and a yield of 73%.

[0218] Example 18

[0219] This embodiment provides a method for preparing a diarylcarbazole material, as shown in K-18:

[0220]

[0221] The synthetic route for the diarylcarbazole material shown in K-18 is as follows:

[0222]

[0223] Synthesis of H-18: Intermediate F-7 (60.2 g, 0.117 mol, 1.0 eq), 2-bromo-1-naphthylamine G-10 (27.3 g, 0.123 mol, 1.05 eq), potassium carbonate (32.3 g, 0.234 mol, 2.0 eq), 400 mL toluene, and 150 mL pure water were added to a 1 L reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, and under continuous nitrogen protection, palladium dichloride bis(triphenylphosphine) chloride (0.9 g, 0.0013 mol, 0.01 eq) was added. The mixture was then heated to reflux for 3 h, and the reaction of intermediate F-7 was monitored by HPLC to ensure complete reaction. After passing the HPLC test, the mixture was cooled to 50 °C, allowed to stand to separate the aqueous layer, and the organic phase was washed once with 100 mL of water. The mixture was then held at 60 °C and passed through a 5 cm thick silica gel column, with the silica gel washed with an appropriate amount of toluene. The organic layers were combined, toluene was removed by evaporation at normal pressure, 150 mL of ethanol was added and the mixture was refluxed and stirred for 1 hour. The mixture was then cooled to 25 °C and filtered to obtain 48.1 g of off-white solid with a purity of 97.4% and a yield of 77.5%.

[0224] Synthesis of I-18: Intermediate H-18 (48.1 g, 0.091 mol, 1.0 eq), potassium tert-butoxide (20.7 g, 0.184 mol, 2.0 eq), and 100 mL of dimethyl sulfoxide were added to a 500 mL reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, nitrogen gas was introduced, and the mixture was heated to 90 °C and maintained at this temperature for 3 h. HPLC monitoring was used to ensure the complete reaction of intermediate H-18. After HPLC confirmation, the mixture was cooled to room temperature, 250 mL of water was added, and the mixture was stirred for 0.5 h. The mixture was then filtered, and the filter cake was thoroughly washed with water. The filter cake was transferred to a flask, and 300 mL of chlorobenzene was added. The mixture was heated to 130 °C and passed through a 5 cm silica gel column. The solution was then concentrated to 100 mL, cooled to 25 °C, and crystallized for 1 h. The mixture was filtered to obtain 37.0 g of an off-white solid with a purity of 97.8% and a yield of 80%.

[0225] Synthesis of K-18: Intermediate I-18 (37.0 g, 0.073 mol, 1.0 eq), 4-bromophenyldibenzofuran J-3 (26.0 g, 0.080 mol, 1.1 eq), sodium tert-butoxide (10.5 g, 0.110 mol, 1.5 eq), and 500 mL of toluene were added to a 1 L reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, nitrogen gas was introduced, and the mixture was heated to 60 °C. Then, a 10% tri-tert-butylphosphine toluene solution (5.7 g, 0.003 mol, 0.04 eq) and tris(benzylideneacetone)dipalladium (0.66 g, 0.0007 mol, 0.01 eq) were added, and the mixture was refluxed for 2 h. HPLC was used to monitor the complete reaction of intermediate I-18. After the reaction was completed, the temperature was lowered to 50°C, and 100 mL of water was added to quench the reaction. The water was separated, and the organic phase was washed with water again. The mixture was kept at 80°C and passed through a 5 cm silica gel column, with the silica gel being washed off. The filtrates were combined, concentrated, and toluene was evaporated. The temperature was lowered to 80°C, and 160 mL of ethanol was added. The temperature was lowered to 25°C, and the mixture was filtered to obtain an off-white solid. After recrystallization twice with toluene and ethyl acetate, 39.5 g of off-white solid was obtained with a purity of 99.93% and a yield of 72%.

[0226] Example 19

[0227] This embodiment provides a method for preparing a diarylcarbazole material, as shown in K-19:

[0228]

[0229] The synthetic route for the diarylcarbazole material shown in K-19 is as follows:

[0230]

[0231] Synthesis of H-19: Intermediate F-8 (59.3 g, 0.115 mol, 1.0 eq), 1-bromo-2-naphthylamine G-9 (26.9 g, 0.121 mol, 1.05 eq), potassium carbonate (31.8 g, 0.231 mol, 2.0 eq), 400 mL toluene, and 150 mL pure water were added to a 1 L reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, and under continuous nitrogen protection, palladium dichloride bis(triphenylphosphine) chloride (0.9 g, 0.0013 mol, 0.01 eq) was added. The mixture was then heated to reflux for 3 h, and the reaction of intermediate F-8 was monitored by HPLC to ensure complete reaction. After passing the HPLC test, the mixture was cooled to 50 °C, allowed to stand to separate the aqueous layer, and the organic phase was washed once with 100 mL of water. The mixture was then held at 60 °C and passed through a 5 cm thick silica gel column, with the silica gel washed with an appropriate amount of toluene. The organic layers were combined, toluene was removed by evaporation under normal pressure, 150 mL of ethanol was added and the mixture was refluxed and stirred for 1 hour. The mixture was then cooled to 25 °C and filtered to obtain 49.2 g of off-white solid with a purity of 98.3% and a yield of 81%.

[0232] Synthesis of I-19: Intermediate H-19 (49.2 g, 0.093 mol, 1.0 eq), potassium tert-butoxide (20.7 g, 0.184 mol, 2.0 eq), and 100 mL of dimethyl sulfoxide were added to a 500 mL reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, nitrogen gas was introduced, and the mixture was heated to 90 °C and maintained at this temperature for 3 h. HPLC monitoring was used to ensure the complete reaction of intermediate H-19. After passing HPLC tests, the mixture was cooled to room temperature, 250 mL of water was added, and the mixture was stirred for 0.5 h. The mixture was then filtered, and the filter cake was thoroughly washed with water. The filter cake was transferred to a flask, and 300 mL of chlorobenzene was added. The mixture was heated to 130 °C and passed through a 5 cm silica gel column. The solution was then concentrated to 100 mL, cooled to 25 °C, and crystallized for 1 h. The mixture was filtered to obtain 37.8 g of an off-white solid with a purity of 98.8% and a yield of 80%.

[0233] Synthesis of K-19: Intermediate I-19 (37.8 g, 0.074 mol, 1.0 eq), 3-bromophenyldibenzofuran J-4 (26.3 g, 0.081 mol, 1.1 eq), sodium tert-butoxide (10.4 g, 0.108 mol, 1.5 eq), and 500 mL of toluene were added to a 1 L reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, nitrogen gas was introduced, and the mixture was heated to 60 °C. Then, a 10% tri-tert-butylphosphine toluene solution (5.9 g, 0.003 mol, 0.04 eq) and tris(benzylideneacetone)dipalladium (0.66 g, 0.0007 mol, 0.01 eq) were added, and the mixture was refluxed for 3 h. HPLC was used to monitor the complete reaction of intermediate I-19. After the reaction was completed, the temperature was lowered to 50°C, and 100 mL of water was added to quench the reaction. The water was separated, and the organic phase was washed with water again. The mixture was kept at 80°C and passed through a 5 cm silica gel column, with the silica gel being washed off. The filtrates were combined, concentrated, and toluene was removed by evaporation. The temperature was lowered to 80°C, and 160 mL of ethanol was added. The temperature was lowered to 25°C, and the mixture was filtered to obtain an off-white solid. After recrystallization twice with toluene and ethyl acetate, 39.4 g of off-white solid was obtained with a purity of 99.92% and a yield of 71%.

[0234] Example 20

[0235] This embodiment provides a method for preparing a diarylcarbazole material, as shown in K-20:

[0236]

[0237] The synthetic route for the diarylcarbazole material shown in K-20 is as follows:

[0238]

[0239] Synthesis of H-20: Intermediate F-8 (59.3 g, 0.115 mol, 1.0 eq), 2-bromo-1-naphthylamine G-10 (26.9 g, 0.121 mol, 1.05 eq), potassium carbonate (31.8 g, 0.231 mol, 2.0 eq), 400 mL toluene, and 150 mL pure water were added to a 1 L reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, and under continuous nitrogen protection, palladium dichloride bis(triphenylphosphine) dichloride (0.9 g, 0.0013 mol, 0.01 eq) was added. The mixture was then heated to reflux for 3 h, and the reaction of intermediate F-8 was monitored by HPLC to ensure complete reaction. After passing the HPLC test, the mixture was cooled to 50 °C, allowed to stand to separate the aqueous layer, and the organic phase was washed once with 100 mL of water. The mixture was then held at 60 °C and passed through a 5 cm thick silica gel column, with the silica gel washed with an appropriate amount of toluene. The organic layers were combined, toluene was removed by evaporation under normal pressure, 150 mL of ethanol was added and refluxed for 1 hour, the mixture was cooled to 25 °C and filtered to obtain 48.1 g of off-white solid with a purity of 97.6% and a yield of 79%.

[0240] Synthesis of I-20: Intermediate H-20 (48.1 g, 0.091 mol, 1.0 eq), potassium tert-butoxide (20.5 g, 0.182 mol, 2.0 eq), and 100 mL of dimethyl sulfoxide were added to a 500 mL reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, nitrogen gas was introduced, and the mixture was heated to 90 °C and maintained at this temperature for 3 h. HPLC monitoring was used to ensure the complete reaction of intermediate H-20. After passing HPLC tests, the mixture was cooled to room temperature, 250 mL of water was added, and the mixture was stirred for 0.5 h. The mixture was then filtered, and the filter cake was thoroughly washed with water. The filter cake was transferred to a flask, and 300 mL of chlorobenzene was added. The mixture was heated to 130 °C and passed through a 5 cm silica gel column. The solution was then concentrated to 100 mL, cooled to 25 °C, and crystallized for 1 h. The mixture was filtered to obtain 37.8 g of a white solid with a purity of 98.2% and a yield of 78%.

[0241] Synthesis of K-20: Intermediate I-20 (36.3 g, 0.071 mol, 1.0 eq), 4-bromophenyldibenzofuran J-3 (25.3 g, 0.078 mol, 1.1 eq), sodium tert-butoxide (10.4 g, 0.108 mol, 1.5 eq), and 500 mL of toluene were added to a 1 L reaction flask equipped with a stirrer, thermometer, and reflux condenser. Stirring was started, nitrogen gas was introduced, and the mixture was heated to 60 °C. Then, a 10% tri-tert-butylphosphine toluene solution (5.9 g, 0.003 mol, 0.04 eq) and tris(benzylideneacetone)dipalladium (0.66 g, 0.0007 mol, 0.01 eq) were added, and the mixture was refluxed for 3 h. HPLC was used to monitor the complete reaction of intermediate I-20. After the reaction was completed, the temperature was lowered to 50°C, and 100 mL of water was added to quench the reaction. The water was separated, and the organic phase was washed with water again. The mixture was kept at 80°C and passed through a 5 cm silica gel column, with the silica gel being washed off. The filtrates were combined, concentrated, and toluene was evaporated. The temperature was lowered to 80°C, and 160 mL of ethanol was added. The temperature was lowered to 25°C, and the mixture was filtered to obtain an off-white solid. After recrystallization twice with toluene and ethyl acetate, 38.4 g of off-white solid was obtained with a purity of 99.91% and a yield of 72%.

[0242] Comparative Example

[0243] The synthetic route for intermediate L5 in the existing method is as follows:

[0244]

[0245] To a 1L reaction flask equipped with a stirrer, thermometer, and reflux condenser, add L4 (37.8g, 0.09mol, 1.0eq), cesium carbonate (60g, 0.18mol, 2.0eq), palladium acetate (0.81g, 3.6mmol, 0.04eq), and 270mL of methylpyrrolidone NMP. Stir and purge with nitrogen gas, then add 30mL of tri-tert-butylphosphine. Heat to 130℃ and react for 3 hours. HPLC monitoring showed that the reaction of starting material L4 was complete, and the ratio of main product L5 to isomer byproducts in the reaction solution was 84%:12%. The mixture was cooled to 50°C, 450 mL of water was added, and 300 mL of toluene was added for extraction. The mixture was washed twice with water. The toluene organic phase was passed through a silica gel column and the silica gel was washed off. The filtrates were combined and concentrated under negative pressure until the material precipitated into a viscous consistency. The mixture was cooled to 25°C, filtered, and the filter cake was washed with 100 mL of ethanol. The toluene recrystallization operation was repeated twice to obtain 21.6 g of off-white material with a purity of 99.61% and a yield of 62.7%.

[0246] Because of the presence of two cyclization sites, isomers are generated, which reduces the purity of the reaction. In addition, in order to remove the isomers, the number of purification steps needs to be increased, resulting in material waste and reduced yield. The yield of this cyclization reaction step is only 62.7%, which is far lower than the average yield of about 80% of the cyclization reaction in this invention.

[0247] Device Examples

[0248] This embodiment provides an organic electroluminescent device, such as... Figure 2 As shown, the device includes an anode 2, a hole injection layer 3, a hole transport layer 4, a light-emitting layer 5, an electron transport layer 6, an electron injection layer 7, and a cathode 8, which are sequentially stacked on a substrate 1. The device structure is: substrate + anode (indium tin oxide (ITO) coated glass substrate) / hole injection layer (HIL) / hole transport layer (HTL) / light-emitting layer (EML) / electron transport layer (ETL) / electron injection layer (EIL) / cathode (Al).

[0249] The materials used to manufacture the organic electroluminescent device are as follows:

[0250]

[0251] The diarylcarbazole materials provided in Examples 1-20.

[0252] The fabrication of the above-mentioned organic electroluminescent device includes the following steps:

[0253] 1) Substrate cleaning:

[0254] The glass substrate coated with transparent ITO was ultrasonically treated in an aqueous cleaning agent (the composition and concentration of the aqueous cleaning agent: ethylene glycol solvent ≤10wt%, triethanolamine ≤1wt%), then rinsed in deionized water, ultrasonically degreased in a mixed solvent of acetone and ethanol (volume ratio of acetone and ethanol 1:1), baked in a clean environment until all moisture was removed, and then cleaned with ultraviolet light and ozone.

[0255] 2) Preparation of organic layer:

[0256] The ITO transparent substrate was transferred to an evaporation equipment and vacuumed to 1×10⁻⁶. -6 Up to 2×10 -4 Pa, sequentially deposited on the anode film a 10nm hole injection layer (HIL) / 80nm hole transport layer (HTL) / 38nm light emission layer (EML) / 30nm electron transport layer (ETL) / 1nm electron injection layer (EIL) / 80nm thick cathode (Al).

[0257] in:

[0258] The hole injection layer (HIL) is a mixture of NDP-9 and HT, wherein the mass ratio of NDP-9 to HT is 3:97.

[0259] The material of the hole transport layer (HTL) is HT;

[0260] The material of the light-emitting layer (EML) includes a host material and a guest material. The host material is an organic electroluminescent composition formed by mixing the K1-K20 compounds prepared in Examples 1-20 with N-type in a certain proportion. The guest material is RD-5. The specific materials and proportions are shown in Table 1.

[0261] The material of the electron transport layer (ETL) is ET-1;

[0262] The electron injection layer (EIL) is made of LiQ; the partial layers of the organic electroluminescent device and their materials and thicknesses are shown in Table 1.

[0263] Table 1. Partial Layers, Materials, and Thicknesses of Organic Electroluminescent Devices

[0264]

[0265] Test case

[0266] The organic electroluminescent devices obtained in Device Examples 1-20 of the Device Examples were tested.

[0267] Instruments: The current, voltage, brightness, emission spectrum and other characteristics of the device were tested simultaneously using a PR 650 spectral scanning luminance meter and a Keithley K 2400 digital source meter system;

[0268] Test conditions: Photoelectric property test conditions: current density 10 mA / cm² 2 .

[0269] Lifetime test: Current density 50mA / cm 2 The recording time (in hours) is recorded when the device brightness drops to 95% of its original brightness.

[0270] The device performance test results are shown in Table 2:

[0271] Table 2 Device performance test results

[0272]

[0273]

[0274] As shown in Table 2, the host material obtained by the preparation method based on diarylcarbazole material provided by this invention has achieved good performance in red OLED devices: driving voltage of 3.30-3.58V, current efficiency of 19.25-24.56Cd / A, and lifetime (T95) of 215.7-296.4hrs. Its low driving voltage, good current efficiency, and long operating lifetime fully demonstrate the structural advantages of diarylcarbazole material. The novel preparation method provided by this invention offers a new solution for the development and research of diarylcarbazole material, greatly expanding the application of carbazole materials in the field of red light host materials.

[0275] The above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

[0276] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a diarylcarbazole-based material, characterized in that, Includes the following steps: Intermediate A was obtained by nitration of 4-bromo-2-chloro-1-fluorobenzene; Coupling intermediate B was obtained by using intermediate A and 1-naphthoboronic acid via a Suzuki coupling reaction; Intermediate C was prepared from intermediate B via a nitro cyclization reaction. Intermediate C is coupled with iodobenzene or iodobenzene derivative D to form intermediate E; Pinaryl borate intermediate F was prepared using intermediate E; Intermediate F and o-bromoaniline or o-bromoaniline derivative G are coupled via a Suzuki reaction to obtain intermediate H; Intermediate H was cyclized under alkaline conditions to obtain intermediate I, specifically through the following steps: Intermediate H, potassium tert-butoxide, and dimethyl sulfoxide were added to a reactor, stirring was started, nitrogen gas was introduced, the material was heated to 90±5℃ and reacted for 2-4 hours, then cooled to 25±5℃, water was added to separate the material, stirring was carried out for 0.5-1 hours, and the mixture was filtered. The filter cake was washed with water. The filter cake was transferred to a reactor, chlorobenzene was added, and the mixture was heated to 120±5℃ and passed through a silica gel column. The mixture was concentrated at normal pressure, cooled to 25±5℃, and crystallized for 1-2 hours. The mixture was then filtered to obtain intermediate I. The intermediate I and the haloaryl derivative J were coupled to obtain the diarylcarbazole material K. The synthesis route is as follows: The diarylcarbazole material K is selected from any one of the following compounds: 。 2. The preparation method of the diarylcarbazole-based material according to claim 1, characterized in that, The iodobenzene or iodobenzene derivative D is selected from the following structures: ； The o-bromoaniline or o-bromoaniline derivative G is selected from one of the following structures: 。 3. The preparation method of the diarylcarbazole-based material according to claim 1, characterized in that, The haloaryl derivative J is selected from one of the following structures: 。 4. The preparation method of the diarylcarbazole-based material according to claim 1, characterized in that, Intermediate A is prepared according to the following steps: Dichloromethane, concentrated sulfuric acid and 4-bromo-2-chloro-1-fluorobenzene are added sequentially to a reactor, stirring is started, nitrogen gas is introduced, 68% concentrated nitric acid is added dropwise at 0°C, the temperature is raised to reflux for 1-2 hours, the temperature is lowered to 25±5°C, the lower acid layer is separated, the organic phase is washed with water, washed with sodium bicarbonate solution, washed with water again and concentrated, then n-hexane is added, the temperature is raised to reflux and stirred for 1-2 hours, the temperature is lowered to 0±5°C, crystallization is carried out for 1-2 hours, filtered and dried to obtain intermediate A; Intermediate B is prepared according to the following steps: Intermediate A, 1-naphthoboric acid, potassium carbonate, toluene, ethanol, and pure water are added to a reactor, stirring is started, nitrogen gas is introduced, tetra(triphenylphosphine)palladium is added, the temperature is raised to 75±5℃ and reacted for 3-6 hours, the temperature is lowered to 35±5℃, the aqueous layer is separated and washed with water, the temperature is maintained at 60±5℃ and passed through a silica gel column, concentrated at normal pressure, ethanol is added and the temperature is raised to reflux and stirred for 1-2 hours, the temperature is lowered to 25±5℃, filtered, and dried to obtain intermediate B; Intermediate C is prepared according to the following steps: Intermediate B, triphenylphosphine, and o-dichlorobenzene are added to a reactor, stirring is started, nitrogen gas is introduced, the temperature is raised to 160±10℃ and reacted for 8-12 hours, the temperature is lowered to 90±5℃, o-dichlorobenzene is removed by vacuum distillation, the temperature is lowered to 70±5℃, ethanol is added, the mixture is refluxed and stirred for 1-2 hours, the temperature is lowered to 25±5℃, filtered, the filter cake is refluxed and stirred with n-hexane for 1-2 hours, the temperature is lowered to 25±5℃, filtered, and dried to obtain intermediate C.

5. The preparation method of the diarylcarbazole-based material according to claim 1, characterized in that, The intermediate E is prepared according to the following steps: intermediate C, iodobenzene or iodobenzene derivative D, cuprous iodide, 1,10-phenanthroline, potassium carbonate, and dioxane are added to a reactor. Stirring is started, nitrogen gas is introduced, and the mixture is heated to reflux and kept at that temperature for 8-12 hours. The temperature is then lowered to 50±5℃, filtered, and the filter cake is washed with dioxane. The dioxane is concentrated and evaporated to remove the filter cake. Toluene and water are added for extraction and phase separation. The toluene phase is concentrated at atmospheric pressure, ethanol is added, and the mixture is heated to reflux and stirred for 1-2 hours. The temperature is then lowered to 25±5℃, filtered, and dried to obtain intermediate E. Intermediate F is prepared according to the following steps: Intermediate E, pinacol diborate, tris(benzylacetone)dipalladium, X-Phos, potassium acetate, and dioxane are added to a reactor. Stirring is started, nitrogen gas is introduced, and the material is heated to reflux for 6-8 hours. The temperature is then lowered to 50±5℃, filtered, and the filter cake is washed with dioxane. The dioxane is concentrated and evaporated to remove the dioxane. Dichloromethane and water are added for phase separation. The dichloromethane phase is concentrated at atmospheric pressure, and n-hexane is added. The temperature is raised to reflux and slurryed for 1-2 hours, then lowered to 25±5℃, filtered, and dried to obtain intermediate F.

6. The method for preparing diarylcarbazole-based materials according to claim 1, characterized in that, The intermediate H is prepared according to the following steps: intermediate F, o-bromoaniline or o-bromoaniline derivative G, potassium carbonate, toluene and pure water are added to a reactor, stirring is started, and palladium dichloride of bis(triphenylphosphine) is added under nitrogen protection. The mixture is heated to reflux for 2-4 hours, cooled to 50±5℃, allowed to stand to separate the aqueous layer, the organic phase is washed with water, kept at 60±5℃ and passed through a silica gel column and the silica gel is washed off, the organic layers are combined, toluene is removed by evaporation at normal pressure, ethanol is added and refluxed for 1-2 hours, the mixture is cooled to 25±5℃ and filtered to obtain off-white intermediate H.

7. The method for preparing diarylcarbazole-based materials according to claim 1, characterized in that, The diarylcarbazole material K is prepared according to the following steps: intermediate I, haloaryl derivative J, sodium tert-butoxide and toluene are added to a reactor, stirring is started, nitrogen gas is introduced, and when the material is heated to 60±5℃, 10% tri-tert-butylphosphine toluene solution and tris(benzylideneacetone)dipalladium are added, and the temperature is raised to reflux for 1-2 hours. After the reaction is completed, the temperature is lowered to 50±5℃, water is added to quench the reaction, water is separated, the organic phase is washed once with water, and the solution is kept at 80±5℃ and passed through a silica gel column and the silica gel is washed. The filtrates are combined, concentrated and toluene is evaporated, the temperature is lowered to 70±5℃, ethanol is added, the temperature is lowered to 25±5℃, and the solution is filtered to obtain an off-white solid. The solution is then recrystallized 2-3 times with toluene / ethyl acetate to obtain the off-white solid diarylcarbazole material K.

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