Cycloalkane substituted compound, hole transport material and organic electroluminescent device

Abstract

The invention relates to the technical field of organic light-emitting display, in particular to a cycloalkane substituted compound, a hole transport material and an organic light-emitting device. The invention provides a compound as shown in a general formula (I), which can be used for hole transport materials. The compound has a parent structure of ortho-dibenzoheterocycle substituted arylamine, has high bond energy between atoms and good thermal stability, is beneficial to solid-state accumulation between molecules, has strong hole transition ability, and can effectively reduce the voltage of a device and prolong the service life of the material when being used as a hole transport material and a light-emitting auxiliary layer material. The invention also provides an organic electroluminescent device and a display device containing the compound shown in the general formula (I). # imgabs0 #

Description

Technical Field

[0001] The present invention relates to the technical field of organic light-emitting display, and particularly relates to a cycloalkane-substituted compound, a hole transport material, and an organic electroluminescent device. Background Art

[0002] Electroluminescence (EL) refers to the phenomenon that a luminescent material emits light under the action of an electric field, being excited by an electric current and an electric field. It is a luminescence process that directly converts electrical energy into light energy. Organic electroluminescent displays (hereinafter referred to as OLEDs) have a series of advantages such as self-luminescence, low-voltage DC drive, all-solid state, wide viewing angle, light weight, simple composition and process. Compared with liquid crystal displays, organic electroluminescent displays do not require a backlight, have a large viewing angle, low power, a response speed that can reach 1000 times that of liquid crystal displays, and a manufacturing cost lower than that of liquid crystal displays with the same resolution. Therefore, organic electroluminescent devices have very broad application prospects.

[0003] With the continuous advancement of OLED technology in the two major fields of lighting and display, people pay more attention to the research on high-efficiency organic materials that affect the performance of OLED devices. An organic electroluminescent device with high efficiency and long life is usually the result of the optimal combination of the device structure and various organic materials, which provides great opportunities and challenges for the design and development of functional materials with various structures.

[0004] Compared with inorganic luminescent materials, organic electroluminescent materials have many advantages. For example, they have good processability and can form films on any substrate by evaporation or spin coating, enabling flexible display and large-area display; the optical, electrical, and stability properties of the materials can be adjusted by changing the molecular structure, and there is a large space for material selection. In the most common OLED device structure, it usually includes the following types of organic materials: hole injection materials, hole transport materials, electron transport materials, as well as various color-emitting materials (dyes or doped guest materials) and corresponding host materials, etc. Among them, as an important functional material, the hole transport material has a direct impact on the hole mobility and ultimately affects the light-emitting efficiency of the OLED. However, the hole transport rate that can be achieved by the hole transport materials currently applied in OLEDs is relatively low, the energy level matching with the adjacent layer is poor, and the efficiency and lifespan cannot be balanced, seriously restricting the display function and development of OLED display devices. Summary of the Invention

[0005] The object of the present invention is to provide a cycloalkane-substituted compound and a hole transport material to improve the working efficiency and extend the service life of an organic electroluminescent device.

[0006] The object of the first aspect of the present invention is to provide a cycloalkane-substituted compound having a structure as shown in formula (I):

[0007]

[0008] Wherein,

[0009] L is selected from a chemical bond, a substituted or unsubstituted C6-C 30 aryl group, or a substituted or unsubstituted C5-C 30 heteroaryl group;

[0010] R 1 and R 2 are each independently selected from a C1-C4 alkyl group, a C3-C6 cycloalkane, a substituted or unsubstituted C6-C 30 aryl group, or a substituted or unsubstituted C5-C 30 heteroaryl group, and adjacent substituents can be connected to form a ring;

[0011] R and R' are each independently selected from hydrogen, a substituted or unsubstituted C6-C 30 aryl group, or a substituted or unsubstituted C5-C 30 [[ID=�1]]heteroaryl group;

[0012] m, n, and o are each independently selected from 0, 1, two, 3, 4;

[0013] X is selected from O, S, N;

[0014] Ar is selected from a substituted or unsubstituted C6-C 30 aryl group, or a substituted or unsubstituted C5-C 30 heteroaryl group;

[0015] A is selected from the following fragments:

[0016]

[0017] The heteroatoms on the heteroaryl group are each independently selected from O, S, or N;

[0018] The hydrogen atoms on the aryl group and heteroaryl group can each independently be replaced by Ra, and Ra are each independently selected from deuterium, halogen, nitro, cyano, a C1-C4 alkyl group, a C5-C 20 cycloalkyl group, phenyl group, biphenyl group, terphenyl group, or naphthyl group.

[0019] Preferably, the Ar is selected from a substituted or unsubstituted C6-C 24 aryl group, or a substituted or unsubstituted C5-C 18 heteroaryl group.

[0020] Preferably, the R 1 and R2 Each independently selected from methyl, ethyl, isopropyl, tert-butyl, cyclopentyl, cyclohexyl, and the following groups which are unsubstituted or substituted by Ra: phenyl, biphenyl, naphthyl, fluorenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl.

[0021] Preferably, R and R' each independently selected from hydrogen and the following groups which are unsubstituted or substituted by Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, dibenzofuranyl, dibenzothiophenyl, 9,9-dimethylfluorenyl, spirofluorene, arylamine group.

[0022] More preferably, Ar is selected from the following groups which are unsubstituted or substituted by Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, benzofuranyl, dibenzofuranyl, benzothiophenyl, dibenzothiophenyl, 9,9-dimethylfluorenyl, spirofluorene, arylamine group, carbazolyl.

[0023] Preferably, the compound is selected from the compounds shown as A1 - A25 below:

[0024]

[0025]

[0026] An object of the second aspect of the present invention is to provide a hole transporting material, which contains at least one of the compounds provided in the first aspect of the present invention.

[0027] An object of the third aspect of the present invention is to provide an organic electroluminescent device, which contains at least one of the hole transporting materials provided in the second aspect of the present invention.

[0028] An object of the fourth aspect of the present invention is to provide a display device, which contains the organic electroluminescent device provided in the third aspect of the present invention.

[0029] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0030] 1. The compounds of the present invention have a parent structure of ortho-dibenzheterocyclic group-substituted arylamine, with high bond energy between atoms, good thermal stability, which is conducive to intermolecular solid-state packing, and strong hole transition ability. When used as a hole transporting material, it can effectively reduce the device voltage and improve the material life.

[0031] 2. The compounds of the present invention are applied in the hole transporting layer, with appropriate energy level levels between adjacent layers, which is conducive to hole injection and migration, can effectively reduce the driving voltage, and at the same time, with a high hole migration rate, can achieve good luminous efficiency in the device.

[0032] 3. The compounds of the present invention have a large conjugated plane, which is conducive to molecular packing, showing good thermodynamic stability and long lifetime in the device.

[0033] Meanwhile, the preparation process of the compounds of the present invention is simple and easy to implement, and the raw materials are readily available, which is suitable for industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required in the description of the embodiments or the prior art. Obviously, the drawings in the following description are only one embodiment of the present invention, and those of ordinary skill in the art can also obtain other embodiments based on these drawings.

[0035] Figure 1 It is a schematic structural diagram of a typical organic electroluminescent device.

[0036] Each part is respectively: 1. Substrate; 2. Reflective anode electrode; 3. Hole injection layer; 4. Hole transport layer; 5. Light-emitting layer; 6. Electron transport layer; 7. Electron injection layer; 8. Cathode electrode. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0037] The following will clearly and completely describe the technical solutions in the present invention in conjunction with the drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all of them. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention belong to the scope of protection of the present invention.

[0038] In the present invention, there is no particular limitation on the type and structure of the organic electroluminescent device, as long as the hole transport material provided by the present invention can be used.

[0039] The organic electroluminescent device of the present invention can be a top-emitting structure light-emitting device. For example, it sequentially includes an anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a transparent or semi-transparent cathode on a substrate.

[0040] The organic electroluminescent device of the present invention can also be a bottom-emitting structure light-emitting device. For example, it sequentially includes a transparent or semi-transparent anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a cathode structure on a substrate.

[0041] The organic electroluminescent device of the present invention can also be a double-sided emitting structure light-emitting device. For example, it sequentially includes a transparent or semi-transparent anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a transparent or semi-transparent cathode structure on a substrate.

[0042] In the organic electroluminescent device of the present invention, except that the hole transport layer contains the hole transport material provided by the present invention, any material used for the layer in the prior art can be used for other layers.

[0043] Figure 1 FIG. shows a schematic diagram of a typical organic electroluminescent device, in which, from bottom to top, a substrate 1, a reflective anode electrode 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 electrode 8 are sequentially arranged.

[0044] It can be understood that Figure 1 only a schematic structure of a typical organic electroluminescent device is shown, and the present invention is not limited to this structure. The hole transport material of the present invention can be used for any type of organic electroluminescent device. For example, the organic electroluminescent device may further include an electron blocking layer, a hole blocking layer, a light extraction layer, etc. In actual applications, these layers can be added or omitted according to specific circumstances.

[0045] For convenience, the organic electroluminescent device of the present invention will be described below with reference to Figure 1 However, this does not mean any limitation to the protection scope of the present invention. It can be understood that all organic electroluminescent devices that can use the hole transport material of the present invention are within the protection scope of the present invention.

[0046] In the present invention, the substrate 1 is not particularly limited, and conventional substrates used in organic electroluminescent devices in the prior art can be used. For example, glass, polymer materials, and glass and polymer materials with TFT components, etc.

[0047] In the present invention, the material of the reflective anode electrode 2 is not particularly limited, and it can be selected from transparent conductive materials known in the prior art such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), zinc oxide (ZnO), low-temperature polycrystalline silicon (LTPS), etc., or metal materials such as silver and its alloys, aluminum and its alloys, etc., or organic conductive materials such as PEDOT (poly-3,4-ethylenedioxythiophene), or a multi-layer structure of the above materials, etc.

[0048] In the present invention, the material of the hole injection layer 3 is not particularly limited, and a hole injection material well-known in the art or the hole transport material provided by the present invention can be selected as the hole injection material.

[0049] For example, the material of the hole injection layer can be selected from at least one of the following compounds HT-1 to HT-31:

[0050]

[0051]

[0052]

[0053] In the present invention, the hole injection layer 3 may further include a p-type dopant. There is no particular limitation on the type of the p-type dopant, and various p-type dopants known in the art can be used. For example, the p-type dopant can be selected from at least one of the following compounds:

[0054]

[0055] In the present invention, there is no particular limitation on the amount of the p-type dopant, and the amount can be a commonly known amount to those skilled in the art.

[0056] In the present invention, the hole transport layer 4 contains at least one of the hole transport materials of the present invention. The hole transport layer 4 may also contain any combination of at least one of the hole transport materials of the present invention and known hole transport materials. Currently known hole transport materials can be selected from at least one of the above-mentioned compounds HT-1 to HT-31, but are not limited to the listed compounds.

[0057] In the present invention, there is no particular limitation on the luminescent material of the light-emitting layer 5, and any luminescent material known to those skilled in the art can be used. For example, the luminescent material may include a host material and a guest material. For example, it can be selected from at least one of the following compounds RH-1 to RH-13, but not limited thereto:

[0058]

[0059] The host material of the light-emitting layer can also use at least one of the known host materials for green light-emitting layers. For example, it can be selected from at least one of the following compounds GPH-1 to GPH-80, but not limited thereto:

[0060]

[0061]

[0062]

[0063]

[0064] The host material of the light-emitting layer can also use at least one of the known host materials for blue light-emitting layers. For example, it can be selected from at least one of the following compounds BH-1 to BH-10, but not limited thereto:

[0065]

[0066] The host material of the light-emitting layer may be a host material for a red light-emitting layer. For example, it may be selected from at least one of the following compounds RPD-1 to RPD-28, but not limited thereto:

[0067]

[0068]

[0069] The host material of the light-emitting layer may be a host material for a green light-emitting layer. For example, it may be selected from at least one of the following compounds GD01 to GD04, but not limited thereto:

[0070]

[0071] The host material of the light-emitting layer may be a host material for a blue light-emitting layer. For example, it may be selected from at least one of the following compounds BD-1 to BD-9, but not limited thereto:

[0072]

[0073] In the present invention, the material of the electron transport layer 6 is not particularly limited and can be made of electron transport materials well-known in the art. For example, the electron transport layer material may be selected from at least one of the following compounds ET-1 to ET-57:

[0074]

[0075]

[0076]

[0077]

[0078] In the present invention, the electron transport layer 6 may further include an n-type dopant. The type of the n-type dopant is not particularly limited, and various n-type dopants known in the art can be used. For example, the n-type dopant may be a compound represented by the following formula:

[0079]

[0080] In the present invention, the amount of the n-type dopant is not particularly limited and can be an amount well-known to those skilled in the art.

[0081] In the present invention, the material of the electron injection layer 7 is not particularly limited, and electron injection materials well-known in the art can be used. For example, it may include at least one of the materials such as LiQ, LiF, NaCl, CsF, Li2O, Cs2CO3, BaO, Na, Li, Ca, etc. in the prior art.

[0082] In the present invention, the material of the cathode electrode 8 is not particularly limited. For example, it can be selected from but not limited to metals, metal mixtures, oxides such as magnesium-silver mixture, LiF / Al, ITO, Al, etc.

[0083] The present invention provides a display device, which includes the organic electroluminescent device provided by the present invention. The display device includes but is not limited to monitors, televisions, tablet computers, mobile communication terminals, etc.

[0084] The method for preparing the organic electroluminescent device of the present invention is not particularly limited, and any method known in the art can be adopted. For example, the present invention can be prepared by the following preparation method, which includes the following steps:

[0085] (1) Clean the reflective anode electrode 2 on the top-emitting OLED device substrate 1, and respectively perform steps such as chemical washing, water washing, brushing, high-pressure water washing, air knife in a cleaning machine, and then perform heat treatment;

[0086] (2) Vacuum deposit a hole injection material on the reflective anode electrode 2 as the hole injection layer 3;

[0087] (3) Vacuum deposit a hole transport material on the hole injection layer 3 as the hole transport layer 4;

[0088] (4) Vacuum deposit a light-emitting layer 5 on the hole transport layer 4, and the light-emitting layer 5 contains a host material and a guest material;

[0089] (5) Vacuum deposit an electron transport material on the light-emitting layer � as the electron transport layer 6;

[0090] (6) Vacuum deposit an electron injection material on the electron transport layer 6 as the electron injection layer 7, and the electron injection material is selected from one or a combination of materials such as LiQ, LiF, NaCl, CsF, Li2O, Cs2CO3, BaO, Na, Li, Ca, etc.;

[0091] (7) Vacuum deposit a cathode material on the electron injection layer 7 as the cathode electrode 8.

[0092] The above only describes the structure and preparation method of a typical organic electroluminescent device. It should be understood that the present invention is not limited to this structure. The hole transport material of the present invention can be used in any structure of organic electroluminescent devices, and the organic electroluminescent devices can be prepared by any method known in the art.

[0093] The synthesis method of the compound of the present invention is not particularly limited, and any method known to those skilled in the art can be adopted for synthesis. The following is an example to illustrate the synthesis process of the compound of the present invention.

[0094] Synthesis Example 1: Synthesis of Compound A2

[0095]

[0096] 100 mmol of 2-bromo-1-chloro-4-iodobenzene, 100 mmol of phenylboronic acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of tetrahydrofuran (THF), and 200 ml of water were added to a reaction flask, and 1 mmol of tetrakis(triphenylphosphine)palladium (Pd(PPh₃)₄) was added. The reaction was carried out at 60 °C for 12 h. After the reaction was completed, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, and the organic phase was concentrated to obtain a white solid. After filtration and washing with water, the obtained solid was purified by recrystallization with toluene to obtain white powder M1.

[0097] 100 mmol of M1, 100 mmol of 3-dibenzothiopheneboronic acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of tetrahydrofuran (THF), and 200 ml of water were added to a reaction flask, and 1 mmol of tetrakis(triphenylphosphine)palladium (Pd(PPh₃)₄) was added. The reaction was carried out at 60 °C for 12 h. After the reaction was completed, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, and the organic phase was concentrated to obtain a white solid. After filtration and washing with water, the obtained solid was purified by recrystallization with toluene to obtain white powder M2.

[0098] 100 mmol of M2, 100 mmol of 2-amino-9,9-dimethylfluorene, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of xylene were added to a reaction flask, and 1 mol% of bis(dibenzylideneacetone)palladium (Pd(dba)) was added. The reaction was carried out at 120 °C for 12 h. After the reaction was completed, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, and after filtration and washing with water, the obtained solid was purified by recrystallization with toluene to obtain white powder M3, where the addition amount of Pd(dba) was 1 mol% of M2.

[0099] After adding 108 g (0.50 mol) of 1-bromoadamantane to 188 g (2.0 mol) of phenol and heating at 120 °C for 12 hours until the reaction ended, it was allowed to cool to room temperature and then added to a 2 L beaker and precipitated while stirring. After filtration, the precipitate was washed with hot water 3 times and thoroughly dried under vacuum to obtain M4.

[0100] After dissolving 91 g (0.40 mol) of M4 and 63 g (0.80 mol) of pyridine in 500 ml of dichloromethane, the temperature was lowered to 0 °C, and 135 g (0.48 mol) of trifluoromethanesulfonic anhydride was slowly added. Stirring was carried out for 3 hours. After the reaction ended, 300 ml of hydrochloric acid was added, and then 300 ml of water was added for extraction. The organic layer was dried with anhydrous magnesium chloride, and after distilling the filtrate, column chromatography was carried out to obtain M5.

[0101] 100 mmol of M3, 100 mmol of M5, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of xylene were added to a reaction flask, and 1 mol% of bis(dibenzylideneacetone)palladium (Pd(dba)) was added. The reaction was carried out at 120 °C for 12 h, wherein the addition amount of Pd(dba) was 1 mol% of M3. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder A2.

[0102] 1 H NMR (400 MHz, Chloroform) δ 8.45 (d, J = 7.2 Hz, 1H), 8.39 (s, 1H), 8.17 (d, J = 7.2 Hz, 1H), 8.08 (s, 1H), 7.97 (d, J = 8.4 Hz, 1H), 7.90 (T, J = 7.6 Hz, 3H), 7.75 (d, J = 7.6 Hz, 2H), 7.65 (d, J = 7.2 Hz, 1H), 7.58 - 7.26 (m, 11H), 7.14 (d, J = 7.2 Hz, 4H), 2.06 - 1.98 (m, 9H), 1.70 (t, J = 7.2 Hz, 6H), 1.67 (s, 6H).

[0103] Synthesis Example 2: Synthesis of Compound A3

[0104]

[0105] 100 mmol of 1-bromo-2-chloro-3-iodobenzene, 100 mmol of 4-(trimethylsilyl)phenylboronic acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of tetrahydrofuran (THF) and 200 ml of water were added to a reaction flask, and 1 mmol of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4) was added. The reaction was carried out at 60 °C for 12 h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, filtered, washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M1.

[0106] 100 mmol of M1, 100 mmol of 3-dibenzofuranboronic acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of tetrahydrofuran (THF) and 200 ml of water were added to a reaction flask, and 1 mmol of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4) was added. The reaction was carried out at 60 °C for 12 h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, filtered, washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M2.

[0107] 100 mmol of M2, 100 mmol of 2-amino-9,9-dimethylfluorene, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of xylene were added to a reaction flask, and 1 mol% of bis(dibenzylideneacetone)palladium (Pd(dba)) was added, where the addition amount of Pd(dba) was 1 mol% of M2. The reaction was carried out at 120 °C for 12 h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M3.

[0108] After adding 108 g (0.50 mol) of 1-bromoadamantane to 188 g (2.0 mol) of phenol and heating at 120 °C for 12 h until the reaction was completed, it was allowed to cool to room temperature and then added to a 2 L beaker and precipitated with stirring. After filtration, the precipitate was washed 3 times with hot water and thoroughly dried under vacuum to obtain M4.

[0109] After dissolving 91 g (0.40 mol) of M4 and 63 g (0.80 mol) of pyridine in 500 ml of dichloromethane, the temperature was lowered to 0 °C, and 135 g (0.48 mol) of trifluoromethanesulfonic anhydride was slowly added. Stir for 3 h. After the reaction was completed, 300 ml of hydrochloric acid was added, and then 300 ml of water was added for extraction. The organic layer was dried with anhydrous magnesium chloride, the filtrate was distilled, and then column chromatography was carried out to obtain M5.

[0110] 100 mmol of M3, 100 mmol of M5, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of xylene were added to a reaction flask, and 1 mol% of bis(dibenzylideneacetone)palladium (Pd(dba)) was added. The reaction was carried out at 120 °C for 12 h, where the addition amount of Pd(dba) was 1 mol% of M3. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder A3.

[0111] 1 H NMR (400 MHz, Chloroform) δ 8.20 (d, J = 8.0 Hz, 2H), 7.95 (d, J = 7.2 Hz, 1H), 7.90 (s, 1H), 7.86 (d, J = 7.2 Hz, 1H), 7.82 (d, J = 8.0 Hz, 1H), 7.75 (t, J = 8.0 Hz, 3H), 7.60 - 7.51 (m, 4H), 7.45 - 7.21 (m, 8H), 7.10 (d, J = 8.0 Hz, 4H), 2.06 - 1.98 (m, 9H), 1.70 (t, J = 7.2 Hz, 6H), 1.67 (s, 6H), 0.25 (s, 9H).

[0112] Synthesis Example 3: Synthesis of Compound A7

[0113]

[0114] 100 mmol of 2-bromo-1-chloro-4-iodobenzene, 100 mmol of phenylboronic acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of tetrahydrofuran (THF), and 200 ml of water were added to a reaction flask, and 1 mmol of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4) was added. The reaction was carried out at 60 °C for 12 h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature. Water was added, and the organic phase was concentrated to obtain a white solid. After filtration and washing with water, the obtained solid was purified by recrystallization with toluene to obtain white powder M1.

[0115] 100 mmol of M1, 100 mmol of 3-dibenzothiopheneboronic acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of tetrahydrofuran (THF), and 200 ml of water were added to a reaction flask, and 1 mmol of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4) was added. The reaction was carried out at 60 °C for 12 h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature. Water was added, and the organic phase was concentrated to obtain a white solid. After filtration and washing with water, the obtained solid was purified by recrystallization with toluene to obtain white powder M2.

[0116] 100 mmol of M2, 100 mmol of 4-amino-9,9-dimethylfluorene, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of xylene were added to a reaction flask, and 1 mol% of bis(dibenzylideneacetone)palladium (Pd(dba)) was added, where the addition amount of Pd(dba) was 1 mol% of M2. The reaction was carried out at 120 °C for 12 h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature. Water was added, and after filtration and washing with water, the obtained solid was purified by recrystallization with toluene to obtain white powder M3.

[0117] After adding 108 g (0.50 mol) of 1-bromoadamantane to 188 g (2.0 mol) of phenol and heating at 120 °C for 12 hours until the reaction was completed, it was left to cool to room temperature and then added to a 2 L beaker and precipitated with stirring. After filtration, the precipitate was washed 3 times with hot water and dried thoroughly under vacuum to obtain M4.

[0118] After dissolving 91 g (0.40 mol) of M4 and 63 g (0.80 mol) of pyridine in 500 ml of dichloromethane, the temperature was lowered to 0 °C, and 135 g (0.48 mol) of trifluoromethanesulfonic anhydride was slowly added. After stirring for 3 hours, 300 ml of hydrochloric acid was added after the reaction was completed, and then 300 ml of water was added for extraction. The organic layer was dried with anhydrous magnesium chloride, and after distilling the filtrate, column chromatography was carried out to obtain M5.

[0119] 100 mmol of M3, 100 mmol of M5, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of xylene were added to a reaction flask, and 1 mol% of bis(dibenzylideneacetone)palladium (Pd(dba)) was added. The reaction was carried out at 120 °C for 12 h, wherein the addition amount of Pd(dba) was 1 mol% of M3. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder A7.

[0120] 1 H NMR (400 MHz, Chloroform) δ8.39 (d, J = 6.8 Hz, 1H), 8.35 (s, 1H), 8.17 (d, J = 7.2 Hz, 1H), 8.05 (s, 1H), 7.94 (d, J = 8.0 Hz, 1H), 7.84 (t, J = 7.6 Hz, 2H), 7.70 (d, J = 8.0 Hz, 2H), 7.62 - 7.15 (m, 13H), 7.05 (d, J = 8.0 Hz, 4H), 2.06 - 1.98 (m, 9H), 1.70 (t, J = 7.2 Hz, 6H), 1.67 (s, 6H).

[0121] Synthesis Example 4: Synthesis of Compound A8

[0122]

[0123] 100 mmol of 2-bromo-1-chloro-4-iodobenzene, 100 mmol of phenylboronic acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of tetrahydrofuran (THF) and 200 ml of water were added to a reaction flask, and 1 mmol of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4) was added. The reaction was carried out at 60 °C for 12 h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, filtered, washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M1.

[0124] Add 100 mmol of 7-chloro-2-phenyldibenzothiophene, 100 mmol of bis(pinacolato)diboron, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of xylene into a reaction flask, and add 1 mol% of bis(dibenzylideneacetone)palladium (Pd(dba)), where the addition amount of Pd(dba) is 1 mol% of 7-chloro-2-phenyldibenzothiophene. React at 120 °C for 12 h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain white powder M2.

[0125] Add 100 mmol of M1, 100 mmol of M2, 41.4 g of potassium carbonate (300 mmol), 800 ml of tetrahydrofuran (THF) and 200 ml of water into a reaction flask, and add 1 mmol of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4). React at 60 °C for 12 h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain white powder M3.

[0126] Add 100 mmol of M3, 100 mmol of 2-amino-9,9-dimethylfluorene, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of xylene into a reaction flask, and add 1 mol% of bis(dibenzylideneacetone)palladium (Pd(dba)), where the addition amount of Pd(dba) is 1 mol% of M3. React at 120 °C for 12 h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain white powder M4.

[0127] After adding 108 g (0.50 mol) of 1-bromoadamantane to 188 g (2.0 mol) of phenol and heating at 120 °C for 12 hours until the reaction is completed, allow it to cool to room temperature, then add it to a 2 L beaker and precipitate while stirring. After filtration, wash the precipitate 3 times with hot water, and obtain M5 after thorough vacuum drying.

[0128] Dissolve 91 g (0.40 mol) of M5 and 63 g (0.80 mol) of pyridine in 500 ml of dichloromethane, then cool the temperature to 0 °C, and slowly add 135 g (0.48 mol) of trifluoromethanesulfonic anhydride. Stir for 3 hours. After the reaction is completed, add 300 ml of hydrochloric acid, and then add 300 ml of water for extraction. Dry the organic layer with anhydrous magnesium chloride, distill the filtrate, and perform column chromatography to obtain M6.

[0129] Add 100 mmol of M4, 100 mmol of M6, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of xylene into a reaction flask, and add 1 mol% of bis(dibenzylideneacetone)palladium (Pd(dba)). React at 120 °C for 12 h, wherein the addition amount of Pd(dba) is 1 mol% of M4. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain white powder A8.

[0130] 1 H NMR(400MHz,Chloroform)δ9.05(s,1H),8.45(s,1H),8.15(t,J=7.2Hz,2H),8.10(s,1H),8.01(t,J=7.2Hz,2H),7.90(d,J=7.2Hz,1H),7.86(d,J=8.0Hz,1H),7.75(d,J=7.2Hz,4H),7.64(d,J=7.2Hz,1H),7.56-7.32(m,11H),7.13(t,J=7.6Hz,1H),7.10(d,J=8.0Hz,4H),2.06-1.98(m,9H),1.70(t,J=7.2Hz,6H),1.67(s,6H).

[0131] Synthesis Example 5: Synthesis of Compound A11

[0132]

[0133] Add 100 mmol of 2-bromo-1-chloro-4-iodobenzene, 100 mmol of phenylboronic acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of tetrahydrofuran (THF) and 200 ml of water into a reaction flask, and add 1 mmol of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4). React at 60 °C for 12 h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain white powder M1.

[0134] Add 100 mmol of M1, 100 mmol of 2-dibenzothiopheneboronic acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of tetrahydrofuran (THF) and 200 ml of water into a reaction flask, and add 1 mmol of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4). React at 60 °C for 12 h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain white powder M2.

[0135] Add 100 mmol of M2, 100 mmol of 2 - amino - 9,9 - dimethylfluorene, 28.83 g of sodium tert - butoxide (300 mmol), 800 ml of xylene into a reaction flask, and add 1 mol% of bis(dibenzylideneacetone)palladium (Pd(dba)). React at 120 °C for 12 h. Here, the addition amount of Pd(dba) is 1 mol% of M2. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain white powder M3.

[0136] After adding 108 g (0.50 mol) of 1 - bromoadamantane to 188 g (2.0 mol) of phenol and heating at 120 °C for 12 h until the reaction ends, let it cool to room temperature, then add it to a 2 L beaker and precipitate while stirring. After filtration, wash the precipitate with hot water 3 times, and obtain M4 after thorough vacuum drying.

[0137] Dissolve 91 g (0.40 mol) of M4 and 63 g (0.80 mol) of pyridine in 500 ml of dichloromethane, then cool the temperature to 0 °C, and slowly add 135 g (0.48 mol) of trifluoromethanesulfonic anhydride. Stir for 3 h. After the reaction is completed, add 300 ml of hydrochloric acid, and then add 300 ml of water for extraction. Dry the organic layer with anhydrous magnesium chloride, distill the filtrate, and then perform column chromatography to obtain M5.

[0138] Add 100 mmol of M5, 100 mmol of 3 - chlorophenylboronic acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of tetrahydrofuran (THF) and 200 ml of water into a reaction flask, and add 1 mmol of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4). React at 60 °C for 12 h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain white powder M6.

[0139] Add 100 mmol of M3, 100 mmol of M6, 28.83 g of sodium tert - butoxide (300 mmol), 800 ml of xylene into a reaction flask, and add 1 mol% of bis(dibenzylideneacetone)palladium (Pd(dba)). Here, the addition amount of Pd(dba) is 1 mol% of M3. React at 120 °C for 12 h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain white powder A11.

[0140] 11H NMR (400 MHz, Chloroform) δ 8.48 (s, 1H), 8.45 (d, J = 7.2 Hz, 1H), 8.11 (t, J = 7.6 Hz, 2H), 8.00 (d, J = 8.0 Hz, 1H), 7.90 (d, J = 7.2 Hz, 1H), 7.85 (d, J = 8.0 Hz, 2H), 7.62 - 7.51 (m, 4H), 7.45 (d, J = 7.2 Hz, 2H), 7.40 - 7.18 (m, 12H), 2.06 - 1.98 (m, 9H), 1.70 (t, J = 7.2 Hz, 6H), 1.67 (s, 6H).

[0141] Synthesis Example 6: Synthesis of Compound A12

[0142]

[0143] Add 100 mmol of 1 - bromo - 2 - chloro - 4,5 - diiodobenzene, 200 mmol of phenylboronic acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of tetrahydrofuran (THF), and 200 ml of water to a reaction flask, and add 2 mmol of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4). React at 60 °C for 12 h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain white powder M1.

[0144] Add 100 mmol of M1, 100 mmol of 3 - dibenzothiopheneboronic acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of tetrahydrofuran (THF), and 200 ml of water to a reaction flask, and add 1 mmol of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4). React at 60 °C for 12 h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain white powder M2.

[0145] Add 100 mmol of M2, 100 mmol of 2 - amino - 9,9 - dimethylfluorene, 28.83 g of sodium tert - butoxide (300 mmol), 800 ml of xylene to a reaction flask, and add 1 mol% of bis(dibenzylideneacetone)palladium (Pd(dba)). React at 120 °C for 12 h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain white powder M3.

[0146] After adding 108 g (0.50 mol) of 1-bromoadamantane to 188 g (2.0 mol) of phenol and heating at 120 °C for 12 hours, after the reaction ended, it was allowed to cool to room temperature and then added to a 2 L beaker and precipitated while stirring. After filtration, the precipitate was washed with hot water 3 times and thoroughly dried under vacuum to obtain M4.

[0147] 91 g (0.40 mol) of M4 and 63 g (0.80 mol) of pyridine were dissolved in 500 ml of dichloromethane, and then the temperature was lowered to 0 °C. 135 g (0.48 mol) of trifluoromethanesulfonic anhydride was slowly added. After stirring for 3 hours, after the reaction ended, 300 ml of hydrochloric acid was added, and then 300 ml of water was added for extraction. The organic layer was dried with anhydrous magnesium chloride, and after distilling the filtrate, column chromatography was carried out to obtain M5.

[0148] 100 mmol of M3, 100 mmol of M5, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of xylene were added to a reaction flask, and 1 mol% of bis(dibenzylideneacetone)palladium (Pd(dba)) was added. The reaction was carried out at 120 °C for 12 h, where the addition amount of Pd(dba) was 1 mol% of M3. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder A12.

[0149] 1 H NMR (400 MHz, Chloroform) δ 8.45 (d, J = 7.2 Hz, 1H), 8.35 (s, 1H), 8.19 (d, J = 7.2 Hz, 1H), 8.14 (s, 1H), 8.00 (d, J = 7.6 Hz, 1H), 7.92 (d, J = 7.2 Hz, 1H), 7.86 (d, J = 7.6 Hz, 2H), 7.80 (d, J = 7.2 Hz, 4H), 7.65 (s, 1H), 7.58 (t, J = 7.2 Hz, 1H), 7.46 - 7.25 (m, 11H), 7.16 - 7.05 (m, 2H), 6.91 (d, J = 7.2 Hz, 1H), 6.74 (s, 1H), 6.22 (d, J = 7.2 Hz, 1H), 2.06 - 1.98 (m, 9H), 1.70 (t, J = 7.2 Hz, 6H), 1.67 (s, 6H).

[0150] Synthesis Example 7: Synthesis of Compound A15

[0151]

[0152] Add 100 mmol of 4-bromo-1-chloro-2-iodobenzene, 100 mmol of 4-triphenylamine borate, 41.4 g of potassium carbonate (300 mmol), 800 ml of tetrahydrofuran (THF) and 200 ml of water into a reaction flask, and add 1 mmol of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4). React at 60 °C for 12 h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain a white powder M1.

[0153] Add 100 mmol of M1, 100 mmol of 3-dibenzothiophene boronic acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of tetrahydrofuran (THF) and 200 ml of water into a reaction flask, and add 1 mmol of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4). React at 60 °C for 12 h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain a white powder M2.

[0154] Add 100 mmol of M2, 100 mmol of 2-amino-9,9-dimethylfluorene, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of xylene into a reaction flask, and add 1 mol% of bis(dibenzylideneacetone)palladium (Pd(dba)), where the addition amount of Pd(dba) is 1 mol% of M2. React at 120 °C for 12 h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain a white powder M3.

[0155] Add 108 g (0.50 mol) of 1-bromoadamantane to 188 g (2.0 mol) of phenol, heat at 120 °C for 12 hours. After the reaction is completed, let it cool to room temperature, then add it to a 2 L beaker and precipitate while stirring. After filtration, wash the precipitate with hot water 3 times, and obtain M4 after sufficient vacuum drying.

[0156] Dissolve 91 g (0.40 mol) of M4 and 63 g (0.80 mol) of pyridine in 500 ml of dichloromethane, then cool the temperature to 0 °C, and slowly add 135 g (0.48 mol) of trifluoromethanesulfonic anhydride. Stir for 3 hours. After the reaction is completed, add 300 ml of hydrochloric acid, then add 300 ml of water for extraction. Dry the organic layer with anhydrous magnesium chloride, distill the filtrate, and perform column chromatography to obtain M5.

[0157] Add 100 mmol of M3, 100 mmol of M5, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of xylene into a reaction flask, and add 1 mol% of bis(dibenzylideneacetone)palladium (Pd(dba)), wherein the addition amount of Pd(dba) is 1 mol% of M3. React at 120 °C for 12 h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain white powder A15.

[0158] 1 H NMR(400MHz,Chloroform)δ8.84(s,1H),8.45(d,J=7.2Hz,1H),8.34(s,1H),8.19(d,J=6.8Hz,1H),7.96(d,J=7.6Hz,1H),7.92(d,J=7.2Hz,1H),7.85(d,J=8.0Hz,2H),7.65(d,J=7.2Hz,1H),7.60 - 7.51(m,5H),7.39 - 7.21(m,9H),7.18 - 6.94(m,10H),6.85(s,1H),6.47(d,J=7.2Hz,1H),2.07 - 1.98(m,9H),1.71(t,J=7.2Hz,6H),1.68(s,6H).

[0159] Synthesis Example 8: Synthesis of Compound A18

[0160]

[0161] Add 100 mmol of 2-chlorobromobenzene, 100 mmol of N-phenyl-3-carbazoleboronic acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of tetrahydrofuran (THF) and 200 ml of water into a reaction flask, and add 1 mmol of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4). React at 60 °C for 12 h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain white powder M1.

[0162] 100 mmol of M1, 100 mmol of 2-amino-9,9-dimethylfluorene, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of xylene were added to a reaction flask, and 1 mol% of bis(dibenzylideneacetone)palladium (Pd(dba)) was added. The reaction was carried out at 120 °C for 12 h, wherein the addition amount of Pd(dba) was 1 mol% of M1. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, water was added, filtered, and washed with water. The obtained solid was purified by recrystallization with toluene to obtain white powder M2.

[0163] After adding 108 g (0.50 mol) of 1-bromoadamantane to 188 g (2.0 mol) of phenol, the mixture was heated at 120 °C for 12 h. After the reaction was completed, it was allowed to cool to room temperature and then added to a 2 L beaker and precipitated while stirring. After filtration, the precipitate was washed 3 times with hot water and dried thoroughly under vacuum to obtain M3.

[0164] After dissolving 91 g (0.40 mol) of M3 and 63 g (0.80 mol) of pyridine in 500 ml of dichloromethane, the temperature was lowered to 0 °C, and 135 g (0.48 mol) of trifluoromethanesulfonic anhydride was slowly added. After stirring for 3 h, 300 ml of hydrochloric acid was added after the reaction was completed, and then 300 ml of water was added for extraction. The organic layer was dried with anhydrous magnesium chloride, and the filtrate was distilled and then subjected to column chromatography to obtain M4.

[0165] 100 mmol of M2, 100 mmol of M4, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of xylene were added to a reaction flask, and 1 mol% of bis(dibenzylideneacetone)palladium (Pd(dba)) was added. The reaction was carried out at 120 °C for 12 h, wherein the addition amount of Pd(dba) was 1 mol% of M2. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, water was added, filtered, and washed with water. The obtained solid was purified by recrystallization with toluene to obtain white powder A18.

[0166] 1 H NMR (400 MHz, Chloroform) δ 8.24 (s, 1H), 8.19 (d, J = 7.2 Hz, 1H), 8.10 (d, J = 7.2 Hz, 1H), 7.96 - 7.85 (m, 3H), 7.70 (d, J = 8.0 Hz, 1H), 7.58 (t, J = 7.2 Hz, 3H), 7.51 - 7.26 (m, 10H), 7.21 - 7.11 (m, 3H), 7.10 (d, J = 7.6 Hz, 4H), 2.07 - 1.98 (m, 9H), 1.71 (t, J = 7.2 Hz, 6H), 1.68 (s, 6H).

[0167] Synthesis Example 9: Synthesis of Compound A22

[0168]

[0169] Add 100 mmol of 2-bromo-1-chloro-4-iodobenzene, 100 mmol of phenylboronic acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of tetrahydrofuran (THF), and 200 ml of water into a reaction flask, and add 1 mmol of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4). React at 60 °C for 12 h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain white powder M1.

[0170] Add 100 mmol of M1, 100 mmol of 3-dibenzothiopheneboronic acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of tetrahydrofuran (THF), and 200 ml of water into a reaction flask, and add 1 mmol of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4). React at 60 °C for 12 h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain white powder M2.

[0171] Add 100 mmol of M2, 100 mmol of 2-amino-9,9-dimethylfluorene, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of xylene into a reaction flask, and add 1 mol% of bis(dibenzylideneacetone)palladium (Pd(dba)). React at 120 °C for 12 h, where the addition amount of Pd(dba) is 1 mol% of M2. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain white powder M3.

[0172] Dissolve 100 mmol of bicyclo[2.2.2]octan-2-ol in 500 ml of dichloromethane, then cool the temperature to 0 °C, and slowly add 110 mmol of trifluoromethanesulfonic anhydride. Stir for 3 hours. After the reaction is completed, add 300 ml of water for extraction. Dry the organic layer with anhydrous magnesium chloride, distill the filtrate, and perform column chromatography to obtain M4.

[0173] 100 mmol of M4, 100 mmol of 4-chlorophenylboronic acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of tetrahydrofuran (THF) and 200 ml of water were added to a reaction flask, and 1 mmol of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4) was added. The reaction was carried out at 60 °C for 12 h. After the reaction was completed, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, and the organic phase was concentrated to obtain a white solid. After filtration and washing with water, the obtained solid was purified by recrystallization with toluene to obtain a white powder M5.

[0174] 100 mmol of M3, 100 mmol of M5, 28.83 g of sodium tert-butoxide (300 mmol) and 800 ml of xylene were added to a reaction flask, and 1 mol% of bis(dibenzylideneacetone)palladium (Pd(dba)) was added. The reaction was carried out at 120 °C for 12 h, wherein the addition amount of Pd(dba) was 1 mol% of M3. After the reaction was completed, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, and after filtration and washing with water, the obtained solid was purified by recrystallization with toluene to obtain a white powder A22.

[0175] 1 H NMR (400 MHz, Chloroform) δ 8.47 (d, J = 7.6 Hz, 1H), 8.42 (s, 1H), 8.16 (d, J = 7.2 Hz, 1H), 8.10 (s, 1H), 7.98 (d, J = 8.0 Hz, 1H), 7.88 (t, J = 7.6 Hz, 2H), 7.75 (d, J = 7.6 Hz, 2H), 7.68 - 7.35 (m, 9H), 7.33 (d, J = 6.8 Hz, 2H), 7.24 (d, J = 7.6 Hz, 1H), 7.20 (d, J = 8.0 Hz, 3H), 7.05 (d, J = 7.6 Hz, 2H), 2.90 (t, J = 6.4 Hz, 1H), 2.48 - 2.32 (m, 1H), 2.10 - 1.85 (m, 4H), 1.68 (s, 6H), 1.65 - 1.32 (m, 7H).

[0176] Other compounds of the present invention can be synthesized by selecting appropriate raw materials according to the ideas of the above Synthesis Examples 1 - 9, or any other appropriate methods and raw materials can also be selected for synthesis.

[0177] Example 1

[0178] The glass plate coated with an ITO transparent conductive layer was ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, ultrasonically degreased in an acetone - ethanol mixed solvent, baked in a clean environment until all moisture was removed, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam on the surface;

[0179] Place the above-mentioned glass substrate with an anode in a vacuum chamber and evacuate to less than 10 -5 Torr. Vacuum-evaporate material A2 on the above-mentioned anode layer film as a hole injection layer at an evaporation rate of 0.1 nm / s and an evaporation film thickness of 10 nm;

[0180] Vacuum-evaporate material A2 on the hole injection layer as a hole transport layer at an evaporation rate of 0.1 nm / s and an evaporation film thickness of 80 nm;

[0181] Vacuum-evaporate a light-emitting layer on the hole transport layer. The light-emitting layer includes a host material BH-1 and a dye material BD-1. Use the method of co-evaporation from multiple sources for evaporation. Adjust the evaporation rate of the host material BH-1 to 0.1 nm / s, and the evaporation rate of the dye BD-1 is 3% of the evaporation rate of the host material. The total evaporation film thickness is 30 nm;

[0182] Vacuum-evaporate an electron transport layer on the light-emitting layer. Select material ET-52 as the electron transport material, with an evaporation rate of 0.1 nm / s and an evaporation film thickness of 30 nm;

[0183] Vacuum-evaporate LiF with a thickness of 0.5 nm on the electron transport layer (ETL) as an electron injection layer at an evaporation rate of 0.1 nm / s;

[0184] Finally, evaporate an aluminum layer with a thickness of 150 nm on the electron injection layer as the cathode of the organic electroluminescent device at an evaporation rate of 0.1 nm / s.

[0185] Example 2-9

[0186] Except for using A3, A7, A8, A11, A12, A15, A18, A22 to replace A2 respectively, the rest are the same as in Example 1.

[0187] Comparative Example 1

[0188] Except for using HT-29 to replace A2, the rest are the same as in Example 1.

[0189] Perform the following performance measurements on the organic electroluminescent devices prepared by the above process. The test results are shown in Table 1:

[0190] At the same brightness, use a digital source meter and a luminance meter to measure the driving voltage, current efficiency, and device lifetime of the organic electroluminescent devices prepared in the examples and comparative examples. Specifically, increase the voltage at a rate of 0.1 V per second, and measure the voltage when the brightness of the organic electroluminescent device reaches 1000 cd / m 2 That is the driving voltage, and at the same time measure the current density at this time; the ratio of brightness to current density is the current efficiency; the LT95 lifetime test is as follows: use a luminance meter at 1000 cd / m 2At a constant current under a certain brightness, measure the time when the brightness of the organic electroluminescent device drops to 950 cd / m 2 in hours.

[0191] Table 1. Performance Results of Organic Electroluminescent Devices

[0192]

[0193] From the data in the above table, it can be seen that the compound prepared by the present invention is used as a hole transport material for organic electroluminescent devices, which can effectively reduce the driving voltage, improve the current efficiency, and extend the device life, and is a hole transport material with good performance.

[0194] Example 10

[0195] The glass plate coated with the ITO transparent conductive layer is ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, ultrasonically degreased in an acetone-ethanol mixed solvent, baked in a clean environment until all moisture is removed, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam on the surface;

[0196] Place the glass substrate with the above anode in a vacuum chamber, evacuate to less than 10 -5 Torr, and vacuum deposit HT27 as a hole injection layer on the above anode layer film at a deposition rate of 0.1 nm / s and a deposited film thickness of 10 nm;

[0197] Vacuum deposit HT27 as a hole transport layer on the hole injection layer at a deposition rate of 0.1 nm / s and a deposited film thickness of 100 nm;

[0198] Vacuum deposit A2 as an auxiliary light-emitting layer on the hole transport layer at a deposition rate of 0.1 nm / s and a deposited film thickness of 80 nm;

[0199] Vacuum deposit a light-emitting layer on the hole transport layer. The light-emitting layer includes a host material RH-12 and a dye material RPD-10, and is deposited by a multi-source co-evaporation method. Adjust the deposition rate of the host material RH-12 to 0.1 nm / s, and the deposition rate of the dye RPD-10 is 5% of the deposition rate of the host material, and the total deposited film thickness is 30 nm;

[0200] Vacuum deposit an electron transport layer on the light-emitting layer. Select the material ET-52 as the electron transport material, and its deposition rate is 0.1 nm / s and the deposited film thickness is 30 nm;

[0201] Vacuum deposit a 0.5-nm-thick LiF as an electron injection layer on the electron transport layer (ETL) at a deposition rate of 0.1 nm / s;

[0202] Finally, an aluminum layer with a thickness of 150 nm is deposited on the electron injection layer as the cathode of the organic electroluminescent device, and the deposition rate is 0.1 nm / s.

[0203] Examples 11 - 18

[0204] Except for using A3, A7, A8, A11, A12, A15, A18, A22 to replace A2 respectively, the rest is the same as in Example 10.

[0205] Comparative Example 2

[0206] Except for using R1 to replace A2, the rest is the same as in Example 10.

[0207]

[0208] The following performance measurements were carried out on the organic electroluminescent devices prepared by the above process, and the test results are shown in Table 2:

[0209] At the same brightness, a digital source meter and a luminance meter were used to measure the driving voltage, current efficiency and device lifetime of the organic electroluminescent devices prepared in the examples and comparative examples. Specifically, the voltage was increased at a rate of 0.1 V per second, and the voltage when the brightness of the organic electroluminescent device reached 5000 cd / m 2 was measured as the driving voltage, and the current density at this time was also measured; the ratio of brightness to current density was the current efficiency; the LT95 lifetime test was as follows: using a luminance meter at 5000 cd / m 2 brightness, keeping a constant current, and measuring the time when the brightness of the organic electroluminescent device dropped to 4750 cd / m 2 , and the unit was hours.

[0210] Table 2. Performance Results of Organic Electroluminescent Devices

[0211]

[0212]

[0213] As can be seen from the data in the above table, the compound prepared by the present invention is used as a light-emitting auxiliary layer material for organic electroluminescent devices, which can effectively reduce the driving voltage, improve the current efficiency, and extend the device lifetime, and is a hole transport material with good performance.

[0214] The above are only the preferred embodiments of the present invention and are not intended to limit the protection scope of the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention are included in the protection scope of the present invention.

Claims

1. A cycloalkane-substituted compound, characterized in that, It has a structure shown in formula (Ⅰ): Among them, L is selected from a chemical bond, a substituted or unsubstituted C6-C 30 aryl group, a substituted or unsubstituted C5-C 30 heteroaryl group; R 1 and R 2 are each independently selected from C1-C4 alkyl, C3-C6 cycloalkane, substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted C5-C 30 heteroaryl, and adjacent substituents can be connected to form a ring; R and R' are each independently selected from hydrogen, a substituted or unsubstituted C6-C 30 aryl group, a substituted or unsubstituted C5-C 30 heteroaryl group; m, n, and o each independently selected from 0, 1, 2, 3, 4; X is selected from O, S, N; Ar is selected from a substituted or unsubstituted C6-C 30 aryl group, a substituted or unsubstituted C5-C 30 heteroaryl group; A is selected from the following fragments: The heteroatoms on the heteroaryl are each independently selected from O, S or N; The hydrogen atoms on the aryl group and heteroaryl group may each independently be replaced by Ra, and Ra are each independently selected from deuterium, halogen, nitro, cyano, C1-C4 alkyl, C5-C 20 cycloalkyl, phenyl, biphenyl, terphenyl or naphthyl.

2. The compound according to claim 1, wherein Ar is selected from a substituted or unsubstituted aryl group having 6 to C 24 and a substituted or unsubstituted heteroaryl group having 5 to C 18 .

3. The compound according to claim 1, wherein Said R 1 and R 2 independently of one another are each selected from methyl, ethyl, isopropyl, tert-butyl, cyclopentyl, cyclohexyl and the following unsubstituted or Ra-substituted groups: phenyl, biphenyl, naphthyl, fluorenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl.

4. The compound according to claim 1, wherein Said R and R' are independently selected from hydrogen and the following groups which are unsubstituted or substituted by Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, dibenzofuranyl, dibenzothiophenyl, 9,9-dimethylfluorenyl, spirofluorene, arylamino.

5. The compound according to claim 1, characterized in that, Said Ar is selected from the following groups which are unsubstituted or substituted by Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, benzofuranyl, dibenzofuranyl, benzothiophenyl, dibenzothiophenyl, 9,9-dimethylfluorenyl, spirofluorene, arylamino, carbazolyl.

6. The compound according to claim 1, characterized in that, Selected from the compounds shown in A1 - A25:

7. A hole transporting material, characterized in that, Comprising at least one of the compounds described in any one of claims 1 - 6.

8. An organic electroluminescent device, characterized in that, Comprising at least one of the hole transport materials of claim 7.

9. A display device, characterized in that, An organic electroluminescent device comprising the compound of claim 8.

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