Compound, hole transport material and organic electroluminescent device

Abstract

The invention provides a compound as shown in a general formula (I). The compound has a parent structure of 1, 2-disubstituted naphthalene biarylamine, is high in bond energy between atoms, has good thermal stability, is beneficial to solid-state accumulation between molecules, is high in hole transition capability, is used as a hole transport material, can effectively reduce the driving voltage of a device and improve the luminous efficiency of the device, and has a good application prospect. The service life of devices is prolonged. 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 application relates to the technical field of organic light-emitting display, and in particular to a compound, a hole transport material and an organic electroluminescent device. Background Art

[0002] Electroluminescence (EL) refers to the phenomenon that luminescent materials emit light under the action of electric field and are stimulated by current and electric field. It is a luminescence process that directly converts electrical energy into light energy. Organic electroluminescent devices (OLEDs) have a series of advantages such as autonomous luminescence, low-voltage DC drive, full curing, wide viewing angle, light weight, simple composition and process. Compared with liquid crystal displays, organic electroluminescent devices do not require backlight sources, have large viewing angles, low power consumption, and their response speed can reach 1000 times that of liquid crystal displays, but their manufacturing cost is lower than that of liquid crystal displays with the same resolution. Therefore, organic electroluminescent devices have a very broad application prospect.

[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 good efficiency and long life is usually the result of the optimized combination of device structure and various organic materials. Compared with inorganic luminescent materials, organic electroluminescent materials have many advantages, such as: good processing performance, can be formed on any substrate by evaporation or spin coating, can achieve flexible display and large-area display; can adjust the optical properties, electrical properties and stability of materials by changing the molecular structure, and there is a lot of room for material selection. In the most common OLED device structure, the following types of organic materials are usually included: hole injection materials, hole transport materials, electron transport materials, and various luminescent materials such as dyes or doped guest materials and corresponding host materials. Among them, hole transport materials, as an important functional material, have a direct impact on the mobility of holes and ultimately affect the luminous efficiency of OLEDs. However, the hole transport materials currently used in OLEDs can achieve a low hole migration rate, poor matching with the energy levels of adjacent layers, and cannot take into account both efficiency and life, which seriously restricts the display function and development of OLED display devices. Summary of the invention

[0004] The purpose of this application is to provide a hole transport material to reduce the driving voltage of an organic electroluminescent device, improve the luminous efficiency and extend the service life. The specific technical solution is as follows:

[0005] In the first aspect, the present application provides a compound of general formula (I):

[0006]

[0007] in,

[0008] R 1 -R 5 are independently selected from hydrogen, deuterium, hydroxyl, thiol, the following groups which are unsubstituted or substituted by Ra: C 1 -C 3 Alkyl, C 2 -C 6 Alkenyl, arylamine, C 6 -C 30 Aromatic or C 6 -C 30 Heteroaryl, the R 1 -R 5 Two adjacent groups in the can be connected to form a ring;

[0009] R 6 -R 8 are independently selected from hydrogen, unsubstituted or substituted by Ra: C 6 -C 30 Aromatic or C 10 -C 30 heteroaryl;

[0010] R, R' are independently selected from C 1 -C 3 Alkyl, C 5 -C 10 Cycloalkyl, unsubstituted or substituted by Ra: C 6 -C 30 Aromatic or C 10 -C 30 Heteroaryl, R and R' can be connected to form a ring;

[0011] R 9 is selected from the following groups which are unsubstituted or substituted by Ra: C 6 -C 30 Aromatic or C 6 -C 30 heteroaryl;

[0012] The heteroatoms on the heteroaryl group are each independently selected from O, S or N;

[0013] The Ra are independently selected from deuterium, halogen, nitro, cyano, C 1 -C 4 Alkyl, C 5 -C 20 Cycloalkyl, phenyl, biphenyl, terphenyl or naphthyl.

[0014] The second aspect of the present application provides a hole transport material, which comprises at least one of the compounds provided in the first aspect of the present application.

[0015] The third aspect of the present application provides an organic electroluminescent device, which comprises at least one of the hole transport materials provided in the second aspect of the present application.

[0016] A fourth aspect of the present application provides a display device, which includes the organic electroluminescent device provided by the third aspect of the present application.

[0017] The present application provides a compound of general formula (I), which has a parent structure of 1,2-disubstituted naphthylene diarylamine, high bond energy between atoms, good thermal stability, and is conducive to solid-state stacking between molecules. The hole transition ability is strong, and it is used as a hole transport layer material, which can effectively reduce the driving voltage of the organic electroluminescent device, improve the luminous efficiency of the organic electroluminescent device, and extend the service life of the organic electroluminescent device. The organic electroluminescent device provided by the present application contains the compound of the present application as a hole transport material, which can effectively reduce the device driving voltage, improve the luminous efficiency, and extend the device life. The display device provided by the present application has an excellent display effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application, and for ordinary technicians in this field, other embodiments can also be obtained based on these drawings.

[0019] Figure 1 A schematic diagram of the structure of a typical organic electroluminescent device. DETAILED DESCRIPTION

[0020] The technical solutions in this application will be described clearly and completely below in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of this application, rather than all the embodiments. All other embodiments obtained by those skilled in the art based on this application are within the scope of protection of this application.

[0021] In the first aspect, the present application provides a compound of general formula (I):

[0022]

[0023] in,

[0024] R 1 -R 5 are independently selected from hydrogen, deuterium, hydroxyl, thiol, the following groups which are unsubstituted or substituted by Ra: C 1 -C 3 Alkyl, C 2 -C 6Alkenyl, arylamine, C 6 -C 30 Aromatic or C 6 -C 30 Heteroaryl, the R 1 -R 5 Two adjacent groups in the can be connected to form a ring;

[0025] R 6 -R 8 are independently selected from hydrogen, unsubstituted or substituted by Ra: C 6 -C 30 Aromatic or C 10 -C 30 heteroaryl;

[0026] R, R' are independently selected from C 1 -C 3 Alkyl, C 5 -C 10 Cycloalkyl, unsubstituted or substituted by Ra: C 6 -C 30 Aromatic or C 10 -C 30 Heteroaryl, R and R' can be connected to form a ring;

[0027] R 9 is selected from the following groups which are unsubstituted or substituted by Ra: C 6 -C 30 Aromatic or C 6 -C 30 heteroaryl;

[0028] The heteroatoms on the heteroaryl group are each independently selected from O, S or N;

[0029] The Ra are independently selected from deuterium, halogen, nitro, cyano, C 1 -C 4 Alkyl, C 5 -C 20 Cycloalkyl, phenyl, biphenyl, terphenyl or naphthyl.

[0030] Preferably, R 1 -R 5 are independently selected from hydrogen, deuterium, the following groups which are unsubstituted or substituted by Ra: C 1 -C 3 Alkyl, C 2 -C 6 Alkenyl, aromatic amine, C 6 -C 18 Aromatic or C 6 -C 18 Heteroaryl, the R 1 -R5 Two adjacent groups in the can be connected to form a ring;

[0031] Preferably, R 6 -R 8 are independently selected from hydrogen, unsubstituted or substituted by Ra: C 6 -C 18 Aromatic or C 10 -C 18 heteroaryl;

[0032] Preferably, R, R' are independently selected from C 1 -C 3 Alkyl, C 5 -C 10 Cycloalkyl, unsubstituted or substituted by Ra: C 6 -C 18 Aromatic or C 10 -C 18 Heteroaryl, R and R' can be connected to form a ring;

[0033] Preferably, R 9 is selected from the following groups which are unsubstituted or substituted by Ra: C 6 -C 18 Aromatic or C 6 -C 18 heteroaryl;

[0034] Preferably, the Ra are independently selected from deuterium, halogen, nitro, cyano, C 1 -C 4 Alkyl, C 5 -C 12 Cycloalkyl, phenyl, biphenyl, terphenyl or naphthyl.

[0035] More preferably, R 1 -R 5 are independently selected from hydrogen, deuterium, hydroxyl, mercapto, the following groups which are unsubstituted or substituted by Ra: methyl, ethyl, n-propyl, isopropyl, vinyl, propenyl, benzocyclohexyl, anilino, biphenylamino, phenyl, biphenyl, naphthyl, phenanthrenyl, fluorenyl, carbazolyl, xanthenyl; said R 1 -R 5 Two adjacent groups can be connected to form a ring.

[0036] More preferably, R 6 -R 8 The following groups are independently selected from hydrogen, unsubstituted or substituted by Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, dibenzofuranyl, dibenzothienyl, 9,9-dimethylfluorenyl, spirofluorenyl, arylamine, carbazolyl.

[0037] More preferably, R and R' are independently selected from methyl, ethyl, propyl, cyclopentyl, cyclohexyl, the following groups which are unsubstituted or substituted by Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, dibenzofuranyl, dibenzothienyl, 9,9-dimethylfluorenyl, spirofluorenyl, aromatic amino, carbazolyl; R and R' can be connected to form a ring.

[0038] More preferably, R 9 The group selected from the following groups which are unsubstituted or substituted by Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, benzofuranyl, dibenzofuranyl, benzothienyl, dibenzothienyl, 9,9-dimethylfluorenyl, spirofluorenyl, carbazolyl.

[0039] In the present application, the halogen may be selected from fluorine.

[0040] In some embodiments, the compound is selected from:

[0041]

[0042]

[0043]

[0044] The second aspect of the present application provides a hole transport material, which comprises at least one of the compounds provided in the first aspect of the present application.

[0045] When the compound of the present application is used as a hole transport material, due to the effect of steric hindrance, the energy level of the high energy molecular orbital (HOMO) is deepened, and has a suitable energy level between adjacent levels, which is beneficial to the injection and migration of holes, and can effectively reduce the driving voltage of the organic electroluminescent device. At the same time, it has a high hole migration rate, which can enable the organic electroluminescent device to achieve good luminous efficiency, and has a large conjugated plane, which is beneficial to molecular stacking, and exhibits good thermodynamic stability, so that the organic electroluminescent device exhibits a long life.

[0046] The third aspect of the present application provides an organic electroluminescent device, which comprises at least one of the hole transport materials provided in the second aspect of the present application. The organic electroluminescent device provided in the present application has a lower driving voltage, higher luminous efficiency and longer service life.

[0047] In the present application, there is no particular limitation on the type and structure of the organic electroluminescent device, and it can be any organic electroluminescent device of different types and structures known in the art, as long as the hole transport material provided in the present application can be used.

[0048] The organic electroluminescent device of the present application may be a light-emitting device with a top-emitting structure, for example, comprising 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 in sequence on a substrate.

[0049] The organic electroluminescent device of the present application may also be a light-emitting device with a bottom-emitting structure, for example, comprising 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 in sequence on a substrate.

[0050] The organic electroluminescent device of the present application may also be a light-emitting device with a double-sided light-emitting structure, for example, comprising 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 in sequence on a substrate.

[0051] In the organic electroluminescent device of the present application, except for the hole transport layer comprising the hole transport material provided in the present application, other layers may use any material used for the layers in the prior art.

[0052] In addition, the organic electroluminescent device of the present application may have an electron blocking layer between the hole transport layer and the light-emitting layer, may have a hole blocking layer between the light-emitting layer and the electron transport layer, and may be provided with a light extraction layer on the transparent electrode on the light-emitting side. However, the structure of the organic electroluminescent device of the present application is not limited to the above-mentioned specific structure, and the above-mentioned layers may be omitted or increased if necessary. The present application has no particular restrictions on the thickness of the above-mentioned layers, as long as the purpose of the present application can be achieved. For example, the organic electroluminescent device may include an anode (100nm to 150nm), a hole injection layer (5nm to 20nm), a hole transport layer (80nm to 140nm), an electron blocking layer (5nm to 20nm), a light-emitting layer (20nm to 45nm), a hole blocking layer (5nm to 20nm), an electron transport layer (30nm to 40nm), an electron injection layer (0.5nm to 20nm), a transparent or semi-transparent cathode (100nm to 200nm) and a light extraction layer (50nm to 90nm) on a substrate in sequence.

[0053] Figure 1 A schematic diagram of a typical organic electroluminescent device is shown, wherein, 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 arranged in sequence.

[0054] Understandably, Figure 1Only a typical structure of an organic electroluminescent device is schematically shown, and the present application is not limited to this structure. The hole transport material of the present application can be used in any type of organic electroluminescent device.

[0055] For convenience, the following reference Figure 1 The organic electroluminescent device of the present application is described, but this does not mean any limitation on the protection scope of the present application. It can be understood that all organic electroluminescent devices that can use the hole transport material of the present application are within the protection scope of the present application.

[0056] In the present application, the substrate 1 is not particularly limited, and conventional substrates used in organic electroluminescent devices in the prior art may be used, such as glass, polymer materials, and glass and polymer materials with thin film transistor (TFT) components.

[0057] In the present application, the material of the reflective anode electrode 2 is not particularly limited, and can be selected from indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO 2 ), zinc oxide (ZnO), low temperature polycrystalline silicon (LTPS) and other transparent conductive materials, or metal materials such as silver and its alloys, aluminum and its alloys, or organic conductive materials such as PEDOT (poly 3,4-ethylenedioxythiophene), or the reflective anode electrode 2 is a multilayer structure formed by the above materials. The present application has no special restrictions on the number of layers of its multilayer structure, which can be selected according to actual needs as long as the purpose of the present application can be achieved, for example, 1 layer, 2 layers, 3 layers or more layers.

[0058] In the present application, the material of the hole injection layer 3 is not particularly limited, and hole injection materials known in the art or hole transport materials provided in the present application can be selected as the hole injection material.

[0059] For example, the material of the hole injection layer 3 may be selected from at least one of the following HT-1 to HT-31 compounds:

[0060]

[0061]

[0062] In the present application, the hole injection layer 3 may further include a p-type dopant, and the type of the p-type dopant is not particularly limited, and various p-type dopants known in the art may be used. For example, the p-type dopant may be selected from at least one of the following compounds:

[0063]

[0064] In the present application, the amount of the p-type dopant is not particularly limited and may be an amount known to those skilled in the art.

[0065] In the present application, the hole transport layer 4 comprises at least one of the hole transport materials of the present application. The hole transport layer 4 may also comprise any combination of at least one of the hole transport materials of the present application and known hole transport materials. Currently known hole transport materials may be selected from at least one of the above-mentioned HT-1 to HT-31 compounds, but are not limited to the above-mentioned compounds. The number of layers of the hole transport layer 4 is not particularly limited and can be adjusted according to actual needs as long as the purpose of the present application can be met, for example, 1 layer, 2 layers, 3 layers, 4 layers or more layers.

[0066] In the present application, the luminescent material of the luminescent layer 5 is not particularly limited, and any luminescent material known to those skilled in the art can be used. For example, the luminescent material can include a host material and a guest material. For example, the known luminescent layer host material can be selected from but not limited to at least one of the following GPH-1 to GPH-80 compounds:

[0067]

[0068]

[0069]

[0070] In the present application, the amount of the main material of the light-emitting layer is not particularly limited and can be an amount known to those skilled in the art.

[0071] In the present application, the light-emitting layer 5 may adopt the technology of phosphorescent electroluminescence. The guest material in the light-emitting layer 5 is a phosphorescent dopant, and the phosphorescent dopant may be selected from but not limited to at least one of the following RPD-1 to RPD-28 compounds. The amount of the phosphorescent dopant is not particularly limited and may be an amount known in the art.

[0072]

[0073] In the present application, the material of the electron transport layer 6 is not particularly limited, and electron transport materials known in the art can be used. The present application does not particularly limit the number of layers of the electron transport layer 6, and can be adjusted according to actual needs as long as it can meet the purpose of the present application, for example, 1 layer, 2 layers, 3 layers, 4 layers or more layers.

[0074] For example, the electron transport material may be selected from at least one of the following ET-1 to ET-57 compounds:

[0075]

[0076]

[0077]

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

[0079]

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

[0081] In the present application, the material of the electron injection layer 7 is not particularly limited, and electron injection materials known in the art can be used, for example, including but not limited to LiQ, LiF, NaCl, CsF, Li 2 O、Cs 2 CO 3 , BaO, Na, Li, Ca and other materials.

[0082] In the present application, the material of the cathode electrode 8 is not particularly limited, for example, it can be selected from but not limited to magnesium-silver mixture, LiF / Al, ITO, Al and other metals, metal mixtures, oxides and the like.

[0083] The method for preparing the organic electroluminescent device of the present application is not particularly limited, and any method known in the art may be used. For example, the present application may be prepared by the following preparation method:

[0084] (1) cleaning the reflective anode electrode 2 on the top-emitting OLED device substrate 1 by using a cleaning machine through steps such as chemical cleaning, water cleaning, brushing, high-pressure water cleaning, and air knife cleaning, and then performing a heat treatment;

[0085] (2) vacuum evaporating a hole injection material on the reflective anode electrode 2 to form a hole injection layer 3;

[0086] (3) vacuum evaporating a hole transport material on the hole injection layer 3 to form a hole transport layer 4;

[0087] (4) vacuum evaporating a light-emitting layer 5 on the hole transport layer 4, wherein the light-emitting layer 5 contains a host material and a guest material;

[0088] (5) vacuum evaporating an electron transport material on the light emitting layer 5 to form an electron transport layer 6;

[0089] (6) Vacuum evaporation of electron injection material on the electron transport layer 6 as the electron injection layer 7, the electron injection material is selected from LiQ, LiF, NaCl, CsF, Li 2 O、Cs 2 CO 3 , BaO, Na, Li, Ca and other materials or a combination of them;

[0090] (7) A cathode material is vacuum-deposited on the electron injection layer 7 to form a cathode electrode 8 .

[0091] The above only describes a typical structure of an organic electroluminescent device and its preparation method. It should be understood that the present application is not limited to this structure. The hole transport material of the present application can be used in an organic electroluminescent device of any structure, and the organic electroluminescent device can be prepared by any preparation method known in the art.

[0092] In a fourth aspect, the present application provides a display device, which includes the organic electroluminescent device provided in the present application. The display device includes but is not limited to a display, a television, a tablet computer, a mobile communication terminal, and the like.

[0093] The synthesis method of the compound of the present application is not particularly limited, and any method known to those skilled in the art can be used for synthesis. The following examples illustrate the synthesis process of the compound of the present application. As used herein, room temperature refers to 25±5°C.

[0094] Synthesis example

[0095] Synthesis Example 1: Synthesis of Compound A1

[0096]

[0097] 100 mmol of 2-bromo-1-naphthol, 100 mmol of phenylboric 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 mol% (1 mol% of 2-bromo-1-naphthol) of tetrakis(triphenylphosphine)palladium (Pd(PPh 3 ) 4 ). The reaction was carried out at 60°C for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, water was added, and the liquid was separated. The organic phase was concentrated to obtain a white solid, which was filtered and washed with water. The obtained solid was recrystallized and purified with toluene to obtain a white powder M1.

[0098] Add 100 mmol of M1 and 200 ml of dichloromethane to the reaction flask, and then drop 110 mmol of trifluoromethanesulfonate at 0°C. After the addition is complete, control the temperature at 0°C for 1 hour, then warm it to room temperature for 12 hours. After the reaction is complete, add water, extract with ethyl acetate, separate the organic phase, and concentrate it to obtain the intermediate M2.

[0099] 100 mmol of 2-amino-9,9-dimethylfluorene, 100 mmol of 2-bromo-9,9-dimethylfluorene, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of toluene were added to the reaction flask, and 1 mol% (1 mol% of 2-amino-9,9-dimethylfluorene) of bis(dibenzylideneacetonepalladium) (Pd(dba) 2 ). The reaction was carried out at 100°C for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder M3.

[0100] Add 100 mmol of M2, 100 mmol of M3, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of xylene, and 1 mol% (1 mol% of M2) of Pd(dba) into the reaction flask. 2 The reaction was carried out at 120°C for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder A1.

[0101] 1 H NMR (400MHz, Chloroform) δ8.20(d,J=7.6Hz,1H),7.92(d,J=8.0Hz,3H),7.87(d,J=8.8Hz,2H),7.75(d,J=7. 6Hz,1H),7.55-7.38(m,10H),7.35(t,J=7.6Hz,3H),7.26(t,J=7.6Hz,3H),7.12-7.06(m,2H),1.69(s,12H).

[0102] M / Z: Exp., 604.1; Calc., 603.3.

[0103] Synthesis Example 2: Synthesis of Compound A3

[0104]

[0105] 100 mmol of 2-bromo-1-naphthol, 100 mmol of 2-naphthoboric acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of THF and 200 ml of water were added to the reaction flask, and 1 mol% (1 mol% of 2-bromo-1-naphthol) of Pd(PPh 3 ) 4The reaction was carried out at 60°C for 12 hours. After the reaction was completed, the reaction was stopped and the reactant was cooled to room temperature. Water was added, the liquid was separated, and the organic phase was concentrated to obtain a white solid. The solid was filtered and washed with water. The obtained solid was recrystallized and purified with toluene to obtain a white powder M1.

[0106] Add 100 mmol of M1 and 200 ml of dichloromethane to the reaction flask, and then drop 110 mmol of trifluoromethanesulfonate at 0°C. After the addition is complete, control the temperature at 0°C for 1 hour, then warm it to room temperature for 12 hours. After the reaction is complete, add water, extract with ethyl acetate, separate the organic phase, and concentrate it to obtain the intermediate M2.

[0107] Add 100 mmol of 2-amino-9,9-dimethylfluorene, 100 mmol of 2-bromo-spirobifluorene, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of toluene, and 1 mol% (1 mol% of 2-amino-9,9-dimethylfluorene) of Pd(dba) into the reaction flask. 2 The reaction was carried out at 100°C for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder M3.

[0108] Add 100 mmol of M2, 100 mmol of M3, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of xylene, and 1 mol% (1 mol% of M2) of Pd(dba) into the reaction flask. 2 The reaction was carried out at 120°C for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder A3.

[0109] 1 H NMR (400MHz, Chloroform) δ8.22(d,J=7.6Hz,1H),8.11-8.06(m,2H),7.98(d,J=7.6Hz,1H),7.92-7.81(m,7H),7.75(d,J=7.2Hz,1H),7.63(t,J=7 .2Hz,1H),7.60-7.50(m,4H),7.48-7.40(m,5H),7.39-7.30(m,5H),7.27 (d,J=7.2Hz,1H),7.24-7.15(m,5H),7.75(d,J=7.6Hz,2H),1.69(s,6H).

[0110] M / Z: Exp., 776.5; Calc., 775.3.

[0111] Synthesis Example 3: Synthesis of Compound A7

[0112]

[0113] 100 mmol of 2-bromo-1-naphthol, 100 mmol of phenylboric acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of THF and 200 ml of water were added to the reaction flask, and 1 mol% (1 mol% of 2-bromo-1-naphthol) of Pd(PPh 3 ) 4 The reaction was carried out at 60°C for 12 hours. After the reaction was completed, the reaction was stopped and the reactant was cooled to room temperature. Water was added, the liquid was separated, and the organic phase was concentrated to obtain a white solid. The solid was filtered and washed with water. The obtained solid was recrystallized and purified with toluene to obtain a white powder M1.

[0114] Add 100 mmol of M1 and 200 ml of dichloromethane to the reaction flask, and then drop 110 mmol of trifluoromethanesulfonate at 0°C. After the addition is complete, control the temperature at 0°C for 1 hour, then warm it to room temperature for 12 hours. After the reaction is complete, add water, extract with ethyl acetate, separate the organic phase, and concentrate it to obtain the intermediate M2.

[0115] 100 mmol of p-bromoaniline, 100 mmol of 2-naphthaleneboronic acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of THF and 200 ml of water were added to the reaction flask, and 1 mol% (1 mol% of p-bromoaniline) of Pd(PPh 3 ) 4 The reaction was carried out at 60°C for 12 hours. After the reaction was completed, the reaction was stopped and the reactant was cooled to room temperature. Water was added, the liquid was separated, and the organic phase was concentrated to obtain a white solid. The solid was filtered and washed with water. The obtained solid was recrystallized and purified with toluene to obtain a white powder M3.

[0116] Add 100 mmol of M3, 100 mmol of 2-bromo-9,9-diphenylfluorene, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of toluene, and 1 mol% (1 mol% of M3) of Pd(dba) into the reaction flask. 2 The reaction was carried out at 100°C for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder M4.

[0117] Add 100 mmol of M2, 100 mmol of M4, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of xylene, and 1 mol% (1 mol% of M2) of Pd(dba) into the reaction flask. 2The reaction was carried out at 120°C for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder A7.

[0118] 1 H NMR (400MHz, Chloroform) δ8.21(d,J=7.2Hz,1H),8.12-8.04(m,2H),8.01-7.95(m,2H),7.90(d,J=9.2Hz,2H),7.84(d,J=10.0H z,1H),7.75(d,J=6.8Hz,2H),7.66-7.50(m,6H),7.48(d,J=7.2Hz,1H),7.40-7.32(m,8H),7.28-7.13(m,9H),7.10-7.02(m,5H).

[0119] M / Z: Exp., 738.2; Calc., 737.3.

[0120] Synthesis Example 4: Synthesis of Compound A9

[0121]

[0122] 100 mmol of 2,4-dibromo-1-naphthol, 200 mmol of phenylboric acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of THF and 200 ml of water were added to the reaction flask, and 2% mmol (2% mmol of 2,4-dibromo-1-naphthol) of Pd(PPh 3 ) 4 The reaction was carried out at 60°C for 12 hours. After the reaction was completed, the reaction was stopped and the reactant was cooled to room temperature. Water was added, the liquid was separated, and the organic phase was concentrated to obtain a white solid. The solid was filtered and washed with water. The obtained solid was recrystallized and purified with toluene to obtain a white powder M1.

[0123] Add 100 mmol of M1 and 200 ml of dichloromethane to the reaction flask, and then drop 110 mmol of trifluoromethanesulfonate at 0°C. After the addition is complete, control the temperature at 0°C for 1 hour, then warm it to room temperature for 12 hours. After the reaction is complete, add water, extract with ethyl acetate, separate the organic phase, and concentrate it to obtain the intermediate M2.

[0124] Add 100 mmol of 2-amino-9,9-dimethylfluorene, 100 mmol of 2-bromo-spirobifluorene, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of toluene, and 1 mol% (1 mol% of 2-amino-9,9-dimethylfluorene) of Pd(dba) into the reaction flask. 2The reaction was carried out at 100°C for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder M3.

[0125] Add 100 mmol of M2, 100 mmol of M3, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of xylene, and 1 mol% (1 mol% of M2) of Pd(dba) into the reaction flask. 2 The reaction was carried out at 120°C for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder A9.

[0126] 1 H NMR(400MHz,Chloroform)δ9.01(d,J=8.4Hz,1H),8.25(d,J=8.4Hz,1H),7.95(d,J=7.6Hz,1H),7.88(d,J=8.0Hz,2H),7.84(d,J=10.0Hz,2H), 7.78(d,J=8.0Hz,2H),7.70(s,1H),7.64(s,1H),7.55(d,J=7.6Hz,1H), 7.49-7.30(m,13H),7.27-7.13(m,8H),7.10-7.04(m,6H),1.69(s,6H).

[0127] M / Z: Exp., 804.1; Calc., 803.4.

[0128] Synthesis Example 5: Synthesis of Compound A11

[0129]

[0130] 100 mmol of 2-bromo-1-naphthol, 100 mmol of phenylboric acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of THF and 200 ml of water were added to the reaction flask, and 1 mol% (1 mol% of 2-bromo-1-naphthol) of Pd(PPh 3 ) 4 The reaction was carried out at 60°C for 12 hours. After the reaction was completed, the reaction was stopped and the reactant was cooled to room temperature. Water was added, the liquid was separated, and the organic phase was concentrated to obtain a white solid. The solid was filtered and washed with water. The obtained solid was recrystallized and purified with toluene to obtain a white powder M1.

[0131] Add 100 mmol of M1 and 200 ml of dichloromethane to the reaction flask, and then drop 110 mmol of trifluoromethanesulfonate at 0°C. After the addition is complete, control the temperature at 0°C for 1 hour, then warm it to room temperature for 12 hours. After the reaction is complete, add water, extract with ethyl acetate, separate the organic phase, and concentrate it to obtain the intermediate M2.

[0132] 100 mmol of 1,4-dibromobenzene, 100 mmol of 2-naphthaleneboric acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of THF and 200 ml of water were added to the reaction flask, and 1 mol% (1 mol% of 1,4-dibromobenzene) of Pd(PPh 3 ) 4 The reaction was carried out at 60°C for 12 hours. After the reaction was completed, the reaction was stopped and the reactant was cooled to room temperature. Water was added, the liquid was separated, and the organic phase was concentrated to obtain a white solid. The solid was filtered and washed with water. The obtained solid was recrystallized and purified with toluene to obtain a white powder M3.

[0133] Add 100 mmol of M3 and 200 ml of THF to the reaction bottle, add 100 mmol of n-butyl lithium dropwise at -78°C, react at -78°C for 1 hour, add 100 mmol of acetonitrile dropwise, react at -78°C for 1 hour, warm to room temperature and react for 12 hours. After the reaction is complete, add water, extract with ethyl acetate, separate the organic phase, concentrate, and purify by column chromatography (ethyl acetate: petroleum ether 1:100) to obtain intermediate M4.

[0134] 100 mmol of 1,2-dibromobenzene, 100 mmol of p-chlorophenylboric acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of THF and 200 ml of water were added to the reaction flask, and 1 mol% (1 mol% of 1,2-dibromobenzene) of Pd(PPh 3 ) 4 The reaction was carried out at 60°C for 12 hours. After the reaction was completed, the reaction was stopped and the reactant was cooled to room temperature. Water was added, the liquid was separated, and the organic phase was concentrated to obtain a white solid. The solid was filtered and washed with water. The obtained solid was recrystallized and purified with toluene to obtain a white powder M5.

[0135] Add 100 mmol of M5 and 200 ml of THF to the reaction bottle, add 100 mmol of n-butyl lithium dropwise at -78°C, react at -78°C for 1 hour, add 100 mmol of M4 dropwise, react at -78°C for 1 hour, warm to room temperature and react for 12 hours. After the reaction is completed, add water, extract with ethyl acetate, separate the organic phase, concentrate, and purify by column chromatography to obtain intermediate M6.

[0136] Add 100 mmol of M6 and 300 ml of glacial acetic acid to the reaction flask, heat to 120°C and reflux for 12 hours. After the reaction is completed, add water, solid precipitates, filter and dry to obtain intermediate M7.

[0137] Add 100 mmol of M7, 100 mmol of 4-benzidine, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of toluene, and 1 mol% (1 mol% of M7) of Pd(dba) into the reaction flask. 2 The reaction was carried out at 100°C for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder M8.

[0138] Add 100 mmol of M2, 100 mmol of M8, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of xylene, and 1 mol% (1 mol% of M2) of Pd(dba) into the reaction flask. 2 The reaction was carried out at 120°C for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder A11.

[0139] 1 H NMR (400MHz, Chloroform) δ8.22(d,J=7.2Hz,1H),8.08(t,J=7.6Hz,2H),8.00(d,J=7.6Hz,1H),7.90(d,J=7.2Hz,2H),7.86(d,J=8.8Hz,1H),7.75(d,J= 8.0Hz,3H),7.68(d,J=7.2Hz,1H),7.61(d,J=7.2Hz,1H),7.56-7.50(m,8H) ,7.47-7.30(m,14H),7.23(t,J=7.6Hz,2H),7.10-7.05(m,2H),2.28(s,3H).

[0140] M / Z: Exp., 752.6; Calc., 751.3.

[0141] Synthesis Example 6: Synthesis of Compound A14

[0142]

[0143] 100 mmol of 2-bromo-1-naphthol, 100 mmol of phenylboric acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of THF and 200 ml of water were added to the reaction flask, and 1 mol% (1 mol% of 2-bromo-1-naphthol) of Pd(PPh 3 ) 4 The reaction was carried out at 60°C for 12 hours. After the reaction was completed, the reaction was stopped and the reactant was cooled to room temperature. Water was added, the liquid was separated, and the organic phase was concentrated to obtain a white solid. The solid was filtered and washed with water. The obtained solid was recrystallized and purified with toluene to obtain a white powder M1.

[0144] Add 100 mmol of M1 and 200 ml of dichloromethane to the reaction flask, and then drop 110 mmol of trifluoromethanesulfonate at 0°C. After the addition is complete, control the temperature at 0°C for 1 hour, then warm it to room temperature for 12 hours. After the reaction is complete, add water, extract with ethyl acetate, separate the organic phase, and concentrate it to obtain the intermediate M2.

[0145] Add 100 mmol of 2-amino-9,9-dimethylfluorene, 100 mmol of 2-bromo-N-phenylcarbazole, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of toluene, and 1 mol% (1 mol% of 2-amino-9,9-dimethylfluorene) of Pd(dba) into the reaction flask. 2 The reaction was carried out at 100°C for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder M3.

[0146] Add 100 mmol of M2, 100 mmol of M3, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of xylene, and 1 mol% (1 mol% of M2) of Pd(dba) into the reaction flask. 2 The reaction was carried out at 120°C for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder A14.

[0147] 1 H NMR (400MHz, Chloroform) δ8.55(d,J=7.2Hz,1H),8.22(d,J=8.4Hz,1H),8.16(d,J=7.6Hz,1H),7.90(d,J=8.0Hz,1H) ,7.86(d,J=8.8Hz,2H),7.73(d,J=7.2Hz,1H),7.65-7.38(m,14H),7.36-7.22(m,5H),7.15-7.06(m,4H),1.69(s,6H).

[0148] M / Z: Exp., 653.5; Calc., 652.3.

[0149] Synthesis Example 7: Synthesis of Compound A15

[0150]

[0151] 100 mmol of 2-bromo-1-naphthol, 100 mmol of 1-naphthoboric acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of THF and 200 ml of water were added to the reaction flask, and 1 mol% (1 mol% of 2-bromo-1-naphthol) of Pd(PPh 3 ) 4 The reaction was carried out at 60°C for 12 hours. After the reaction was completed, the reaction was stopped and the reactant was cooled to room temperature. Water was added, the liquid was separated, and the organic phase was concentrated to obtain a white solid. The solid was filtered and washed with water. The obtained solid was recrystallized and purified with toluene to obtain a white powder M1.

[0152] Add 100 mmol of M1 and 200 ml of dichloromethane to the reaction flask, and then drop 110 mmol of trifluoromethanesulfonate at 0°C. After the addition is complete, control the temperature at 0°C for 1 hour, then warm it to room temperature for 12 hours. After the reaction is complete, add water, extract with ethyl acetate, separate the organic phase, and concentrate it to obtain the intermediate M2.

[0153] Add 100 mmol of 3-amino-dibenzofuran, 100 mmol of 2-bromo-9,9-diphenylfluorene, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of toluene, and 1 mol% (1 mol% of 3-amino-dibenzofuran) of Pd(dba) into the reaction flask. 2 The reaction was carried out at 100°C for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder M3.

[0154] Add 100 mmol of M2, 100 mmol of M3, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of xylene, and 1 mol% (1 mol% of M2) of Pd(dba) into the reaction flask. 2 The reaction was carried out at 120°C for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder A15.

[0155] 1H NMR (400MHz, Chloroform) δ8.95(d,J=7.6Hz,1H),8.50(t,J=7.6Hz,1H),8.20(d,J=7.6Hz,1H),8.04(d,J=7.2Hz,1H),8.01(t,J=7.2Hz,2 H),7.92(d,J=7.6Hz,3H),7.88(d,J=10.0Hz,1H),7.76(d,J=9.2Hz,4H),7.55(d,J=8.8Hz,2H),7.45-7.15(m,17H),7.08(d,J=8.8Hz,4H).

[0156] M / Z: Exp., 752.4; Calc., 751.3.

[0157] Synthesis Example 8: Synthesis of Compound A17

[0158]

[0159] 100 mmol of 2-bromo-5-chloro-1-naphthol, 100 mmol of phenylboric acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of THF and 200 ml of water were added to the reaction flask, and 1% mmol (1% mmol of 2-bromo-5-chloro-1-naphthol) of Pd(PPh 3 ) 4 The reaction was carried out at 60°C for 12 hours. After the reaction was completed, the reaction was stopped and the reactant was cooled to room temperature. Water was added, the liquid was separated, and the organic phase was concentrated to obtain a white solid. The solid was filtered and washed with water. The obtained solid was recrystallized and purified with toluene to obtain a white powder M1.

[0160] 100 mmol of M1, 100 mmol of 3-dibenzothiophene boronic acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of THF and 200 ml of water were added to the reaction flask, and 1% mmol (1% mmol of M1) of Pd(PPh 3 ) 4 The reaction was carried out at 60°C for 12 hours. After the reaction was completed, the reaction was stopped and the reactant was cooled to room temperature. Water was added, the liquid was separated, and the organic phase was concentrated to obtain a white solid. The solid was filtered and washed with water. The obtained solid was recrystallized and purified with toluene to obtain a white powder M2.

[0161] Add 100 mmol of M2 and 200 ml of dichloromethane to the reaction flask, and then drop 110 mmol of trifluoromethanesulfonate at 0°C. After the addition is complete, control the temperature at 0°C for 1 hour, then warm it to room temperature for 12 hours. After the reaction is complete, add water, extract with ethyl acetate, separate the organic phase, and concentrate it to obtain the intermediate M3.

[0162] Add 100 mmol of 2-amino-9,9-dimethylfluorene, 100 mmol of 2-bromo-9,9-dimethylfluorene, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of toluene, and 1 mol% (1 mol% of 2-amino-9,9-dimethylfluorene) of Pd(dba) into the reaction flask. 2 The reaction was carried out at 100°C for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder M4.

[0163] Add 100 mmol of M3, 100 mmol of M4, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of xylene, and 1 mol% (1 mol% of M3) of Pd(dba) into the reaction flask. 2 The reaction was carried out at 120°C for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder A17.

[0164] 1 H NMR (400MHz, Chloroform) δ8.52(d,J=8.0Hz,2H),8.41(s,1H),8.16(d,J=8.0Hz,2H),7.93(d,J=10.4Hz,2H),7.88(d,J=.6Hz,4H),7.79(t,J=7.6 Hz,1H),7.73(d,J=8.4Hz,1H),7.56(d,J=8.0Hz,3H),7.51(s,2H),7.45- 7.28(m,9H),7.21(t,J=7.6Hz,2H),7.08(d,J=8.4Hz,2H),1.69(s,12H).

[0165] M / Z: Exp., 786.2; Calc., 785.3.

[0166] Synthesis Example 9: Synthesis of Compound A20

[0167]

[0168] 100 mmol of 2-chloro-6-bromo-1-naphthol, 200 mmol of phenylboric acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of THF and 200 ml of water were added to the reaction flask, and 2% mmol (2% mmol of 2-chloro-6-bromo-1-naphthol) of Pd(PPh 3 ) 4The reaction was carried out at 60°C for 12 hours. After the reaction was completed, the reaction was stopped and the reactant was cooled to room temperature. Water was added, the liquid was separated, and the organic phase was concentrated to obtain a white solid. The solid was filtered and washed with water. The obtained solid was recrystallized and purified with toluene to obtain a white powder M1.

[0169] Add 100 mmol of M1 and 200 ml of dichloromethane to the reaction flask, and then drop 110 mmol of trifluoromethanesulfonate at 0°C. After the addition is complete, control the temperature at 0°C for 1 hour, then warm it to room temperature for 12 hours. After the reaction is complete, add water, extract with ethyl acetate, separate the organic phase, and concentrate it to obtain the intermediate M2.

[0170] 100 mmol of 1,4-dibromonaphthalene, 100 mmol of 1-naphthaleneboric acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of THF and 200 ml of water were added to the reaction flask, and 2% mmol (2% mmol of 1,4-dibromonaphthalene) of Pd(PPh 3 ) 4 The reaction was carried out at 60°C for 12 hours. After the reaction was completed, the reaction was stopped and the reactant was cooled to room temperature. Water was added, the liquid was separated, and the organic phase was concentrated to obtain a white solid. The solid was filtered and washed with water. The obtained solid was recrystallized and purified with toluene to obtain a white powder M3.

[0171] Add 100 mmol of 2-amino-9,9-dimethylfluorene, 100 mmol of M3, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of toluene, and 1 mol% (1 mol% of M3) of Pd(dba) into the reaction flask. 2 The reaction was carried out at 100°C for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder M4.

[0172] Add 100 mmol of M2, 100 mmol of M4, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of xylene, and 1 mol% (1 mol% of M2) of Pd(dba) into the reaction flask. 2 The reaction was carried out at 120°C for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain a white powder A20.

[0173] 1H NMR (400MHz, Chloroform) δ8.95(d,J=7.6Hz,2H),8.50(d,J=7.6Hz,1H),8.27(d,J=7.2Hz,1H),8.23(d,J=7.6Hz,1H),8.17(d,J= 8.4Hz,1H),7.88(d,J=7.6Hz,3H),7.80-7.68(m,5H),7.55-7.31(m,18H),7.21(t,J=7.2Hz,1H),7.09-7.02(m,2H),1.69(s,6H).

[0174] M / Z: Exp., 740.1; Calc., 739.3.

[0175] Synthesis Example 10: Synthesis of Compound A22

[0176]

[0177] 100 mmol of 2-bromo-1-naphthol, 100 mmol of deuterated phenylboronic acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of THF and 200 ml of water were added to the reaction flask, and 1 mol% (1 mol% of 2-bromo-1-naphthol) of Pd(PPh 3 ) 4 The reaction was carried out at 60°C for 12 hours. After the reaction was completed, the reaction was stopped and the reactant was cooled to room temperature. Water was added, the liquid was separated, and the organic phase was concentrated to obtain a white solid. The solid was filtered and washed with water. The obtained solid was recrystallized and purified with toluene to obtain a white powder M1.

[0178] Add 100 mmol of M1 and 200 ml of dichloromethane to the reaction flask, and then drop 110 mmol of trifluoromethanesulfonate at 0°C. After the addition is complete, control the temperature at 0°C for 1 hour, then warm it to room temperature for 12 hours. After the reaction is complete, add water, extract with ethyl acetate, separate the organic phase, and concentrate it to obtain the intermediate M2.

[0179] Add 100 mmol of 2-amino-9,9-dimethylfluorene, 100 mmol of 2-bromo-9,9-dimethylfluorene, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of toluene, and 1 mol% (1 mol% of 2-amino-9,9-dimethylfluorene) of Pd(dba) into the reaction flask. 2 The reaction was carried out at 100°C for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder M3.

[0180] Add 100 mmol of M2, 100 mmol of M3, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of xylene, and 1 mol% (1 mol% of M2) of Pd(dba) into the reaction flask. 2 The reaction was carried out at 120°C for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder A22.

[0181] 1 H NMR (400MHz, Chloroform) δ8.20(d,J=7.2Hz,1H),7.90(d,J=7.6Hz,3H),7.85(d,J=8.4Hz,2H),7.75(d,J=7.2Hz,1H ),7.51(d,J=7.6Hz,3H),7.45-7.38(m,4H),7.35(t,J=7.6Hz,2H),7.24(d,J=7.6Hz,4H),2.14(s,6H),1.65(s,6H).

[0182] M / Z: Exp., 609.1; Calc., 608.3.

[0183] Synthesis Example 11: Synthesis of Compound A23

[0184]

[0185] 100 mmol of 2-bromo-1-naphthol, 100 mmol of phenylboric acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of THF and 200 ml of water were added to the reaction flask, and 1 mol% (1 mol% of 2-bromo-1-naphthol) of Pd(PPh 3 ) 4 The reaction was carried out at 60°C for 12 hours. After the reaction was completed, the reaction was stopped and the reactant was cooled to room temperature. Water was added, the liquid was separated, and the organic phase was concentrated to obtain a white solid. The solid was filtered and washed with water. The obtained solid was recrystallized and purified with toluene to obtain a white powder M1.

[0186] Add 100 mmol of M1 and 200 ml of dichloromethane to the reaction flask, and then drop 110 mmol of trifluoromethanesulfonate at 0°C. After the addition is complete, control the temperature at 0°C for 1 hour, then warm it to room temperature for 12 hours. After the reaction is complete, add water, extract with ethyl acetate, separate the organic phase, and concentrate it to obtain the intermediate M2.

[0187] Add 100mmol of 3-bromo-N-phenylcarbazole and 200ml of THF to the reaction bottle, add 100mmol of n-butyl lithium dropwise at -78°C, react at -78°C for 1h, add 100mmol of acetonitrile dropwise, react at -78°C for 1h, warm to room temperature and react for 12h. After the reaction is complete, add water, extract with ethyl acetate, separate the organic phase, concentrate, and purify by column chromatography (ethyl acetate: petroleum ether 1:100) to obtain intermediate M3.

[0188] 100 mmol of 1,2-dibromobenzene, 100 mmol of p-chlorophenylboric acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of THF and 200 ml of water were added to the reaction flask, and 1 mol% (1 mol% of 1,2-dibromobenzene) of Pd(PPh 3 ) 4 The reaction was carried out at 60°C for 12 hours. After the reaction was completed, the reaction was stopped and the reactant was cooled to room temperature. Water was added, the liquid was separated, and the organic phase was concentrated to obtain a white solid. The solid was filtered and washed with water. The obtained solid was recrystallized and purified with toluene to obtain a white powder M4.

[0189] Add 100 mmol of M4 and 200 ml of THF to the reaction bottle, add 100 mmol of n-butyl lithium dropwise at -78°C, react at -78°C for 1 hour, add 100 mmol of M3 dropwise, react at -78°C for 1 hour, warm to room temperature and react for 12 hours. After the reaction is completed, add water, extract with ethyl acetate, separate the organic phase, concentrate, and purify by column chromatography to obtain intermediate M5.

[0190] Add 100 mmol of M5 and 300 ml of glacial acetic acid to the reaction flask, heat to 120°C and reflux for 12 hours. After the reaction is completed, add water, solid precipitates, filter and dry to obtain intermediate M6.

[0191] Add 100 mmol of M6, 100 mmol of 4-benzidine, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of toluene, and 1 mol% (1 mol% of M6) of Pd(dba) into the reaction flask. 2 The reaction was carried out at 100°C for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder M7.

[0192] Add 100 mmol of M2, 100 mmol of M7, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of xylene, and 1 mol% (1 mol% of M2) of Pd(dba) into the reaction flask. 2The reaction was carried out at 120°C for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder A23.

[0193] 1 H NMR (400MHz, Chloroform) δ8.55(d,J=8.0Hz,1H),8.20(d,J=8.0Hz,1H),8.05(s,1H),7.92(t,J=9.2Hz,4H),7.75(d,J=8.0Hz,3H),7.68(d,J=7.6Hz,1 H),7.62(t,J=7.2Hz,4H),7.50-7.31(m,17H),7.24(t,J=7.2Hz,1H),7.18( d,J=7.2Hz,3H),7.10(d,J=8.0Hz,2H),7.01(d,J=7.2Hz,1H),2.28(s,3H).

[0194] M / Z: Exp., 791.6; Calc., 790.3.

[0195] Synthesis Example 12: Synthesis of Compound A25

[0196]

[0197] 100 mmol of 2-bromo-1-naphthol, 100 mmol of phenylboric acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of THF and 200 ml of water were added to the reaction flask, and 1 mol% (1 mol% of 2-bromo-1-naphthol) of Pd(PPh 3 ) 4 The reaction was carried out at 60°C for 12 hours. After the reaction was completed, the reaction was stopped and the reactant was cooled to room temperature. Water was added, the liquid was separated, and the organic phase was concentrated to obtain a white solid. The solid was filtered and washed with water. The obtained solid was recrystallized and purified with toluene to obtain a white powder M1.

[0198] Add 100 mmol of M1 and 200 ml of dichloromethane to the reaction flask, and then drop 110 mmol of trifluoromethanesulfonate at 0°C. After the addition is complete, control the temperature at 0°C for 1 hour, then warm it to room temperature for 12 hours. After the reaction is complete, add water, extract with ethyl acetate, separate the organic phase, and concentrate it to obtain the intermediate M2.

[0199] Add 100 mmol of 2-bromonaphthalene and 200 ml of THF to the reaction bottle, add 100 mmol of n-butyl lithium dropwise at -78°C, react at -78°C for 1 hour, add 100 mmol of acetonitrile dropwise, react at -78°C for 1 hour, warm to room temperature and react for 12 hours. After the reaction is complete, add water, extract with ethyl acetate, separate the organic phase, concentrate, and purify by column chromatography (ethyl acetate: petroleum ether 1:100) to obtain intermediate M3.

[0200] 100 mmol of 1,2-dibromobenzene, 100 mmol of p-chlorophenylboric acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of THF and 200 ml of water were added to the reaction flask, and 1 mol% (1 mol% of 1,2-dibromobenzene) of Pd(PPh 3 ) 4 The reaction was carried out at 60°C for 12 hours. After the reaction was completed, the reaction was stopped and the reactant was cooled to room temperature. Water was added, the liquid was separated, and the organic phase was concentrated to obtain a white solid. The solid was filtered and washed with water. The obtained solid was recrystallized and purified with toluene to obtain a white powder M4.

[0201] Add 100 mmol of M4 and 200 ml of THF to the reaction bottle, add 100 mmol of n-butyl lithium dropwise at -78°C, react at -78°C for 1 hour, add 100 mmol of M3 dropwise, react at -78°C for 1 hour, warm to room temperature and react for 12 hours. After the reaction is completed, add water, extract with ethyl acetate, separate the organic phase, concentrate, and purify by column chromatography to obtain intermediate M5.

[0202] Add 100 mmol of M5 and 300 ml of glacial acetic acid to the reaction flask, heat to 120°C and reflux for 12 hours. After the reaction is completed, add water, solid precipitates, filter and dry to obtain intermediate M6.

[0203] 100 mmol of 3,5-diisopropyl bromobenzene, 100 mmol of p-aminophenylboronic acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of THF and 200 ml of water were added to the reaction flask, and 1 mol% (1 mol% of 3,5-diisopropyl bromobenzene) of Pd(PPh 3 ) 4 The reaction was carried out at 60°C for 12 hours. After the reaction was completed, the reaction was stopped and the reactant was cooled to room temperature. Water was added, the liquid was separated, and the organic phase was concentrated to obtain a white solid. The solid was filtered and washed with water. The obtained solid was recrystallized and purified with toluene to obtain a white powder M7.

[0204] Add 100 mmol of M6, 100 mmol of M7, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of toluene, and 1 mol% (1 mol% of M6) of Pd(dba) into the reaction flask. 2 The reaction was carried out at 100°C for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder M8.

[0205] Add 100 mmol of M2, 100 mmol of M8, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of xylene, and 1 mol% (1 mol% of M2) of Pd(dba) into the reaction flask. 2 The reaction was carried out at 120°C for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder A25.

[0206] 1 H NMR (400MHz, Chloroform) δ8.20(d,J=7.6Hz,1H),7.96(d,J=7.6Hz,3H),7.90(d,J=9.6Hz,1H),7.80-7.71(m,6H),7.64(d,J =7.6Hz,2H),7.57-7.49(m,6H),7.45-7.32(m,9H),7.30(d,J=7.6Hz,2H),7.26(d,J=7.2Hz,2H),2.34(s,3H),1.32(s,18H).

[0207] M / Z: Exp., 788.5; Calc., 787.4.

[0208] Synthesis Example 13: Synthesis of Compound A26

[0209]

[0210] 100 mmol of 2-bromo-1-naphthol, 100 mmol of 3-dibenzofuran boronic acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of THF and 200 ml of water were added to the reaction flask, and 1 mol% (1 mol% of 2-bromo-1-naphthol) of Pd(PPh 3 ) 4 The reaction was carried out at 60°C for 12 hours. After the reaction was completed, the reaction was stopped and the reactant was cooled to room temperature. Water was added, the liquid was separated, and the organic phase was concentrated to obtain a white solid. The solid was filtered and washed with water. The obtained solid was recrystallized and purified with toluene to obtain a white powder M1.

[0211] Add 100 mmol of M1 and 200 ml of dichloromethane to the reaction flask, and then drop 110 mmol of trifluoromethanesulfonate at 0°C. After the addition is complete, control the temperature at 0°C for 1 hour, then warm it to room temperature for 12 hours. After the reaction is complete, add water, extract with ethyl acetate, separate the organic phase, and concentrate it to obtain the intermediate M2.

[0212] Add 100 mmol of 2-amino-9,9-dimethylfluorene, 100 mmol of 2-bromo-9,9-dimethylfluorene, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of toluene, and 1 mol% (1 mol% of 2-amino-9,9-dimethylfluorene) of Pd(dba) into the reaction flask. 2 The reaction was carried out at 100°C for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder M3.

[0213] Add 100 mmol of M2, 100 mmol of M3, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of xylene, and 1 mol% (1 mol% of M2) of Pd(dba) into the reaction flask. 2 The reaction was carried out at 120°C for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder A26.

[0214] 1 H NMR(400MHz,Chloroform)δ8.20(d,J=7.6Hz,1H),8.01(d,J=7.6Hz,2H),7.88(d,J=8.0Hz,3H),7.84(d,J=9.6Hz,2H),7 .76(t,J=7.6Hz,3H),7.55(t,J=7.6Hz,3H),7.51-7.39(m,6H),7.36-7.24(m,5H),7.24(d,J=7.2Hz,2H),1.69(s,12H).

[0215] M / Z: Exp., 694.2; Calc., 693.3.

[0216] Synthesis Example 14: Synthesis of Compound A30

[0217]

[0218] 100 mmol of 2-bromo-1-naphthol, 100 mmol of phenylboric acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of THF and 200 ml of water were added to the reaction flask, and 1 mol% (1 mol% of 2-bromo-1-naphthol) of Pd(PPh 3 ) 4 The reaction was carried out at 60°C for 12 hours. After the reaction was completed, the reaction was stopped and the reactant was cooled to room temperature. Water was added, the liquid was separated, and the organic phase was concentrated to obtain a white solid. The solid was filtered and washed with water. The obtained solid was recrystallized and purified with toluene to obtain a white powder M1.

[0219] Add 100 mmol of M1 and 200 ml of dichloromethane to the reaction flask, and then drop 110 mmol of trifluoromethanesulfonate at 0°C. After the addition is complete, control the temperature at 0°C for 1 hour, then warm it to room temperature for 12 hours. After the reaction is complete, add water, extract with ethyl acetate, separate the organic phase, and concentrate it to obtain the intermediate M2.

[0220] Add 100 mmol of 4-benzidine, 100 mmol of bromobenzene, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of toluene, and 1 mol% (1 mol% of 4-benzidine) of Pd(dba) into the reaction flask. 2 The reaction was carried out at 100°C for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder M3.

[0221] Add 100 mmol of M3, 100 mmol of m-chlorobromobenzene, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of toluene, and 1 mol% (1 mol% of M3) of Pd(dba) into the reaction flask. 2 The reaction was carried out at 100°C for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder M4.

[0222] Add 100 mmol of 2-amino-9,9-dimethylfluorene, 100 mmol of M4, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of toluene, and 1 mol% (1 mol% of M4) of Pd(dba) into the reaction flask. 2 The reaction was carried out at 100°C for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder M5.

[0223] Add 100 mmol of M2, 100 mmol of M5, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of xylene, and 1 mol% (1 mol% of M2) of Pd(dba) into the reaction flask. 2 The reaction was carried out at 120°C for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain a white powder A30.

[0224] 1 H NMR(400MHz,Chloroform)δ8.18(d,J=7.2Hz,1H),7.91(d,J=7.6Hz,2H),7.86(d,J=8.8Hz,1H),7.75(d,J=7.2Hz,3H),7.57-7.31(m,16H), 7.25(t,J=7.6Hz,4H),7.17(d,J=7.6Hz,1H),7.08(d,J=7.6Hz,4H),7.02(t,J=7.2Hz,1H),6.84(s,1H),6.74(d,J=7.6Hz,2H),1.68(s,6H).

[0225] M / Z: Exp., 731.2; Calc., 730.3.

[0226] Synthesis Example 15: Synthesis of Compound A31

[0227]

[0228] 100 mmol of 2-bromo-1-naphthol, 100 mmol of phenylboric acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of THF and 200 ml of water were added to the reaction flask, and 1 mol% (1 mol% of 2-bromo-1-naphthol) of Pd(PPh 3 ) 4 The reaction was carried out at 60°C for 12 hours. After the reaction was completed, the reaction was stopped and the reactant was cooled to room temperature. Water was added, the liquid was separated, and the organic phase was concentrated to obtain a white solid. The solid was filtered and washed with water. The obtained solid was recrystallized and purified with toluene to obtain a white powder M1.

[0229] Add 100 mmol of M1 and 200 ml of dichloromethane to the reaction flask, and then drop 110 mmol of trifluoromethanesulfonate at 0°C. After the addition is complete, control the temperature at 0°C for 1 hour, then warm it to room temperature for 12 hours. After the reaction is complete, add water, extract with ethyl acetate, separate the organic phase, and concentrate it to obtain the intermediate M2.

[0230] 100 mmol of 3-bromocarbazole, 100 mmol of phenylboronic acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of THF and 200 ml of water were added to the reaction flask, and 1 mol% (1 mol% of 3-bromocarbazole) of Pd(PPh 3 ) 4 The reaction was carried out at 60°C for 12 hours. After the reaction was completed, the reaction was stopped and the reactant was cooled to room temperature. Water was added, the liquid was separated, and the organic phase was concentrated to obtain a white solid. The solid was filtered and washed with water. The obtained solid was recrystallized and purified with toluene to obtain a white powder M3.

[0231] Add 100 mmol of M3, 100 mmol of m-chlorofluorobenzene, 41.4 g of potassium carbonate (300 mmol), and 800 ml of N,N-dimethylformamide (DMF) to the reaction flask. React at 120°C for 12 hours. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain white powder M4.

[0232] Add 100 mmol of 2-amino-9,9-dimethylfluorene, 100 mmol of M4, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of toluene, and 1 mol% (1 mol% of M4) of Pd(dba) into the reaction flask. 2 The reaction was carried out at 100°C for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder M5.

[0233] Add 100 mmol of M2, 100 mmol of M5, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of xylene, and 1 mol% (1 mol% of M2) of Pd(dba) into the reaction flask. 2 The reaction was carried out at 120°C for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain a white powder A31.

[0234] 1H NMR(400MHz,Chloroform)δ8.16(d,J=7.2Hz,1H),7.90(d,J=7.6Hz,2H),7.86(d,J=8.8Hz,1H),7.72(d,J=7.2Hz,3H),7.55-7.31(m,14H), 7.24(t,J=7.6Hz,4H),7.18(d,J=7.6Hz,1H),7.10(d,J=7.6Hz,4H),7.04(t,J=7.2Hz,1H),6.84(s,1H),6.76(d,J=7.6Hz,2H),1.68(s,6H).

[0235] M / Z: Exp., 729.4; Calc., 728.3.

[0236] Synthesis Example 16: Synthesis of Compound A37

[0237]

[0238] 100 mmol of 2-bromo-1-naphthol, 100 mmol of phenylboric acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of THF and 200 ml of water were added to the reaction flask, and 1 mol% (1 mol% of 2-bromo-1-naphthol) of Pd(PPh 3 ) 4 The reaction was carried out at 60°C for 12 hours. After the reaction was completed, the reaction was stopped and the reactant was cooled to room temperature. Water was added, the liquid was separated, and the organic phase was concentrated to obtain a white solid. The solid was filtered and washed with water. The obtained solid was recrystallized and purified with toluene to obtain a white powder M1.

[0239] Add 100 mmol of M1 and 200 ml of dichloromethane to the reaction flask, and then drop 110 mmol of trifluoromethanesulfonate at 0°C. After the addition is complete, control the temperature at 0°C for 1 hour, then warm it to room temperature for 12 hours. After the reaction is complete, add water, extract with ethyl acetate, separate the organic phase, and concentrate it to obtain the intermediate M2.

[0240] 100 mmol of 2-bromofluorenone, 300 mmol of phenol, and 800 ml of polyphosphoric acid were added to the reaction flask and reacted at 100°C for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder M3.

[0241] Add 100 mmol of 2-amino-9,9-dimethylfluorene, 100 mmol of M3, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of toluene, and 1 mol% (1 mol% of 2-amino-9,9-dimethylfluorene) of Pd(dba) into the reaction flask. 2 The reaction was carried out at 100°C for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder M4.

[0242] Add 100 mmol of M2, 100 mmol of M4, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of xylene, and 1 mol% (1 mol% of M2) of Pd(dba) into the reaction flask. 2 The reaction was carried out at 120°C for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder A37.

[0243] 1 H NMR (400MHz, Chloroform) δ8.20(d,J=7.6Hz,1H),7.94(d,J=8.4Hz,3H),7.88(d,J=9.6Hz,2H),7.75(d,J=7.6Hz,1H ),7.55-7.40(m,10H),7.35-7.26(m,6H),7.24-7.11(m,6H),7.11-7.05(s,2H),7.00(t,J=7.6Hz,2H),1.69(s,6H).

[0244] M / Z: Exp., 742.5; Calc., 741.3.

[0245] Synthesis Example 17: Synthesis of Compound A39

[0246]

[0247] 100 mmol of 2-bromo-1-naphthol, 100 mmol of 3-phenanthrene boronic acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of THF and 200 ml of water were added to the reaction flask, and 1 mol% (1 mol% of 2-bromo-1-naphthol) of Pd(PPh 3 ) 4 The reaction was carried out at 60°C for 12 hours. After the reaction was completed, the reaction was stopped and the reactant was cooled to room temperature. Water was added, the liquid was separated, and the organic phase was concentrated to obtain a white solid. The solid was filtered and washed with water. The obtained solid was recrystallized and purified with toluene to obtain a white powder M1.

[0248] Add 100 mmol of M1 and 200 ml of dichloromethane to the reaction flask, and then drop 110 mmol of trifluoromethanesulfonate at 0°C. After the addition is complete, control the temperature at 0°C for 1 hour, then warm it to room temperature for 12 hours. After the reaction is complete, add water, extract with ethyl acetate, separate the organic phase, and concentrate it to obtain the intermediate M2.

[0249] Add 100 mmol of 2-amino-9,9-dimethylfluorene, 100 mmol of 2-bromo-9,9-dimethylfluorene, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of toluene, and 1 mol% (1 mol% of 2-amino-9,9-dimethylfluorene) of Pd(dba) into the reaction flask. 2 The reaction was carried out at 100°C for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder M3.

[0250] Add 100 mmol of M2, 100 mmol of M3, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of xylene, and 1 mol% (1 mol% of M2) of Pd(dba) into the reaction flask. 2 The reaction was carried out at 120°C for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder A39.

[0251] 1 H NMR (400MHz, Chloroform) δ9.11(d,J=7.6Hz,1H),8.70(d,J=7.2Hz,1H),8.60(s,1H),8.45(d,J=7.2Hz,1H),8.20(d,J=7.2Hz,1H),7.9 5-7.86(m,7H),7.73(d,J=7.6Hz,2H),7.68(t,J=7.2Hz,2H),7.52-7.41(m,7H),7.38-7.29(m,4H),7.24(d,J=7.6Hz,2H),1.69(s,12H).

[0252] M / Z: Exp., 704.3; Calc., 703.3.

[0253] Synthesis Example 18: Synthesis of Compound A41

[0254]

[0255] 100 mmol of 2-bromo-1-naphthol, 100 mmol of phenylboric acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of THF and 200 ml of water were added to the reaction flask, and 1 mol% (1 mol% of 2-bromo-1-naphthol) of Pd(PPh 3 ) 4 The reaction was carried out at 60°C for 12 hours. After the reaction was completed, the reaction was stopped and the reactant was cooled to room temperature. Water was added, the liquid was separated, and the organic phase was concentrated to obtain a white solid. The solid was filtered and washed with water. The obtained solid was recrystallized and purified with toluene to obtain a white powder M1.

[0256] Add 100 mmol of M1 and 200 ml of dichloromethane to the reaction flask, and then drop 110 mmol of trifluoromethanesulfonate at 0°C. After the addition is complete, control the temperature at 0°C for 1 hour, then warm it to room temperature for 12 hours. After the reaction is complete, add water, extract with ethyl acetate, separate the organic phase, and concentrate it to obtain the intermediate M2.

[0257] Add 100 mmol of 2-amino-9,9-dimethylfluorene, 100 mmol of bromobenzene, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of toluene, and 1 mol% (1 mol% of 2-amino-9,9-dimethylfluorene) of Pd(dba) into the reaction flask. 2 The reaction was carried out at 100°C for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder M3.

[0258] Add 100 mmol of M2, 100 mmol of M3, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of xylene, and 1 mol% (1 mol% of M2) of Pd(dba) into the reaction flask. 2 The reaction was carried out at 120°C for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain a white powder A41.

[0259] 1H NMR (400MHz, Chloroform) δ8.20(d,J=7.2Hz,1H),7.90(d,J=7.6Hz,2H),7.86(d,J=7.2Hz,1H),7.75(d,J=7.2Hz,1H),7.51(d,J=6.8Hz,2H),7. 47-7.37(m,6H),7.34(t,J=7.2Hz,1H),7.28(d,J=7.2Hz,1H),7.25(t,J=7.6Hz,3H),7.08(d,J=7.6Hz,4H),7.00(d,J=7.2Hz,1H),1.69(s,6H).

[0260] M / Z: Exp., 488.1; Calc., 487.2.

[0261] Synthesis Example 19: Synthesis of Compound A42

[0262]

[0263] 100 mmol of 2-bromo-1-naphthol, 100 mmol of 3-biphenylboronic acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of THF and 200 ml of water were added to the reaction flask, and 1 mol% (1 mol% of 2-bromo-1-naphthol) of Pd(PPh 3 ) 4 The reaction was carried out at 60°C for 12 hours. After the reaction was completed, the reaction was stopped and the reactant was cooled to room temperature. Water was added, the liquid was separated, and the organic phase was concentrated to obtain a white solid. The solid was filtered and washed with water. The obtained solid was recrystallized and purified with toluene to obtain a white powder M1.

[0264] Add 100 mmol of M1 and 200 ml of dichloromethane to the reaction flask, and then drop 110 mmol of trifluoromethanesulfonate at 0°C. After the addition is complete, control the temperature at 0°C for 1 hour, then warm it to room temperature for 12 hours. After the reaction is complete, add water, extract with ethyl acetate, separate the organic phase, and concentrate it to obtain the intermediate M2.

[0265] Add 100 mmol of 2-amino-9,9-dimethylfluorene, 100 mmol of bromobenzene, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of toluene, and 1 mol% (1 mol% of 2-amino-9,9-dimethylfluorene) of Pd(dba) into the reaction flask. 2 The reaction was carried out at 100°C for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder M3.

[0266] Add 100 mmol of M2, 100 mmol of M3, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of xylene, and 1 mol% (1 mol% of M2) of Pd(dba) into the reaction flask. 2 The reaction was carried out at 120°C for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain a white powder A42.

[0267] 1 H NMR (400MHz, Chloroform) δ8.20(d,J=7.2Hz,1H),7.90(d,J=7.6Hz,2H),7.86(d,J=8.8Hz,2H),7.75(d,J=7.6Hz,3H),7.68(d,J=7.2Hz,1H),7. 61(d,J=7.6Hz,2H),7.54-7.40(m,8H),7.34(d,J=7.6Hz,2H),7.24(t,J=8.4Hz,3H),7.08(d,J=7.6Hz,2H),7.00(t,J=7.2Hz,1H),1.69(s,6H).

[0268] M / Z: Exp., 564.3; Calc., 563.3.

[0269] Synthesis Example 20: Synthesis of Compound A43

[0270]

[0271] 100 mmol of 2-bromo-1-naphthol, 100 mmol of phenylboric acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of THF and 200 ml of water were added to the reaction flask, and 1 mol% (1 mol% of 2-bromo-1-naphthol) of Pd(PPh 3 ) 4 The reaction was carried out at 60°C for 12 hours. After the reaction was completed, the reaction was stopped and the reactant was cooled to room temperature. Water was added, the liquid was separated, and the organic phase was concentrated to obtain a white solid. The solid was filtered and washed with water. The obtained solid was recrystallized and purified with toluene to obtain a white powder M1.

[0272] Add 100 mmol of M1 and 200 ml of dichloromethane to the reaction flask, and then drop 110 mmol of trifluoromethanesulfonate at 0°C. After the addition is complete, control the temperature at 0°C for 1 hour, then warm it to room temperature for 12 hours. After the reaction is complete, add water, extract with ethyl acetate, separate the organic phase, and concentrate it to obtain the intermediate M2.

[0273] Add 100 mmol of bromobenzene and 200 ml of THF to the reaction bottle, add 100 mmol of n-butyl lithium dropwise at -78°C, react for 1 h at -78°C, add 100 mmol of acetonitrile dropwise, react for 1 h at -78°C, warm to room temperature and react for 12 h. After the reaction is complete, add water, extract with ethyl acetate, separate the organic phase, concentrate, and purify by column chromatography (ethyl acetate: petroleum ether 1:100) to obtain intermediate M3.

[0274] 100 mmol of 1,2-dibromobenzene, 100 mmol of p-chlorophenylboric acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of THF and 200 ml of water were added to the reaction flask, and 1 mol% (1 mol% of 1,2-dibromobenzene) of Pd(PPh 3 ) 4 The reaction was carried out at 60°C for 12 hours. After the reaction was completed, the reaction was stopped and the reactant was cooled to room temperature. Water was added, the liquid was separated, and the organic phase was concentrated to obtain a white solid. The solid was filtered and washed with water. The obtained solid was recrystallized and purified with toluene to obtain a white powder M4.

[0275] Add 100 mmol of M4 and 200 ml of THF to the reaction bottle, add 100 mmol of n-butyl lithium dropwise at -78°C, react at -78°C for 1 hour, add 100 mmol of M3 dropwise, react at -78°C for 1 hour, warm to room temperature and react for 12 hours. After the reaction is completed, add water, extract with ethyl acetate, separate the organic phase, concentrate, and purify by column chromatography to obtain intermediate M5.

[0276] Add 100 mmol of M5 and 300 ml of glacial acetic acid to the reaction flask, heat to 120°C and reflux for 12 hours. After the reaction is completed, add water, solid precipitates, filter and dry to obtain intermediate M6.

[0277] Add 100 mmol of M6, 100 mmol of 4-aminobiphenyl, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of toluene, and 1 mol% (1 mol% of M6) of Pd(dba) into the reaction flask. 2 The reaction was carried out at 100°C for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder M7.

[0278] Add 100 mmol of M2, 100 mmol of M7, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of xylene, and 1 mol% (1 mol% of M2) of Pd(dba) into the reaction flask. 2The reaction was carried out at 120°C for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder A43.

[0279] 1 H NMR(400MHz,Chloroform)δ7.88(d,J=10.0Hz,1H),7.82(d,J=9.6Hz,2H),7.76(d,J=8.4Hz,3H),7.7 0(s,1H),7.60-7.51(m,5H),7.47-7.28(m,12H),7.25-7.13(m,6H),7.10-7.06(m,2H),2.28(s,3H).

[0280] M / Z: Exp., 626.2; Calc., 625.3.

[0281] Synthesis Example 21: Synthesis of Compound A44

[0282]

[0283] 100 mmol of 2-bromo-1-naphthol, 100 mmol of phenylboric acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of THF and 200 ml of water were added to the reaction flask, and 1 mol% (1 mol% of 2-bromo-1-naphthol) of Pd(PPh 3 ) 4 The reaction was carried out at 60°C for 12 hours. After the reaction was completed, the reaction was stopped and the reactant was cooled to room temperature. Water was added, the liquid was separated, and the organic phase was concentrated to obtain a white solid. The solid was filtered and washed with water. The obtained solid was recrystallized and purified with toluene to obtain a white powder M1.

[0284] Add 100 mmol of M1 and 200 ml of dichloromethane to the reaction flask, and then drop 110 mmol of trifluoromethanesulfonate at 0°C. After the addition is complete, control the temperature at 0°C for 1 hour, then warm it to room temperature for 12 hours. After the reaction is complete, add water, extract with ethyl acetate, separate the organic phase, and concentrate it to obtain the intermediate M2.

[0285] 100 mmol of pentafluorobromobenzene, 100 mmol of p-chlorophenylboric acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of THF and 200 ml of water were added to the reaction flask, and 1 mol% (1 mol% of pentafluorobromobenzene) of Pd(PPh 3 ) 4The reaction was carried out at 60°C for 12 hours. After the reaction was completed, the reaction was stopped and the reactant was cooled to room temperature. Water was added, the liquid was separated, and the organic phase was concentrated to obtain a white solid. The solid was filtered and washed with water. The obtained solid was recrystallized and purified with toluene to obtain a white powder M3.

[0286] Add 100 mmol of 2-amino-9,9-dimethylfluorene, 100 mmol of M3, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of toluene, and 1 mol% (1 mol% of 2-amino-9,9-dimethylfluorene) of Pd(dba) into the reaction flask. 2 The reaction was carried out at 100°C for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder M4.

[0287] Add 100 mmol of M2, 100 mmol of M4, 28.83 g of sodium tert-butoxide (300 mmol), 800 ml of xylene, and 1 mol% (1 mol% of M2) of Pd(dba) into the reaction flask. 2 The reaction was carried out at 120°C for 12 hours. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder A44.

[0288] 1 H NMR (400MHz, Chloroform) δ8.20(d,J=7.2Hz,1H),7.90(d,J=7.6Hz,2H),7.88(d,J=9.2Hz,1H),7.76(d,J =7.2Hz,1H),7.56-7.47(m,5H),7.41-7.30(m,8H),7.25(d,J=8.0Hz,2H),7.10-7.6(m,2H),1.69(s,6H).

[0289] M / Z: Exp., 654.3; Calc., 653.2.

[0290] Other compounds of the present application can be synthesized by selecting suitable raw materials according to the ideas of the above synthesis examples, or by selecting any other suitable methods and raw materials for synthesis.

[0291] Example 1

[0292] A glass substrate coated with a 150 nm thick 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 the water was completely removed, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam to obtain a glass substrate with an anode;

[0293] Place the glass substrate with the anode in a vacuum chamber and evacuate the chamber to a pressure less than 10 -5 HT-11 was vacuum-deposited on the anode layer of the glass substrate with an anode as a hole injection layer at a rate of 0.1 nm / s and a thickness of 10 nm; the hole injection material HT-11 is as follows:

[0294]

[0295] Compound A1 of the present application is vacuum-deposited on the hole injection layer as a hole transport layer, with a deposition rate of 0.1 nm / s and a deposition film thickness of 80 nm; the hole transport material A1 is as follows:

[0296]

[0297] A light-emitting layer is vacuum-deposited on the hole transport layer. The light-emitting layer includes a main material GHP-10 and a dye material RPD-1. The deposition is performed by a multi-source co-evaporation method. The deposition rate of the main material GHP-10 is adjusted to 0.1 nm / s, and the deposition rate of the dye material RPD-1 is adjusted to 3% of the deposition rate of the main material GHP-10. The total deposition film thickness is 30 nm. The main material GHP-10 and the dye material RPD-1 are as follows:

[0298]

[0299] ET-30 was vacuum-deposited on the light-emitting layer as an electron transport layer. The deposition rate was 0.1 nm / s and the deposition film thickness was 30 nm. The electron transport material ET-30 was as follows:

[0300]

[0301] LiF with a thickness of 0.5 nm was vacuum-deposited on the electron transport layer as an electron injection layer at a rate of 0.1 nm / s;

[0302] Finally, an aluminum layer with a thickness of 150 nm was evaporated on the electron injection layer as a cathode of the organic electroluminescent device, and the evaporation rate was 0.1 nm / s.

[0303] Example 2-21

[0304] The same as Example 1 except that the hole transport materials are replaced by compounds A3, A7, A9, A11, A14, A15, A17, A20, A22, A23, A25, A26, A30, A31, A37, A39, A41, A42, A43, and A44 respectively instead of A1.

[0305] Comparative Example 1

[0306] Except that the hole transport material is HT-28 instead of A1, the rest is the same as Example 1; HT-28 is as follows:

[0307]

[0308] Comparative Example 2

[0309] Except that the hole transport material is HT-R1 instead of A1, the rest is the same as Example 1; HT-R1 is as follows:

[0310]

[0311] Comparative Example 3

[0312] Except that the hole transport material is HT-R2 instead of A1, the rest is the same as Example 1; HT-R2 is as follows:

[0313]

[0314] Comparative Example 4

[0315] Except that the hole transport material is HT-R3 instead of A1, the rest is the same as Example 1; HT-R3 is as follows:

[0316]

[0317] The organic electroluminescent device prepared by the above process was subjected to the following performance tests:

[0318] At the same brightness, a digital source meter and a brightness meter were used to measure the driving voltage, current efficiency and device life of the organic electroluminescent devices prepared in the embodiment and the comparative example. Specifically, the voltage was increased at a rate of 0.1 V per second, and the brightness of the organic electroluminescent device was measured when it reached 5000 cd / m 2 The voltage at which the light is on is the driving voltage, and the current density at this time is measured at the same time; the ratio of brightness to current density is the current efficiency; the life test of LT95 is as follows: use a brightness meter at 5000cd / m 2 At the same brightness, the current is kept constant and the brightness of the organic electroluminescent device is measured to drop to 4750cd / m 2 The time is in hours. The results are shown in Table 1.

[0319] Table 1 Performance results of organic electroluminescent devices

[0320]

[0321]

[0322] As can be seen from Table 1, compared with Comparative Examples 1-4, the use of the compounds of the present application as hole transport materials for organic electroluminescent devices has significantly lower driving voltage, significantly higher current efficiency, and significantly longer LT95 life. Among them, when HT-R1 used in Comparative Example 2 is used for the hole transport layer, the driving voltage of the device is relatively high due to the shallow HOMO energy level; and when the compound A41 of the present application is used for the hole transport layer, the driving voltage of the device can be significantly reduced. When HT-R2 used in Comparative Example 3 is used for the hole transport layer, although HT-R2 introduces the structure of 1,8 disubstituted naphthalene, forming a large steric hindrance, which deepens the HOMO energy level, its mobility is suppressed due to the destruction of planarity, which reduces the hole transport ability, and also leads to a higher driving voltage of the device; and when the compound A42 of the present application is used for the hole transport layer, the driving voltage of the device can be significantly reduced. When HT-R3 used in comparative example 4 is used for the hole transport layer, the injection of holes is hindered due to the shallow HOMO energy level, resulting in a higher driving voltage of the device; however, when compound A43 of the present application is used for the hole transport layer, the driving voltage of the device can be significantly reduced.

[0323] The above results show that the compounds provided in the present application can be used as hole transport materials in organic electroluminescent devices to effectively reduce the driving voltage, improve the current efficiency, and extend the service life, and are hole transport materials with good performance.

[0324] The above description is only a preferred embodiment of the present application and is not intended to limit the present application. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present application shall be included in the scope of protection of the present application.

Claims

1. A compound of general formula (I): in, R 1 -R 5 are independently selected from hydrogen, deuterium, hydroxyl, thiol, the following groups which are unsubstituted or substituted by Ra: C1-C3 alkyl, C2-C6 alkenyl, arylamine, C6-C 30 Aromatic or C6-C 30 Heteroaryl, the R 1 -R 5 Two adjacent groups in the can be connected to form a ring; R 6 -R 8 are independently selected from hydrogen, unsubstituted or substituted by Ra: C6-C 30 Aromatic or C 10 -C 30 heteroaryl; R, R' are independently selected from C1-C3 alkyl, C5-C 10 Cycloalkyl, unsubstituted or substituted by Ra: C6-C 30 Aromatic or C 10 -C 30 Heteroaryl, R and R' can be connected to form a ring; R 9 Selected from the following groups which are unsubstituted or substituted by Ra: C6-C 30 Aromatic or C6-C 30 heteroaryl; The heteroatoms on the heteroaryl group are each independently selected from O, S or N; The Ra are 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 R 1 -R 5 are independently selected from hydrogen, deuterium, the following groups which are unsubstituted or substituted by Ra: C1-C3 alkyl, C2-C6 alkenyl, arylamine, C6-C 18 Aromatic or C6-C 18 Heteroaryl, the R 1 -R 5 Two adjacent groups in the can be connected to form a ring; R 6 -R 8 are independently selected from hydrogen, unsubstituted or substituted by Ra: C6-C 18 Aromatic or C 10 -C 18 heteroaryl; R, R' are independently selected from C1-C3 alkyl, C5-C 10 Cycloalkyl, unsubstituted or substituted by Ra: C6-C 18 Aromatic or C 10 -C 18 Heteroaryl, R and R' can be connected to form a ring; R 9 Selected from the following groups which are unsubstituted or substituted by Ra: C6-C 18 Aromatic or C6-C 18 heteroaryl; The Ra are independently selected from deuterium, halogen, nitro, cyano, C1-C4 alkyl, C5-C 12 Cycloalkyl, phenyl, biphenyl, terphenyl or naphthyl.

3. The compound according to claim 1, wherein R 1 -R 5 are independently selected from hydrogen, deuterium, hydroxyl, mercapto, the following groups which are unsubstituted or substituted by Ra: methyl, ethyl, n-propyl, isopropyl, vinyl, propenyl, benzocyclohexyl, anilino, biphenylamino, phenyl, biphenyl, naphthyl, phenanthrenyl, fluorenyl, carbazolyl, xanthenyl; said R 1 -R 5 Two adjacent groups can be connected to form a ring.

4. The compound according to claim 1, wherein R 6 -R 8 The following groups are independently selected from hydrogen, unsubstituted or substituted by Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, dibenzofuranyl, dibenzothienyl, 9,9-dimethylfluorenyl, spirofluorenyl, arylamine, carbazolyl.

5. The compound according to claim 1, wherein R and R' are independently selected from methyl, ethyl, propyl, cyclopentyl, cyclohexyl, the following groups which are unsubstituted or substituted by Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, dibenzofuranyl, dibenzothienyl, 9,9-dimethylfluorenyl, spirofluorenyl, aromatic amino, carbazolyl; R and R' can be connected to form a ring.

6. The compound according to claim 1, wherein R 9 The group selected from the following groups which are unsubstituted or substituted by Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, benzofuranyl, dibenzofuranyl, benzothienyl, dibenzothienyl, 9,9-dimethylfluorenyl, spirofluorenyl, carbazolyl.

7. The compound according to claim 1, wherein The compound is selected from:

8. A hole transport material comprising at least one of the compounds according to any one of claims 1 to 7. 9 . An organic electroluminescent device comprising at least one of the hole transport materials according to claim 8 . 10 . A display device comprising the organic electroluminescent device according to claim 9 .

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