A kind of aromatic ring-linked electron-absorbing bibenzoxazole compound and its application

Abstract

The present application provides a compound of general formula (I), which can be used as an electron transport material. The compound has high bond energy between atoms, good thermal stability, is conducive to solid-state accumulation between molecules, has strong electron transition ability, and can be used as an electron transport material to effectively reduce the driving voltage of an organic electroluminescent device, improve its current efficiency, and extend its service life. The present application also provides an organic electroluminescent device and a display device comprising the compound of 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 an aromatic ring-linked electron-withdrawing bibenzoxazole compound and its application. Background Art

[0002] With the continuous advancement of OLED technology in the two major fields of lighting and display, people are paying more attention to the research on high-efficiency organic materials that affect the performance of OLED devices. An organic electroluminescent device with high efficiency and long life is usually the result of an optimized combination of device structure and various organic materials. This provides great opportunities and challenges for chemists to design and develop functional materials of various structures.

[0003] 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 realize 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. It is of great significance for domestic materials to break through patent barriers. 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 (dyes or doped guest materials) and corresponding host materials. Among them, electron transport materials, as an important functional material, have a direct impact on the mobility of electrons, and ultimately affect the luminous efficiency of OLEDs by affecting the matching with the hole layer and affecting the exciton recombination. The electron migration rate that can be achieved by the electron transport materials currently used in OLEDs is significantly lower than that of the hole layer materials used, and the energy level matching with the adjacent layers is poor, which seriously restricts the luminous efficiency of OLEDs and the display function of OLED display devices. The present invention is committed to developing electron transport materials with higher mobility to match high-mobility hole transport materials to achieve higher luminous efficiency. Summary of the invention

[0004] The purpose of the present application is to provide an aromatic ring-linked electron-withdrawing bibenzoxazole compound, which is used as an electron transport material to improve the working efficiency and extend the service life of an organic electroluminescent device.

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

[0006]

[0007]

[0008] in,

[0009] Ar and Ar 1Each independently selected from C6-C 30 Aryl or C3-C 30 The hydrogen atoms on the aryl and heteroaryl groups may each independently be replaced by Ra;

[0010] Ar 2 Selected from the following groups:

[0011]

[0012] Wherein, R is selected from C1-C6 alkyl or cycloalkyl, m is selected from 0-3; Z1-Z5 are each independently selected from N or CR1, R1 is selected from hydrogen, C6-C30 aryl or C3-C30 heteroaryl, and the hydrogen atoms on the aryl and heteroaryl can be independently replaced by Ra;

[0013] X 1 -X 3 are each independently selected from CH or N, and X 1 -X 3 At least two of them are selected from N;

[0014] L is selected from chemical bonds, C6-C 30 Arylene or C3-C 30 The hydrogen atoms on the arylene group and the heteroarylene group can be independently replaced by Ra, and adjacent Ra can be connected to form a ring;

[0015] The heteroatoms on the heteroaryl or the heteroarylene are each independently selected from O, S or N;

[0016] The substituents Ra of each group are each independently selected from deuterium, halogen, nitro, cyano, C1-C4 alkyl, phenyl, biphenyl, terphenyl, naphthyl or pyridyl.

[0017] A second aspect of the present application provides an electron transport material comprising at least one of the compounds provided in the present application.

[0018] The third aspect of the present application provides an organic electroluminescent device, comprising at least one of the electron transport materials provided in the present application.

[0019] A fourth aspect of the present application provides a display device, comprising the organic electroluminescent device provided by the present application.

[0020] The compound provided by the present application has a parent structure of a benzoxazole-linked electron-withdrawing fragment, a high bond energy between atoms, good thermal stability, and is conducive to solid-state accumulation between molecules, and the transition ability of electrons is strong. When used as an electron transport material, it has a matching energy level with the adjacent levels, which is conducive to the injection and migration of electrons, and can effectively reduce the driving voltage. It also has a high electron migration rate and can achieve good luminous efficiency in an organic electroluminescent device. The organic electroluminescent device of the present application includes the compound of the present application as an electron transport material, which can effectively reduce the driving voltage, improve the luminous efficiency, and extend the life of the organic electroluminescent device. The display device provided by the present application has an excellent display effect.

[0021] Of course, implementing any product or method of the present application does not necessarily require achieving all of the advantages described above at the same time. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] 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 one embodiment of the present application, and for ordinary technicians in this field, other embodiments can also be obtained based on these drawings.

[0023] Figure 1 A schematic diagram of the structure of a typical organic electroluminescent device. DETAILED DESCRIPTION

[0024] In order to make the purpose, technical scheme, and advantages of the present application more clearly understood, the present application is further described in detail with reference to the accompanying drawings and examples. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. All other embodiments obtained by ordinary technicians in this field based on the embodiments in the present application belong to the scope of protection of the present application.

[0025] The first aspect of the present application provides a compound of general formula (I):

[0026]

[0027] in,

[0028] Ar and Ar 1 Each independently selected from C6-C 30 Aryl or C3-C 30 The hydrogen atoms on the aryl and heteroaryl groups may each independently be replaced by Ra;

[0029] Ar 2 Selected from the following groups:

[0030]

[0031] Wherein, R is selected from C1-C6 alkyl or cycloalkyl, m is selected from 0-3; Z1-Z5 are each independently selected from N or CR1, R1 is selected from hydrogen, C6-C30 aryl or C3-C30 heteroaryl, and the hydrogen atoms on the aryl and heteroaryl can be independently replaced by Ra;

[0032] X 1 -X 3 are each independently selected from CH or N, and X 1 -X 3 At least two of them are selected from N;

[0033] L is selected from chemical bonds, C6-C 30 Arylene or C3-C 30 The hydrogen atoms on the arylene group and the heteroarylene group can be independently replaced by Ra, and adjacent Ra can be connected to form a ring;

[0034] The heteroatoms on the heteroaryl or the heteroarylene are each independently selected from O, S or N;

[0035] The substituents Ra of each group are each independently selected from deuterium, halogen, nitro, cyano, C1-C4 alkyl, phenyl, biphenyl, terphenyl, naphthyl or pyridyl.

[0036] The compound provided by the present application has a parent structure of a benzoxazole-linked electron-withdrawing fragment, a high bond energy between atoms, good thermal stability, and is conducive to solid-state accumulation between molecules, and the transition ability of electrons is strong. At the same time, this type of structure, its energy level is adjusted by the oxazole fragment, and it is more matched with the adjacent layer. It can be used as an electron transport layer material to effectively reduce the driving voltage of the organic electroluminescent device, improve the current efficiency of the organic electroluminescent device, and extend its service life. At the same time, the preparation process of the derivative of the benzoxazole-linked electron-withdrawing fragment described in the present application is simple and easy, and the raw materials are easily available, which is suitable for industrial production.

[0037] Preferably, Ar and Ar 1 Each independently selected from C6-C 18 Aryl or C3-C 18 The hydrogen atoms on the aryl and heteroaryl groups may each independently be replaced by Ra;

[0038] Preferably, Ar 2 Selected from the following groups:

[0039]

[0040] Wherein, R is selected from C1-C6 alkyl or cycloalkyl, m is selected from 0-3; Z1-Z5 are each independently selected from N or CR1;

[0041] Preferably, R1 is selected from hydrogen, C6-C 18 Aryl or C3-C 18 The hydrogen atoms on the aryl and heteroaryl groups may each independently be replaced by Ra;

[0042] Preferably, L is selected from a chemical bond, a C6-C 18 Arylene or C3-C 18 The hydrogen atoms on the arylene group and the heteroarylene group may be substituted by Ra independently, and adjacent Ra may be connected to form a ring.

[0043] More preferably, Ar and Ar 1 Each is independently selected from the following groups which are unsubstituted or substituted by Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazine, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9,9-dimethylfluorenyl, arylamine, carbazolyl.

[0044] More preferably, R1 is selected from the following groups which are hydrogen, unsubstituted or substituted with Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthrenyl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazine, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9,9-dimethylfluorenyl.

[0045] More preferably, R is selected from methyl, ethyl, isopropyl, tert-butyl, cyclopentyl, and cyclohexyl.

[0046] More preferably, L is selected from the subunits of the following compounds which are chemically bonded, unsubstituted or substituted with Ra: benzene, biphenyl, terphenyl, naphthalene, phenanthrene, triphenylene, fluorene, pyridine, pyridazine, pyrimidine, pyrazine, quinoline, isoquinoline, quinazoline, quinoxaline, cinnoline, naphthyridine, triazine, pyridopyrazine, benzofuran, dibenzofuran, aza-dibenzofuran, benzothiophene, dibenzothiophene, aza-dibenzothiophene, 9,9-dimethylfluorene, spirofluorene.

[0047] For example, the compound of general formula (I) is selected from the following compounds:

[0048]

[0049]

[0050] The second aspect of the present application provides an electron transport material, comprising at least one of the compounds provided in the present application. When the electron transport material of the present application is used in the electron transport layer, it has a matching energy level between adjacent layers, which is conducive to the injection and migration of electrons, can effectively reduce the driving voltage, and has a high electron migration rate, and can achieve good luminous efficiency in organic electroluminescent devices. The electron transport material provided by the present application also has a larger conjugated plane, which is conducive to molecular stacking, exhibits good thermodynamic stability, and exhibits a long life in organic electroluminescent devices.

[0051] The third aspect of the present application provides an organic electroluminescent device, comprising at least one of the electron transport materials provided in the present application as an electron transport layer. Therefore, the organic electroluminescent device provided in the present application can effectively reduce the driving voltage, improve the luminous efficiency, and extend the life of the organic electroluminescent device.

[0052] In the present application, there is no particular limitation on the type and structure of the organic electroluminescent device, and it can be any type and structure of organic electroluminescent device known in the art, as long as at least one of the electron transport materials provided in the present application can be used.

[0053] The organic electroluminescent device of the present application may be a light-emitting device with a top-emitting structure, which may include 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.

[0054] The organic electroluminescent device of the present application may also be a light-emitting device with a bottom-emitting structure, which may include 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.

[0055] The organic electroluminescent device of the present application may also be a light-emitting device with a double-sided light-emitting structure, which may include 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.

[0056] In addition, there may be an electron blocking layer between the hole transport layer and the light-emitting layer, there may be a hole blocking layer between the light-emitting layer and the electron transport layer, and a light extraction layer may be provided 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 made of metal, 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 (150nm to 400nm), a hole blocking layer (5nm to 20nm), an electron transport layer (300nm to 800nm), an electron injection layer (5nm to 20nm), a transparent or semi-transparent cathode, and a light extraction layer (50nm to 90nm) on a substrate in sequence.

[0057] 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.

[0058] Understandably, Figure 1 Only a typical structure of an organic electroluminescent device is schematically shown, and the present application is not limited to this structure. The electron transport material of the present application can be used in any type of organic electroluminescent device.

[0059] In the organic electroluminescent device of the present application, except for the electron transport layer comprising the electron transport material provided in the present application, other layers may use various materials used for the layers in the prior art.

[0060] 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 electron transport material of the present application are within the protection scope of the present application.

[0061] In the present application, the material of 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, glass and polymer materials with thin film transistor (TFT) components, etc.

[0062] In the present application, the material of the reflective anode electrode 2 is not particularly limited, and can be selected from transparent conductive materials such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), zinc oxide (ZnO), low-temperature polycrystalline silicon (LTPS) known in the prior art, or metal materials such as silver and its alloys, aluminum and its alloys, or organic conductive materials such as poly (3,4-ethylenedioxythiophene) (PEDOT), as well as multilayer structures of the above materials.

[0063] In the present application, the material of the hole injection layer 3 is not particularly limited, and hole transport materials or hole injection materials known in the art can be selected. For example, at least one of the known hole transport materials (HTM) can be selected as the hole injection material.

[0064] In the present application, the hole injection layer 3 may further include a p-type dopant. 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:

[0065]

[0066] 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.

[0067] In the present application, the hole transport layer 4 is not particularly limited and can be made of a hole transport material (HTM) known in the art. For example, the material for the hole injection layer main body and the material for the hole transport layer can be selected from but not limited to at least one of the following HT-1 to HT-31 compounds:

[0068]

[0069]

[0070]

[0071] In the present application, the luminescent material in the luminescent layer 5 is not particularly limited, and various luminescent materials known to those skilled in the art can be used. For example, the luminescent material can include a host material and a guest material. In the present application, there is no particular limitation on the amount of the host material and the guest material, and the amount can be any amount known to those skilled in the art.

[0072] In the present application, the light-emitting layer 5 may include a green light-emitting layer, a red light-emitting layer or a blue light-emitting layer. In the present application, the host material of the light-emitting layer is not particularly limited, and at least one of the light-emitting layer host materials known in the art may be used. For example, the green light-emitting layer host material may be selected from but not limited to at least one of the following GPH-1 to GPH-80 compounds:

[0073]

[0074]

[0075]

[0076] In the present application, the host material of the red light-emitting layer is not particularly limited, and at least one of the host materials of the red light-emitting layer known in the art can be used. For example, it can be selected from but not limited to the above GPH-1 to GPH-80 compounds, and at least one of the following RH-1 to RH-13 compounds:

[0077]

[0078] In the present application, the host material of the blue light-emitting layer is not particularly limited, and at least one of the blue light-emitting layer host materials known in the art can be used. For example, it can be selected from but not limited to at least one of the following BH-1 to BH-36 compounds:

[0079]

[0080]

[0081]

[0082] In the present application, the guest material of the red light-emitting layer is not particularly limited, and at least one of the red light-emitting layer guest materials known in the art can be used. For example, it can be selected from but not limited to at least one of the following RPD-1 to RPD-28 compounds:

[0083]

[0084]

[0085] In the present application, the guest material of the green light-emitting layer is not particularly limited, and at least one of the green light-emitting layer guest materials known in the art can be used. For example, it can be selected from but not limited to at least one of the following GD01 to GD04 compounds:

[0086]

[0087] In the present application, the guest material of the blue light-emitting layer is not particularly limited, and at least one of the blue light-emitting layer guest materials known in the art can be used. For example, it can be selected from but not limited to at least one of the following BD01 to BD04 compounds:

[0088]

[0089] In the present application, the electron transport layer 6 may include at least one of the electron transport materials of the present application, or may include a combination of at least one of the electron transport materials of the present application and at least one of the following known electron transport materials. For example, the known electron transport material may be selected from but not limited to at least one of the following ET-1 to ET-57 compounds:

[0090]

[0091]

[0092]

[0093] In the present application, the electron transport layer 6 may further include an n-type dopant. The type of the n-type dopant is not particularly limited, and various n-type dopants known in the art may be used. For example, the following n-type dopants may be used:

[0094]

[0095] 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.

[0096] 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, it can include but is not limited to at least one of the materials such as LiQ, LiF, NaCl, CsF, Li2O, Cs2CO3, BaO, Na, Li, Ca, etc. in the prior art.

[0097] In the present application, the material of the cathode electrode 8 is not particularly limited, and can be selected from but not limited to magnesium-silver mixture, magnesium-aluminum mixture, LiF / Al, ITO, Al and other metals, metal mixtures, oxides and the like.

[0098] The fourth aspect of the present application provides a display device, which includes the organic electroluminescent device provided by the present application and has an excellent display effect. The display device includes but is not limited to a display, a television, a tablet computer, a mobile communication terminal, etc.

[0099] 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:

[0100] (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;

[0101] (2) vacuum evaporating a hole injection material on the reflective anode electrode 2 to form a hole injection layer 3, wherein the hole injection layer 3 includes a main material and a p-type dopant;

[0102] (3) vacuum evaporating a hole transport material on the hole injection layer 3 to form a hole transport layer 4;

[0103] (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;

[0104] (5) vacuum evaporating an electron transport material on the light emitting layer 5 to form an electron transport layer 6;

[0105] (6) vacuum evaporating an electron injection material on the electron transport layer 6 to form an electron injection layer 7;

[0106] (7) A cathode material is vacuum-deposited on the electron injection layer 7 to form a cathode electrode 8 .

[0107] 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 electron 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.

[0108] The synthesis method of the compounds 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 compounds of the present application.

[0109] Synthesis Example

[0110] Synthesis of compound A1:

[0111]

[0112] Add 100mmol of 9-phenanthrene boronic acid, 100mmol of fenthiocarb, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water to a reaction flask, and add 1mol% of Pd(PPh3)4. React at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder M1. Among them, the amount of Pd(PPh3)4 added is 1mol% of fenthiocarb.

[0113] Add 100mmol of 4-chlorophenylboric acid, 100mmol of M1, 41.4g of potassium carbonate (300mmol), 800ml of tetrahydrofuran (THF) and 200ml of water to a reaction flask, and add 1mol% of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4). React at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder M2. Among them, the amount of Pd(PPh3)4 added is 1mol% of M1.

[0114] Add 100mmol of M2, 110mmol of bipyraclostrobin, 29.4g of potassium acetate (300mmol), 800ml of dioxane, and 1mol% of dichloro[1,1'-di(diphenylphosphino)ferrocene]palladium (Pd(dppf)Cl2) into a reaction flask. React at 100°C for 12h. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, separate the organic phase, concentrate to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder M3. Among them, the amount of Pd(dppf)Cl2 added is 1mol% of M2.

[0115] Add 100mmol of 2,6-dichlorobenzoxazole, 100mmol of phenylboric acid, 41.4g of potassium carbonate (300mmol), 800ml of tetrahydrofuran (THF) and 200ml of water to the reaction flask, and add 1mol% of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4). React at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder M4. Among them, the amount of Pd(PPh3)4 added is 1mol% of 2,6-dichlorobenzoxazole.

[0116] Add 100mmol of M3, 100mmol of M4, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water to a reaction flask, and add 1mol% of Pd(PPh3)4. React at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder A1. Among them, the amount of Pd(PPh3)4 added is 1mol% of M3.

[0117] 1 H NMR(400MHz,Chloroform)δ9.08(s,1H),8.84(s,1H),8.30(s,1H),8.24(d,J=12.4Hz,2 H),8.18(d,J=8.0Hz,2H),7.87–7.80(m,5H),7.75(d,J=10.0Hz,4H),7.68–7.50(m,6H).

[0118] Synthesis of compound A4:

[0119]

[0120] Add 100mmol of 9,9-dimethylfluorene-2-boric acid, 100mmol of 2,4-dichloro-6-phenylpyrimidine, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water to the reaction bottle, and add 1mol% of Pd(PPh3)4. React at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder M1. Among them, the amount of Pd(PPh3)4 added is 1mol% of 2,4-dichloro-6-phenylpyrimidine.

[0121] Add 100mmol of 4-chlorophenylboric acid, 100mmol of M1, 41.4g of potassium carbonate (300mmol), 800ml of tetrahydrofuran (THF) and 200ml of water to a reaction flask, and add 1mol% of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4). React at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder M2. Among them, the amount of Pd(PPh3)4 added is 1mol% of M1.

[0122] Add 100mmol of M2, 110mmol of bipyraclostrobin, 29.4g of potassium acetate (300mmol), 800ml of dioxane, and 1mol% of dichloro[1,1'-di(diphenylphosphino)ferrocene]palladium (Pd(dppf)Cl2) into a reaction flask. React at 100°C for 12h. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, separate the organic phase, concentrate to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder M3. Among them, the amount of Pd(dppf)Cl2 added is 1mol% of M2.

[0123] Add 100mmol of 2,6-dichlorobenzoxazole, 100mmol of phenylboric acid, 41.4g of potassium carbonate (300mmol), 800ml of tetrahydrofuran (THF) and 200ml of water to the reaction flask, and add 1mol% of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4). React at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder M4. Among them, the amount of Pd(PPh3)4 added is 1mol% of 2,6-dichlorobenzoxazole.

[0124] Add 100 mmol of M3, 100 mmol of M4, 41.4 g of potassium carbonate (300 mmol), 800 ml of THF and 200 ml of water to a reaction flask, and add 1 mol% of Pd(PPh3)4. React at 60°C for 12 hours. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder A4. Among them, the amount of Pd(PPh3)4 added is 1 mol% of M3.

[0125] 1 H NMR(400MHz,Chloroform)δ8.18(s,1H),8.11(d,J=8.8Hz,2H),7.98–7.86(m,5H),7.83–7.75(m, 3H),7.72–7.57(m,4H),7.55-7.49(m,3H),7.38(d,J=7.2Hz,4H),7.33–7.26(m,3H),1.69(s,6H).

[0126] Synthesis of compound A6:

[0127]

[0128] Add 100mmol of 3-pyridineboronic acid, 100mmol of p-bromoiodobenzene, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water to a reaction flask, and add 1mol% of Pd(PPh3)4. React at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder M1. Among them, the amount of Pd(PPh3)4 added is 1mol% of 3-pyridineboronic acid.

[0129] Add 100mmol of M1, 110mmol of bipyralidinol borate, 29.4g of potassium acetate (300mmol), 800ml of dioxane, and 1mol% of dichloro[1,1'-di(diphenylphosphino)ferrocene]palladium (Pd(dppf)Cl2) into a reaction flask. React at 100℃ for 12h. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, separate the organic phase, concentrate to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder M2. Among them, the amount of Pd(dppf)Cl2 added is 1mol% of M1.

[0130] Add 100mmol of 2,4-dichloro-6-phenyltriazine, 100mmol of M2, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water to the reaction flask, and add 1mol% of Pd(PPh3)4. React at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder M3. Among them, the amount of Pd(PPh3)4 added is 1mol% of 2,4-dichloro-6-phenyltriazine.

[0131] Add 100mmol of 4-chlorophenylboric acid, 100mmol of M3, 41.4g of potassium carbonate (300mmol), 800ml of tetrahydrofuran (THF) and 200ml of water to a reaction flask, and add 1mol% of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4). React at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder M4. Among them, the amount of Pd(PPh3)4 added is 3mol% of M3.

[0132] Add 100mmol of M4, 110mmol of bipyraclostrobin, 29.4g of potassium acetate (300mmol), 800ml of dioxane, and 1mol% of dichloro[1,1'-di(diphenylphosphino)ferrocene]palladium (Pd(dppf)Cl2) into a reaction flask. React at 100℃ for 12h. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, separate the organic phase, concentrate to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder M5. Among them, the amount of Pd(dppf)Cl2 added is 1mol% of M4.

[0133] Add 100mmol of 2,6-dichlorobenzoxazole, 100mmol of 3-pyridineboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of tetrahydrofuran (THF) and 200ml of water to the reaction flask, and add 1mol% of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4). React at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder M6. Among them, the amount of Pd(PPh3)4 added is 1mol% of 2,6-dichlorobenzoxazole.

[0134] Add 100 mmol of M5, 100 mmol of M6, 41.4 g of potassium carbonate (300 mmol), 800 ml of THF and 200 ml of water to a reaction flask, and add 1 mol% of Pd(PPh3)4. React at 60°C for 12 hours. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder A6. Among them, the amount of Pd(PPh3)4 added is 1 mol% of M5.

[0135] 1 H NMR(400MHz,Chloroform)δ9.24(s,1H),8.72(d,J=10.0Hz,2H),8.34(d,J=10.0Hz,2H),7.96(s ,1H),7.88(d,J=10.4Hz,4H),7.79(d,J=8.0Hz,4H),7.48(d,J=12.0Hz,4H),7.43-7.25(m,6H).

[0136] Synthesis of compound A10:

[0137]

[0138] Add 100mmol of p-tert-butylphenylboronic acid, 100mmol of 2,4-dichloro-6-phenyltriazine, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water to the reaction flask, and add 1mol% of Pd(PPh3)4. React at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder M1. Among them, the amount of Pd(PPh3)4 added is 1mol% of 2,4-dichloro-6-phenyltriazine.

[0139] Add 100mmol of 4-chlorophenylboric acid, 100mmol of M1, 41.4g of potassium carbonate (300mmol), 800ml of tetrahydrofuran (THF) and 200ml of water to a reaction flask, and add 1mol% of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4). React at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder M2. Among them, the amount of Pd(PPh3)4 added is 1mol% of M1.

[0140] Add 100mmol of M2, 110mmol of bipyraclostrobin, 29.4g of potassium acetate (300mmol), 800ml of dioxane, and 1mol% of dichloro[1,1'-di(diphenylphosphino)ferrocene]palladium (Pd(dppf)Cl2) into a reaction flask. React at 100°C for 12h. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, separate the organic phase, concentrate to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder M3. Among them, the amount of Pd(dppf)Cl2 added is 1mol% of M2.

[0141] Add 100mmol of 2,6-dichlorobenzoxazole, 100mmol of 9,9-dimethylfluorene-2-boric acid, 41.4g of potassium carbonate (300mmol), 800ml of tetrahydrofuran (THF) and 200ml of water to the reaction bottle, and add 1mol% of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4). React at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder M4. Among them, the amount of Pd(PPh3)4 added is 1mol% of 2,6-dichlorobenzoxazole.

[0142] Add 100mmol of M3, 100mmol of M4, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water to a reaction flask, and add 1mol% of Pd(PPh3)4. React at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder A10. Among them, the amount of Pd(PPh3)4 added is 1mol% of M3.

[0143] 1 H NMR(400MHz,Chloroform)δ8.42(d,J=8.0Hz,2H),8.19–7.94(m,3H),7.84–7.75(m,6H),7 .58-7.50(m,4H),7.36(d,J=7.6Hz,4H),7.25(d,J=7.6Hz,4H),1.69(s,6H),1.33(s,9H).

[0144] Synthesis of compound A11:

[0145]

[0146] Add 100mmol of 2-spirobifluoreneboronic acid, 100mmol of 2,4-dichloro-6-phenylpyrimidine, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water to the reaction bottle, and add 1mol% of Pd(PPh3)4. React at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder M1. Among them, the amount of Pd(PPh3)4 added is 1mol% of 2,4-dichloro-6-phenylpyrimidine.

[0147] Add 100mmol of 4-chlorophenylboric acid, 100mmol of M1, 41.4g of potassium carbonate (300mmol), 800ml of tetrahydrofuran (THF) and 200ml of water to a reaction flask, and add 1mol% of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4). React at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder M2. Among them, the amount of Pd(PPh3)4 added is 1mol% of M1.

[0148] Add 100mmol of M2, 110mmol of bipyraclostrobin, 29.4g of potassium acetate (300mmol), 800ml of dioxane, and 1mol% of dichloro[1,1'-di(diphenylphosphino)ferrocene]palladium (Pd(dppf)Cl2) into a reaction flask. React at 100°C for 12h. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, separate the organic phase, concentrate to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder M3. Among them, the amount of Pd(dppf)Cl2 added is 1mol% of M2.

[0149] Add 100mmol of 2,6-dichlorobenzoxazole, 100mmol of phenylboric acid, 41.4g of potassium carbonate (300mmol), 800ml of tetrahydrofuran (THF) and 200ml of water to the reaction flask, and add 1mol% of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4). React at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder M4. Among them, the amount of Pd(PPh3)4 added is 1mol% of 2,6-dichlorobenzoxazole.

[0150] Add 100 mmol of M3, 100 mmol of M4, 41.4 g of potassium carbonate (300 mmol), 800 ml of THF and 200 ml of water to a reaction flask, and add 1 mol% of Pd(PPh3)4. React at 60°C for 12 hours. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder A11. Among them, the amount of Pd(PPh3)4 added is 1 mol% of M3.

[0151] 1 H NMR(400MHz,Chloroform)δ8.23(s,1H),8.21–8.04(m,3H),7.98(s,1H),7.95–7.89(m,5H),7. 84(d,J=7.6Hz,6H),7.75–7.68(m,5H),7.65–7.47(m,7H),7.34(s,1H),7.24(t,J=7.2Hz,4H).

[0152] Synthesis of compound A13:

[0153]

[0154] Add 100mmol of 2,6-dichlorobenzoxazole, 100mmol of phenylboric acid, 41.4g of potassium carbonate (300mmol), 800ml of tetrahydrofuran (THF) and 200ml of water to the reaction flask, and add 1mol% of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4). React at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder M1. Among them, the amount of Pd(PPh3)4 added is 1mol% of 2,6-dichlorobenzoxazole.

[0155] Add 100mmol of 1-bromo-4-naphthaleneboric acid, 100mmol of M1, 41.4g of potassium carbonate (300mmol), 800ml of tetrahydrofuran (THF) and 200ml of water to a reaction flask, and add 1mol% of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4). React at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder M2. Among them, the amount of Pd(PPh3)4 added is 1mol% of 1-bromo-4-naphthaleneboric acid.

[0156] Add 100mmol of M2, 110mmol of bipyraclostrobin, 29.4g of potassium acetate (300mmol), 800ml of dioxane, and 1mol% of dichloro[1,1'-di(diphenylphosphino)ferrocene]palladium (Pd(dppf)Cl2) into a reaction flask. React at 100°C for 12h. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, separate the organic phase, concentrate to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder M3. Among them, the amount of Pd(dppf)Cl2 added is 1mol% of M2.

[0157] Add 100mmol of M3, 100mmol of 4,6-diphenyl-2-chlorotriazine, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water to the reaction flask, and add 1mol% of Pd(PPh3)4. React at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder A13. Among them, the amount of Pd(PPh3)4 added is 1mol% of M3.

[0158] 1H NMR (400MHz, Chloroform) δ8.95(s,1H),8.36(s,2H),7.84–7.75(m,6H),7.72–7.56(m,6H),7.50-7.40(m,4H),7.34-7.16(m,5H).

[0159] Synthesis of compound A15:

[0160]

[0161] Add 100mmol of 2,6-dichlorobenzoxazole, 100mmol of phenylboric acid, 41.4g of potassium carbonate (300mmol), 800ml of tetrahydrofuran (THF) and 200ml of water to the reaction flask, and add 1mol% of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4). React at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder M1. Among them, the amount of Pd(PPh3)4 added is 1mol% of 2,6-dichlorobenzoxazole.

[0162] Add 100mmol of M1, 110mmol of bipyralidinol borate, 29.4g of potassium acetate (300mmol), 800ml of dioxane, and 1mol% of dichloro[1,1'-di(diphenylphosphino)ferrocene]palladium (Pd(dppf)Cl2) into a reaction flask. React at 100℃ for 12h. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, separate the organic phase, concentrate to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder M2. Among them, the amount of Pd(dppf)Cl2 added is 1mol% of M1.

[0163] Add 100mmol of 1-bromo-4-chlorodibenzofuran, 100mmol of M2, 41.4g of potassium carbonate (300mmol), 800ml of tetrahydrofuran (THF) and 200ml of water to a reaction flask, and add 1mol% of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4). React at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder M3. Among them, the amount of Pd(PPh3)4 added is 1mol% of 1-bromo-4-chlorodibenzofuran.

[0164] Add 100mmol of M3, 110mmol of bipyraclostrobin, 29.4g of potassium acetate (300mmol), 800ml of dioxane, and 1mol% of dichloro[1,1'-di(diphenylphosphino)ferrocene]palladium (Pd(dppf)Cl2) into a reaction flask. React at 100°C for 12h. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, separate the organic phase, concentrate to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder M4. Among them, the amount of Pd(dppf)Cl2 added is 1mol% of M3.

[0165] Add 100mmol of 2-bromotriphenylene, 110mmol of bipyraclostrobin, 29.4g of potassium acetate (300mmol), 800ml of dioxane, and 1mol% of dichloro[1,1'-di(diphenylphosphino)ferrocene]palladium (Pd(dppf)Cl2) to the reaction flask. React at 100℃ for 12h. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, separate the organic phase, concentrate to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder M5. Among them, the amount of Pd(dppf)Cl2 added is 1mol% of 2-bromotriphenylene.

[0166] Add 100mmol of 2,4-dichloro-6-phenyltriazine, 100mmol of M5, 41.4g of potassium carbonate (300mmol), 800ml of tetrahydrofuran (THF) and 200ml of water to the reaction flask, and add 1mol% of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4). React at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder M6. Among them, the amount of Pd(PPh3)4 added is 1mol% of 2,4-dichloro-6-phenyltriazine.

[0167] Add 100mmol of M4, 100mmol of M6, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water to a reaction flask, and add 1mol% of Pd(PPh3)4. React at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder A15. Among them, the amount of Pd(PPh3)4 added is 1mol% of M4.

[0168] 1H NMR(400MHz,Chloroform)δ9.40(s,1H),8.38–8.23(m,3H),8.15–8.03(m,4H),7.98-7.9 0(m,4H),7.85–7.74(m,5H),7.64(t,J=7.6Hz,4H),7.56–7.43(m,6H),7.39-7.31(m,3H).

[0169] Synthesis of compound A16:

[0170]

[0171] Add 100mmol of 3-bromo-5-chloroiodobenzene, 100mmol of phenylboric acid, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water to a reaction flask, and add 1mol% of Pd(PPh3)4. React at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder M1. Among them, the amount of Pd(PPh3)4 added is 1mol% of 3-bromo-5-chloroiodobenzene.

[0172] Add 100mmol of M1, 110mmol of bipyralidinol borate, 29.4g of potassium acetate (300mmol), 800ml of dioxane, and 1mol% of dichloro[1,1'-di(diphenylphosphino)ferrocene]palladium (Pd(dppf)Cl2) into a reaction flask. React at 100℃ for 12h. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, separate the organic phase, concentrate to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder M2. Among them, the amount of Pd(dppf)Cl2 added is 1mol% of M1.

[0173] Add 100mmol of 2,6-dichlorobenzoxazole, 100mmol of 4-pyridineboric acid, 41.4g of potassium carbonate (300mmol), 800ml of tetrahydrofuran (THF) and 200ml of water to the reaction bottle, and add 1mol% of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4). React at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder M3. Among them, the amount of Pd(PPh3)4 added is 1mol% of 2,6-dichlorobenzoxazole.

[0174] Add 100mmol of M2, 100mmol of M3, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water to the reaction flask, and add 1mol% of Pd(PPh3)4. React at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder M4. Among them, the amount of Pd(PPh3)4 added is 1mol% of M2.

[0175] Add 100mmol of M4, 110mmol of bipyraclostrobin, 29.4g of potassium acetate (300mmol), 800ml of dioxane, and 1mol% of dichloro[1,1'-di(diphenylphosphino)ferrocene]palladium (Pd(dppf)Cl2) into a reaction flask. React at 100℃ for 12h. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, separate the organic phase, concentrate to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder M5. Among them, the amount of Pd(dppf)Cl2 added is 1mol% of M4.

[0176] Add 100mmol of 9-phenanthrene boronic acid, 100mmol of 2,4-dichloro-6-phenylpyrimidine, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water to the reaction bottle, and add 1mol% of Pd(PPh3)4. React at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder M6. Among them, the amount of Pd(PPh3)4 added is 1mol% of fenthiocarb.

[0177] Add 100 mmol of M5, 100 mmol of M6, 41.4 g of potassium carbonate (300 mmol), 800 ml of THF and 200 ml of water to a reaction flask, and add 1 mol% of Pd(PPh3)4. React at 60°C for 12 hours. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder A16. Among them, the amount of Pd(PPh3)4 added is 1 mol% of M5.

[0178] 1H NMR(400MHz,Chloroform)δ9.08(s,1H),8.84(s,1H),8.34(t,J=7.6Hz,3H),8.22(d,J=6.8Hz,2H),8 .17(s,2H),7.99(d,J=10.0Hz,4H),7.69(d,J=8.8Hz,4H),7.60(t,J=10.0Hz,6H),7.43–7.32(m,7H).

[0179] Synthesis of compound A22:

[0180]

[0181] Add 100mmol of 2,6-dimethylbenzeneboronic acid, 100mmol of 2,4-dichloro-6-phenyltriazine, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water to the reaction bottle, and add 1mol% of Pd(PPh3)4. React at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder M1. Among them, the amount of Pd(PPh3)4 added is 1mol% of 2,4-dichloro-6-phenyltriazine.

[0182] Add 100mmol of 4-chlorophenylboric acid, 100mmol of M1, 41.4g of potassium carbonate (300mmol), 800ml of tetrahydrofuran (THF) and 200ml of water to a reaction flask, and add 1mol% of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4). React at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder M2. Among them, the amount of Pd(PPh3)4 added is 1mol% of M1.

[0183] Add 100mmol of M2, 110mmol of bipyraclostrobin, 29.4g of potassium acetate (300mmol), 800ml of dioxane, and 1mol% of dichloro[1,1'-di(diphenylphosphino)ferrocene]palladium (Pd(dppf)Cl2) into a reaction flask. React at 100°C for 12h. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, separate the organic phase, concentrate to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder M3. Among them, the amount of Pd(dppf)Cl2 added is 1mol% of M2.

[0184] Add 100mmol of 3-pyridineboronic acid, 100mmol of m-bromoiodobenzene, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water to a reaction flask, and add 1mol% of Pd(PPh3)4. React at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder M4. Among them, the amount of Pd(PPh3)4 added is 1mol% of 3-pyridineboronic acid.

[0185] Add 100mmol of M4, 110mmol of bipyraclostrobin, 29.4g of potassium acetate (300mmol), 800ml of dioxane, and 1mol% of dichloro[1,1'-di(diphenylphosphino)ferrocene]palladium (Pd(dppf)Cl2) into a reaction flask. React at 100℃ for 12h. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, separate the organic phase, concentrate to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder M5. Among them, the amount of Pd(dppf)Cl2 added is 1mol% of M4.

[0186] Add 100mmol of 2,6-dichlorobenzoxazole, 100mmol of M5, 41.4g of potassium carbonate (300mmol), 800ml of tetrahydrofuran (THF) and 200ml of water to the reaction flask, and add 1mol% of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4). React at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder M6. Among them, the amount of Pd(PPh3)4 added is 1mol% of 2,6-dichlorobenzoxazole.

[0187] Add 100mmol of M3, 100mmol of M6, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water to a reaction flask, and add 1mol% of Pd(PPh3)4. React at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder A22. Among them, the amount of Pd(PPh3)4 added is 1mol% of M3.

[0188] 1H NMR(400MHz,Chloroform)δ9.24(s,1H),8.70(s,1H),8.34(d,J=12.0Hz,3H),8.16(d,J=11.2Hz,2H),7.87 (s,1H),7.79(d,J=10.0Hz,2H),7.70-7.61(m,4H),7.52(d,J=8.0Hz,3H),7.40–7.22(m,6H),2.58(s,6H).

[0189] Synthesis of compound A23:

[0190]

[0191] Add 100mmol of 3-dibenzothiophene boronic acid, 100mmol of 2,4-dichloro-6-phenyltriazine, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water to the reaction flask, and add 1mol% of Pd(PPh3)4. React at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder M1. Among them, the amount of Pd(PPh3)4 added is 1mol% of 2,4-dichloro-6-phenyltriazine.

[0192] Add 100mmol of 1-bromo-4-naphthaleneboric acid, 100mmol of M1, 41.4g of potassium carbonate (300mmol), 800ml of tetrahydrofuran (THF) and 200ml of water to a reaction flask, and add 1mol% of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4). React at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder M2. Among them, the amount of Pd(PPh3)4 added is 1mol% of 1-bromo-4-naphthaleneboric acid.

[0193] Add 100mmol of M2, 100mmol of p-chlorophenylboric acid, 41.4g of potassium carbonate (300mmol), 800ml of tetrahydrofuran (THF) and 200ml of water to a reaction flask, and add 1mol% of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4). React at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder M3. Among them, the amount of Pd(PPh3)4 added is 1mol% of M2.

[0194] Add 100mmol of M3, 110mmol of bipyraclostrobin, 29.4g of potassium acetate (300mmol), 800ml of dioxane, and 1mol% of dichloro[1,1'-di(diphenylphosphino)ferrocene]palladium (Pd(dppf)Cl2) into a reaction flask. React at 100°C for 12h. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, separate the organic phase, concentrate to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder M4. Among them, the amount of Pd(dppf)Cl2 added is 1mol% of M3.

[0195] Add 100mmol of 2,6-dichlorobenzoxazole, 100mmol of phenylboric acid, 41.4g of potassium carbonate (300mmol), 800ml of tetrahydrofuran (THF) and 200ml of water to the reaction flask, and add 1mol% of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4). React at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder M5. Among them, the amount of Pd(PPh3)4 added is 1mol% of 2,6-dichlorobenzoxazole.

[0196] Add 100 mmol of M4, 100 mmol of M5, 41.4 g of potassium carbonate (300 mmol), 800 ml of THF and 200 ml of water to a reaction flask, and add 1 mol% of Pd(PPh3)4. React at 60°C for 12 hours. After the reaction is completed, stop the reaction, cool the reactants to room temperature, add water, concentrate the organic phase to obtain a white solid, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain a white powder A23. Among them, the amount of Pd(PPh3)4 added is 1 mol% of M4.

[0197] 1 H NMR(400MHz,Chloroform)δ9.00(s,1H),8.95-8.76(m,4H),8.36-8.18(m,4H),7.98(d,J=1 0.0Hz,2H),7.88–7.75(m,3H),7.72–7.60(m,7H),7.56-7.40(m,5H),7.33(d,J=8.0Hz,4H).

[0198] Example 1

[0199] The glass plate coated with the 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 to completely remove the water, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam;

[0200] Then, the glass substrate with the anode is placed in a vacuum chamber and evacuated to less than 10 -5 A hole injection layer is vacuum-deposited on the anode layer film. The hole injection layer material is a hole transport material HT-11 and a p-type dopant (p-1) with a mass ratio of 3%. The evaporation rate is 0.1 nm / s, the evaporation film thickness is 10 nm, and the materials of the hole injection layer HT-11 and the p-type dopant are:

[0201]

[0202] Then, a hole transport material HT-5 material is vacuum evaporated on the hole injection layer as a hole transport layer, wherein the evaporation rate is 0.1 nm / s, the evaporation film thickness is 80 nm, and the material of the hole transport layer is:

[0203]

[0204] Then, a light-emitting layer is vacuum-deposited on the hole transport layer. The light-emitting layer includes a main material GHP-16 and a guest material RPD-1. The evaporation is performed by a multi-source co-evaporation method. The evaporation rate of the main material GHP-16 is adjusted to 0.1 nm / s, and the evaporation rate of the guest material RPD-1 is 3% of the evaporation rate of the main material GHP-16. The total evaporation film thickness is 30 nm. The main material and the guest material are respectively the following materials:

[0205]

[0206] Then, an electron transport material A1 is vacuum-deposited on the light-emitting layer as an electron transport layer. The deposition rate is 0.1 nm / s and the deposition film thickness is 30 nm. The selected electron transport material A1 is as follows:

[0207]

[0208] Then, LiF with a thickness of 0.5 nm was vacuum-deposited on the electron transport layer as an electron injection layer, wherein the evaporation rate was 0.1 nm / s and the evaporation film thickness was 10 nm;

[0209] Then, an aluminum layer with a thickness of 150 nm was vacuum-evaporated on the electron injection layer as a cathode electrode of the organic electroluminescent device, wherein the evaporation rate was 1 nm / s and the evaporation film thickness was 50 nm.

[0210] The organic electroluminescent device of this embodiment emits red light.

[0211] Example 2-Example 10

[0212] Except that A4, A6, A10, A11, A13, A15, A16, A22, and A23 are used to replace A1, the rest is the same as Example 1. See Table 1 for details.

[0213] Embodiment 11

[0214] The process was the same as Example 1 except that compound GPH-44 was used instead of GHP-16 and compound GD04 was used instead of RPD-1.

[0215] The organic electroluminescent device of this embodiment emits green light.

[0216] Example 12

[0217] The process was the same as Example 1 except that compound BH-1 was used instead of GHP-16 and compound BD01 was used instead of RPD-1.

[0218] The organic electroluminescent device of this embodiment emits blue light.

[0219] Comparative Example 1

[0220] Except for replacing A1 with ET-2, the rest is the same as Example 1.

[0221]

[0222] Comparative Example 2

[0223] Except for using R-1 instead of A1, the rest is the same as Example 1.

[0224]

[0225] Comparative Example 3

[0226] The process was the same as Example 11 except that compound ET-2 was used instead of A1.

[0227] Comparative Example 4

[0228] The process was the same as Example 12 except that compound ET-2 was used instead of A1.

[0229] Organic electroluminescent device performance test method:

[0230] At the same brightness, the driving voltage, current efficiency and device life of the organic electroluminescent devices prepared in Examples 1 to 12 and Comparative Examples 1 to 4 were measured using a digital source meter and a brightness meter, as follows:

[0231] <Measurement of Driving Voltage and Current Efficiency>

[0232] (1) Red light device: Increase the voltage at a rate of 0.1 V per second, and measure the voltage (i.e., the driving voltage) when the brightness of the organic electroluminescent device reaches 5000 cd / m 2 At the same time, measure the current density at this time; the ratio of brightness to current density is the current efficiency.

[0233] (2) Green light device: Increase the voltage at a rate of 0.1 V per second, and measure the voltage (i.e., the driving voltage) when the brightness of the organic electroluminescent device reaches 10000 cd / m 2 At the same time, measure the current density at this time; the ratio of brightness to current density is the current efficiency.

[0234] (3) Blue light device: Increase the voltage at a rate of 0.1 V per second, and measure the voltage (i.e., the driving voltage) when the brightness of the organic electroluminescent device reaches 1000 cd / m 2 At the same time, measure the current density at this time; the ratio of brightness to current density is the current efficiency.

[0235] <LT95 Lifetime Test>

[0236] (1) Red light device: Use a luminance meter to keep a constant current at a brightness of 5000 cd / m 2 Measure the time (in hours) when the brightness of the organic electroluminescent device drops to 4750 cd / m 2 .

[0237] (2) Green light device: Use a luminance meter to keep a constant current at a brightness of 10000 cd / m 2 Measure the time (in hours) when the brightness of the organic electroluminescent device drops to 9500 cd / m 2 .

[0238] (3) Blue light device: Use a luminance meter to keep a constant current at a brightness of 1000 cd / m 2 Measure the time (in hours) when the brightness of the organic electroluminescent device drops to 950 cd / m 2 .

[0239] Table 1 Performance Results of Organic Electroluminescent Devices

[0240]

[0241]

[0242] From the data in Table 1, it can be seen that in Examples 1 to 12, the compounds A1, A4, A6, A10, A11, A13, A15, A16, A22, and A23 provided by the present application are used as electron transport materials for organic electroluminescent devices. Compared with the known materials in the prior art used as electron transport materials for organic electroluminescent devices in Comparative Examples 1 to Comparative Examples 4, at the same brightness, the driving voltage of red, green, and blue light-emitting devices can be lower, the luminous efficiency is higher, and the LT95 life is longer. This shows that using the compounds of the present application as electron transport materials for organic electroluminescent devices can effectively reduce the driving voltage of organic electroluminescent devices, improve their luminous efficiency, and extend their service life, and is an electron transport material with good performance.

[0243] The above description is only a preferred embodiment of the present application and is not intended to limit the protection scope of the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application are included in the protection scope of the present application.

Claims

1. A compound selected from the following compounds: 2 . An electron transport material comprising at least one of the compounds according to claim 1 . 3 . An organic electroluminescent device comprising at least one of the electron transport materials according to claim 2 .

4. A display device comprising the organic electroluminescent device according to claim 3.

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