A compound containing a naphthyl-substituted naphthylamine fragment and uses thereof

Abstract

The application provides a compound of formula (I), the bond energy between atoms is high, the compound has good thermal stability, and the solid-state stacking between molecules is favorable, and the energy level between adjacent layers is suitable, which is favorable for the injection and migration of excitons. When used as an electron transport material, the compound can effectively reduce the driving voltage of an organic electroluminescent device, improve the light-emitting efficiency of the organic electroluminescent device, and prolong the service life of the organic electroluminescent device. The application also provides an organic electroluminescent device and a display device comprising the compound of formula (I).

Description

Technical Field

[0001] This application relates to the field of organic light-emitting display technology, and in particular to a compound containing a naphthyl-substituted electron-withdrawing fragment and its applications. Background Technology

[0002] Electroluminescence (EL) refers to the phenomenon where a luminescent material emits light when excited by an electric field and subjected to current and voltage. It is a process that directly converts electrical energy into light energy. Organic electroluminescent displays (OLEDs) possess a series of advantages, including self-illumination, low-voltage DC drive, all-solid-state operation, wide viewing angle, light weight, and simple composition and manufacturing process. Compared to liquid crystal displays (LCDs), OLEDs do not require a backlight, have a wider viewing angle, lower power consumption, and a response speed up to 1000 times faster than LCDs, while their manufacturing cost is lower than that of LCDs with equivalent resolution. Therefore, organic electroluminescent devices have a very broad application prospect.

[0003] With the continuous advancement of OLED technology in the fields of lighting and display, people are paying more attention to the research of high-efficiency organic materials that affect the performance of OLED devices. An efficient and long-life organic electroluminescent device is usually the result of the optimized combination of device structure and various organic materials, which provides chemists with great opportunities and challenges to design and develop functional materials with various structures.

[0004] Compared to inorganic light-emitting materials, organic electroluminescent materials have many advantages, such as: good processability (they can be deposited on any substrate through evaporation or spin coating), the ability to achieve flexible and large-area displays, and the ability to adjust the optical, electrical, and stability properties of the materials by modifying their molecular structure, offering a wide range of material choices. The most common OLED device structures typically include the following types of organic materials: hole injection materials, hole transport materials, electron transport materials, and light-emitting materials (including host and guest materials). Currently, electron transport materials, as an important functional material, directly affect electron mobility and ultimately the luminous efficiency of OLEDs. However, currently commercially available electron transport materials suffer from low mobility, therefore, materials with higher mobility need to be developed. Summary of the Invention

[0005] The purpose of this application is to provide a compound that, when used as an electron transport material, can improve the working efficiency and extend the lifespan of organic electroluminescent devices.

[0006] The first aspect of this application provides a compound of formula (I):

[0007]

[0008]

[0009] in,

[0010] Ar 1 and Ar 2 Each is independently selected from unsubstituted or Rc-substituted C6-C. 30 Aryl, unsubstituted or Rc-substituted C3-C 30 heteroaryl; Ar 1 and Ar 2 At least one of them has at least 10 C atoms, and at least one is selected from unsubstituted or Rc-substituted C6-C atoms. 30 Aryl;

[0011] X 1 -X 3 Each is independently selected from C or N, and at least two are selected from N;

[0012] R 1 and R 2 Each is independently selected from hydrogen, deuterium, unsubstituted or Rc-substituted C6-C. 30 Aryl, unsubstituted or Rc-substituted C3-C 30 Mixed aromatics;

[0013] L is selected from chemical bonds, unsubstituted or Rc-substituted C6-C. 30 aryl, unsubstituted or Rc-substituted C3-C 30 heteroaryl;

[0014] The heteroatoms on the heteroaryl group or the heteroalkylene group are each independently selected from O, S or N;

[0015] The substituents Rc of each group are independently selected from deuterium, halogen, nitro, cyano, C1-C4 alkyl, phenyl, biphenyl, terphenyl or naphthyl.

[0016] A second aspect of this application provides an electron transport material comprising at least one of the compounds provided in the first aspect of this application.

[0017] A third aspect of this application provides an organic electroluminescent device comprising at least one of the electron transport materials provided in the second aspect of this application.

[0018] A fourth aspect of this application provides a display device that includes the organic electroluminescent device provided in the third aspect of this application.

[0019] The compounds provided in this application have a parent structure with naphthyl-substituted electron-withdrawing fragments, high interatomic bond energies, good thermal stability, and are conducive to solid-state molecular stacking. When used as electron transport materials, they exhibit suitable energy level levels with adjacent layers, facilitating exciton injection and migration, effectively reducing the driving voltage, and possessing high electron mobility, enabling good luminous efficiency and lifespan in organic electroluminescent devices. The compounds in this application also possess large conjugated planes, which are beneficial for molecular stacking and exhibit good thermodynamic stability, resulting in long lifetimes in devices. Organic electroluminescent devices comprising these compounds as electron transport materials can effectively reduce driving voltage, improve luminous efficiency, and extend the lifespan of organic electroluminescent devices. The display devices provided in this application have excellent display effects.

[0020] Of course, implementing any product or method of this application does not necessarily require achieving all of the advantages described above at the same time. Attached Figure Description

[0021] To more clearly illustrate the technical solutions in this application or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other embodiments can be obtained based on these drawings.

[0022] Figure 1 This is a schematic diagram of a typical organic electroluminescent device. Detailed Implementation

[0023] The technical solutions of this application will now be clearly and completely described with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art based on this application are within the scope of protection of this application.

[0024] The first aspect of this application provides a compound of formula (I):

[0025]

[0026] in,

[0027] Ar 1 and Ar 2 Each is independently selected from unsubstituted or Rc-substituted C6-C. 30 Aryl, unsubstituted or Rc-substituted C3-C 30 heteroaryl; Ar 1 and Ar 2At least one of them has at least 10 C atoms, and Ar 1 and Ar 2 At least one of them is selected from unsubstituted or Rc-substituted C6-C. 30 Aryl;

[0028] X 1 -X 3 Each is independently selected from C or N, and at least two are selected from N;

[0029] R 1 and R 2 Each is independently selected from hydrogen, deuterium, unsubstituted or Rc-substituted C6-C. 30 Aryl, unsubstituted or Rc-substituted C3-C 30 Mixed aromatics;

[0030] L is selected from chemical bonds, unsubstituted or Rc-substituted C6-C. 30 aryl, unsubstituted or Rc-substituted C3-C 30 heteroaryl;

[0031] The heteroatoms on the heteroaryl group or the heteroalkylene group are each independently selected from O, S or N;

[0032] The substituents Rc of each group are independently selected from deuterium, halogen, nitro, cyano, C1-C4 alkyl, phenyl, biphenyl, terphenyl or naphthyl.

[0033] Preferably, R 1 and R 2 Each is independently selected from hydrogen, deuterium, unsubstituted or Rc-substituted C6-C. 18 Aryl, unsubstituted or Rc-substituted C3-C 18 Mixed aromatic compounds.

[0034] Preferably, L is selected from chemically bonded, unsubstituted, or Rc-substituted C6-C bonds. 18 aryl, unsubstituted or Rc-substituted C3-C 18 Hybrid aryl.

[0035] More preferably, the R 1 and R 2 Each of the following groups, independently selected from unsubstituted or Rc-substituted groups, is selected from: hydrogen, deuterium, phenyl, biphenyl, terphenyl, naphthyl, phenanthrene, triphenylene, fluorenyl, pyridinyl, pyridinyl, pyrazinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, cyclolinyl, naphthinyl, triazinyl, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, benzothiophene, dibenzothiophene, aza-dibenzothiophene, 9,9-dimethylfluorenyl, spirofluorenyl.

[0036] More preferably, the Ar 1 and Ar 2 Each of the following groups, independently selected from unsubstituted or Rc-substituted groups, is selected: biphenyl, terphenyl, naphthyl, phenanthrene, triphenylene, fluorenyl, dibenzofuranyl, aza-dibenzofuranyl, thiophene, dibenzothiophene, aza-dibenzothiophene, 9,9-dimethylfluorenyl, spirofluorenyl.

[0037] More preferably, the L is selected from the subunits of the following compounds that are chemically bonded, unsubstituted, or Rc-substituted: benzene, biphenyl, terphenyl, naphthalene, phenanthrene, triphenylene, fluorene, pyridine, pyridazine, pyrimidine, pyrazine, quinoline, isoquinoline, quinazoline, quinoxaline, cyclophosphine, triazine, pyridopyrazine, furan, benzofuran, dibenzofuran, aza-dibenzofuran, benzothiophene, dibenzothiophene, aza-dibenzothiophene, 9,9-dimethylfluorene, and spirofluorene.

[0038] For example, the compounds of formula (I) can be selected from the compounds shown in A1 to A30 below:

[0039]

[0040]

[0041] The compound of formula (I) provided in this application has high interatomic bond energy, good thermal stability, and is conducive to solid-state packing between molecules. Furthermore, the preparation process of the compound of formula (I) provided in this application is simple and easy, the raw materials are readily available, and it is suitable for industrial production.

[0042] A second aspect of this application provides an electron transport material comprising at least one of the compounds provided in the first aspect of this application.

[0043] When the compounds of this application are used as electron transport materials in electron transport layers, they exhibit energy level matching with adjacent layers, which is beneficial for electron injection and migration, and can effectively reduce the driving voltage. They also possess high electron mobility, enabling good luminous efficiency and lifespan in organic electroluminescent devices. Furthermore, the compounds provided in this application have large conjugated planes, which are beneficial for molecular stacking and exhibit good thermodynamic stability, thus extending the lifespan of organic electroluminescent devices.

[0044] A third aspect of this application provides an organic electroluminescent device comprising at least one of the electron transport materials provided in the second aspect of this application. Therefore, the organic electroluminescent device provided by this application has a low driving voltage, high luminous efficiency, and a long lifespan.

[0045] In this application, there are no particular restrictions on the type and structure of organic electroluminescent devices. They can be organic electroluminescent devices of different types and structures known in the art, as long as the electron transport material provided in this application can be used.

[0046] The organic electroluminescent device of this application can be a top-emitting structure, which may include, in order on a substrate, an anode, a hole injection layer, a hole transport layer, an emitting layer, an electron transport layer, an electron injection layer, and a transparent or semi-transparent cathode.

[0047] The organic electroluminescent device of this application can also be a bottom-emitting device, which may include a transparent or semi-transparent anode, a hole injection layer, a hole transport layer, an emitting layer, an electron transport layer, an electron injection layer and a cathode structure sequentially on a substrate.

[0048] The organic electroluminescent device of this application can also be a light-emitting device with a dual-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 sequentially on a substrate.

[0049] Furthermore, the organic electroluminescent device of this application may have an electron blocking layer between the hole transport layer and the light-emitting layer, and a hole blocking layer between the light-emitting layer and the electron transport layer. A light extraction layer may be disposed on the transparent electrode on the light-emitting side. However, the structure of the organic electroluminescent device of this application is not limited to the specific structure described above. If necessary, the above layers may be omitted or added. This application does not impose any particular limitation on the thickness of the above layers, as long as the purpose of this application can be achieved. For example, the organic electroluminescent device may sequentially 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.

[0050] Figure 1 A schematic diagram of a typical organic electroluminescent device is shown, in which, from bottom to top, a substrate 1, a reflective anode electrode 2, a hole injection layer 3, a hole transport layer 4, a light-emitting layer 5, an electron transport layer 6, an electron injection layer 7, and a cathode electrode 8 are arranged sequentially.

[0051] Understandable. Figure 1 The structure of a typical organic electroluminescent device is shown only schematically. This application is not limited to this structure, and the electron transport material of this application can be used in any type of organic electroluminescent device.

[0052] In the organic electroluminescent device of this application, except for the electron transport layer which contains the electron transport material provided in this application, the other layers can use various materials used for the layers in the prior art.

[0053] For convenience, the following references Figure 1 The organic electroluminescent devices described in this application are not intended to limit the scope of protection of this application in any way. It is understood that all organic electroluminescent devices capable of using the electron transport materials of this application are within the scope of protection of this application.

[0054] In this application, the substrate 1 is not particularly limited and can be a conventional substrate used in organic electroluminescent devices in the prior art, such as glass, polymer materials, and glass and polymer materials with thin-film transistor (TFT) components.

[0055] In this application, the reflective anode material 2 is not particularly limited and can be selected from transparent conductive materials known in the prior art such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), and zinc oxide (ZnO), or metallic materials such as silver and its alloys, aluminum and its alloys, or organic conductive materials such as poly(3,4-ethylenedioxythiophene) (PEDOT), or multilayer structures of the above materials.

[0056] In this application, the material of the hole injection layer 3 is not particularly limited, and it can be made of hole injection layer materials known in the art. For example, at least one of the known hole transport materials (HTM) can be selected as the hole injection material.

[0057] In this application, the hole injection layer 3 may further include a p-type dopant. The type of p-type dopant is not particularly limited, and various p-type dopants known in the art can be used. For example, the p-type dopant may be selected from, but is not limited to, at least one of the following p-1 to p-3 compounds:

[0058]

[0059] In this application, the amount of p-type dopant used is not particularly limited and can be any amount known to those skilled in the art.

[0060] In this application, the material of the hole transport layer 4 is not particularly limited and can be made of hole transport materials (HTM) known in the art. 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 it meets the purpose of this application, for example, 1 layer, 2 layers, 3 layers, 4 layers or more.

[0061] For example, HTM for hole injection layer materials and HTM for hole transport layer materials can be selected from, but are not limited to, at least one of the following HT-1 to HT-31 compounds:

[0062]

[0063]

[0064] In this application, the light-emitting layer 5 may include a blue light-emitting layer, a green light-emitting layer, or a red light-emitting layer. There are no particular limitations on the light-emitting material in the light-emitting layer 5, and various light-emitting materials known to those skilled in the art can be used. For example, the material of the light-emitting layer 5 may include a host material and a guest material.

[0065] In this application, the host material may be selected from, but is not limited to, at least one of the following BH-1 to BH-10 compounds:

[0066]

[0067] In this application, the guest material is not particularly limited, and at least one of the luminescent layer guest materials known in the art can be used. For example, the luminescent layer guest material can be selected from, but is not limited to, at least one of the following BD-1 to BD-9 compounds:

[0068]

[0069] In this application, there is no particular limitation on the amount of the luminescent layer guest material, and it can be any amount known to those skilled in the art.

[0070] In this application, the electron transport layer 6 comprises at least one of the electron transport materials of this application, and the electron transport layer 6 may also comprise a combination of at least one of the electron transport materials of this application and at least one of known electron transport materials. The number of electron transport layers 6 is not particularly limited and can be adjusted according to actual needs, as long as it meets the purpose of this application; for example, 1 layer, 2 layers, 3 layers, 4 layers, or more layers.

[0071] For example, it is known that electron transport materials can be selected from, but are not limited to, at least one of the following ET-1 to ET-57 compounds:

[0072]

[0073]

[0074]

[0075]

[0076] In this application, the electron transport layer 6 may further include an n-type dopant. The type of n-type dopant is not particularly limited, and various n-type dopants known in the art can be used, such as the following n-type dopants:

[0077]

[0078] In this application, there is no particular limitation on the amount of the n-type dopant, and it can be any amount known to those skilled in the art.

[0079] In this application, the material of the electron injection layer 7 is not particularly limited, and electron injection materials known in the art can be used, such as at least one of the following materials in the prior art: LiQ, LiF, NaCl, CsF, Li2O, Cs2CO3, BaO, Na, Li, Ca, etc.

[0080] In this application, the material of the cathode electrode 8 is not particularly limited and can be selected from, but is not limited to, magnesium-silver mixtures, LiF / Al, ITO, Al and other metals, metal mixtures, oxides and the like.

[0081] A fourth aspect of this application provides a display device that includes the organic electroluminescent device provided in the third aspect of this application. The display device includes, but is not limited to, a monitor, a television, a tablet computer, a mobile communication terminal, etc.

[0082] There are no particular limitations on the method for preparing the organic electroluminescent device of this application; any method known in the art can be used. For example, this application can be prepared using the following method:

[0083] (1) Clean the reflective anode electrode 2 on the substrate 1 of the top-emitting OLED device. In the cleaning machine, the electrode is cleaned by chemical washing, water washing, brushing, high-pressure water washing, air knife and other steps, and then heated.

[0084] (2) Hole injection material is vacuum-deposited on the reflective anode electrode 2 as a hole injection layer 3;

[0085] (3) Hole transport material is vacuum-deposited on hole injection layer 3 as hole transport layer 4;

[0086] (4) A light-emitting layer 5 is vacuum-deposited on the hole transport layer 4, the light-emitting layer 5 containing a host material and a guest material;

[0087] (5) Electron transport material is vacuum-deposited on the light-emitting layer 5 as electron transport layer 6;

[0088] (6) Vacuum evaporation of electron injection material on electron transport layer 6 to serve as electron injection layer 7;

[0089] (7) Vacuum evaporation of cathode material on electron injection layer 7 to serve as cathode electrode 8.

[0090] The above describes only a typical structure and fabrication method of an organic electroluminescent device. It should be understood that this application is not limited to this structure. The electron transport material of this application can be used in organic electroluminescent devices of any structure, and the organic electroluminescent device can be fabricated using any fabrication method known in the art.

[0091] There are no particular limitations on the synthesis method of the compounds in this application; any method known to those skilled in the art can be used for synthesis. The following examples illustrate the synthesis process of the compounds in this application.

[0092] Synthesis of compound A1:

[0093]

[0094] 100 mmol of 1-naphthoboric acid, 100 mmol of p-bromoiodobenzene, 41.4 g of potassium carbonate (300 mmol), 800 mL of tetrahydrofuran (THF), and 200 mL of water were added to a reaction flask, along with 1 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 60 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder M1. The amount of Pd(PPh3)4 added was 1 mol% of 1-naphthoboric acid.

[0095] Under nitrogen protection, M1 (100 mmol, 1 eq.) and 1 L of tetrahydrofuran were added to a 3 L three-necked flask equipped with a mechanical stirrer and a cryostat. The flask was cooled to -90°C to -80°C with liquid nitrogen, and n-butyllithium (250 mmol, 2.5 eq.) was added dropwise. After the addition was complete, the flask was kept at -90°C to -80°C for 30 min. Then, tri-tert-butyl borate (120 mmol, 1.2 eq.) was added. After the addition was complete, the flask was allowed to cool naturally to 0°C and stirred for 8 hours. After the reaction was complete, 1000 mL of 10 wt% ammonium chloride aqueous solution was added. The mixture was separated, and the organic phase was washed with 300 mL of 10 wt% ammonium chloride aqueous solution each time. The filtrate was concentrated to obtain a black solid, which was then crystallized from toluene to obtain a pale yellow granular solid M2.

[0096] 100 mmol of M2, 100 mmol of 2,4-dichloro-6-phenyl-1,3,5-triazine, 41.4 g of potassium carbonate (300 mmol), 800 mL of tetrahydrofuran (THF), and 200 mL of water were added to a reaction flask, along with 1 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 60 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, M3. The amount of Pd(PPh3)4 added was 1 mol% of M2.

[0097] 100 mmol of M3, 100 mmol of 9,9'-spirodifluorene-2-boric 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, along with 1 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 60 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, Al. The amount of Pd(PPh3)4 added was 1 mol% of M3.

[0098] 1 H NMR(400MHz,Chloroform)8.95(s,1H),8.36-8.19(m,3H),7.96(s,1H),7.89(d,J=8.0Hz,4H),7.78(d,J=8 .0Hz,2H),7.68(s,1H),7.63(d,J=8.0Hz,4H),7.50-7.40(m,4H),7.34(d,J=8.4Hz,5H),7.30–7.19(m,6H).

[0099] Synthesis of compound A3:

[0100]

[0101] 100 mmol of 3-pyridineboronic acid, 100 mmol of 1,4-dibromonaphthalene, 41.4 g of potassium carbonate (300 mmol), 800 mL of tetrahydrofuran (THF), and 200 mL of water were added to a reaction flask, along with 1 mol% tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 60 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder M1. The amount of Pd(PPh3)4 added was 1 mol% of 3-pyridineboronic acid.

[0102] 100 mmol of M1, 100 mmol of p-chlorophenylboronic acid, 41.4 g of potassium carbonate (300 mmol), 800 mL of tetrahydrofuran (THF), and 200 mL of water were added to a reaction flask, along with 1 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 60 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, M2. The amount of Pd(PPh3)4 added was 1 mol% of M1.

[0103] 100 mmol of M2, 100 mmol of pinacol diborate, 41.4 g of potassium carbonate (300 mmol), and 800 mL of xylene were added to a reaction flask, along with 1 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 100 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, M3. The amount of Pd(PPh3)4 added was 1 mol% of M2.

[0104] 100 mmol of M3, 100 mmol of 2-chloro-4-(2-naphthyl)-6-phenyl-1,3,5-triazine, 41.4 g of potassium carbonate (300 mmol), 800 mL of tetrahydrofuran (THF), and 200 mL of water were added to a reaction flask, along with 1 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 60 °C for 12 h. After the reaction was completed, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder A3. The amount of Pd(PPh3)4 added was 1 mol% of M3.

[0105] 1 H NMR(400MHz,Chloroform)9.09(s,1H),8.95-8.70(m,3H),8.65–8.23(m,5H),7.96(d,J=10. 0Hz,4H),7.65(t,J=8.8Hz,4H),7.57(s,1H),7.57(d,J=8.0Hz,4H),7.48(d,J=11.2Hz,4H).

[0106] Synthesis of compound A5:

[0107]

[0108] 100 mmol of phenylboronic acid, 100 mmol of 1,4-dibromonaphthalene, 41.4 g of potassium carbonate (300 mmol), 800 mL of tetrahydrofuran (THF), and 200 mL of water were added to a reaction flask, along with 1 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 60 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder M1. The amount of Pd(PPh3)4 added was 1 mol% of 3-pyridineboronic acid.

[0109] Under nitrogen protection, M1 (100 mmol, 1 eq.) and 1 L of tetrahydrofuran were added to a 3 L three-necked flask equipped with a mechanical stirrer and a cryostat. The flask was cooled to -90°C to -80°C with liquid nitrogen, and n-butyllithium (120 mmol, 1.2 eq.) was added dropwise. After the addition was complete, the flask was kept at -90°C to -80°C for 30 min. Then, tri-tert-butyl borate (120 mmol, 1.2 eq.) was added. After the addition was complete, the flask was allowed to rise naturally to 0°C and stirred for 8 hours. After the reaction was complete, 1000 mL of 10 wt% ammonium chloride aqueous solution was added. The mixture was separated, and the organic phase was washed with 300 mL of 10 wt% ammonium chloride aqueous solution each time. The filtrate was concentrated to obtain a black solid, which was then crystallized from toluene to obtain a pale yellow granular solid M2.

[0110] 100 mmol of M2, 100 mmol of 2,4-dichloro-6-phenyl-1,3,5-triazine, 41.4 g of potassium carbonate (300 mmol), 800 mL of tetrahydrofuran (THF), and 200 mL of water were added to a reaction flask, along with 1 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 60 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder A5. The amount of Pd(PPh3)4 added was 1 mol% of M2.

[0111] 1 H NMR (400MHz, Chloroform) δ9.00 (s, 1H), 8.95 (s, 2H), 7.78 (d, J = 8.0Hz, 4H), 7.66- 7.53(m,6H),7.44(d,J=10.0Hz,4H),7.40(d,J=8.0Hz,4H),7.40(d,J=12.4Hz,6H).

[0112] Synthesis of compound A6:

[0113]

[0114] 100 mmol of phenylboronic acid, 100 mmol of 1,5-dibromonaphthalene, 41.4 g of potassium carbonate (300 mmol), 800 mL of tetrahydrofuran (THF), and 200 mL of water were added to a reaction flask, along with 1 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 60 °C for 12 h. After the reaction was completed, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder M1. The amount of Pd(PPh3)4 added was 1 mol% of 1-naphthaleneboronic acid.

[0115] 100 mmol of M1, 100 mmol of p-chlorophenylboronic acid, 41.4 g of potassium carbonate (300 mmol), 800 mL of tetrahydrofuran (THF), and 200 mL of water were added to a reaction flask, along with 1 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 60 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, M2. The amount of Pd(PPh3)4 added was 1 mol% of M1.

[0116] 100 mmol of M2, 100 mmol of pinacol diborate, 41.4 g of potassium carbonate (300 mmol), and 800 mL of xylene were added to a reaction flask, along with 1 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 100 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, M3. The amount of Pd(PPh3)4 added was 1 mol% of M2.

[0117] 100 mmol of M3, 100 mmol of 2,4-dichloro-6-phenyl-1,3,5-triazine, 41.4 g of potassium carbonate (300 mmol), 800 mL of tetrahydrofuran (THF), and 200 mL of water were added to a reaction flask, along with 1 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 60 °C for 12 h. After the reaction was completed, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, M4. The amount of Pd(PPh3)4 added was 1 mol% of M3.

[0118] 100 mmol of 2-bromo-9-fluorenone and 1000 mmol of phenol were added to a reaction flask, and the mixture was heated to reflux for 12 h. After the reaction was completed, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder M5.

[0119] 100 mmol of M5, 100 mmol of pinacol diborate, 41.4 g of potassium carbonate (300 mmol), and 800 mL of xylene were added to a reaction flask, along with 1 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 100 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, M6. The amount of Pd(PPh3)4 added was 1 mol% of M5.

[0120] 100 mmol of M4, 100 mmol of M6, 41.4 g of potassium carbonate (300 mmol), 800 mL of tetrahydrofuran (THF), and 200 mL of water were added to a reaction flask, along with 1 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 60 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, A6. The amount of Pd(PPh3)4 added was 1 mol% of M4.

[0121] 1 H NMR(400MHz,Chloroform)8.89(s,1H),8.36(d,J=8.0Hz,2H),8.09(s,1H),8.03–7.87(m,4H),7.79(d,J=8.0Hz,3H),7.7 2-7.63(m,5H),7.48(d,J=10.0Hz,4H),7.41(s,1H),7.33(d,J=8.4Hz,4H),7.25(d,J=7.6Hz,4H),7.18(d,J=12.0Hz,6H).

[0122] Synthesis of compound A8:

[0123]

[0124] 100 mmol of pyridine-3-boronic acid, 100 mmol of 1,5-dibromonaphthalene, 41.4 g of potassium carbonate (300 mmol), 800 mL of tetrahydrofuran (THF), and 200 mL of water were added to a reaction flask, along with 1 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 60 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder M1. The amount of Pd(PPh3)4 added was 1 mol% of pyridine-3-boronic acid.

[0125] 100 mmol of M1, 100 mmol of p-chlorophenylboronic acid, 41.4 g of potassium carbonate (300 mmol), 800 mL of tetrahydrofuran (THF), and 200 mL of water were added to a reaction flask, along with 1 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 60 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, M2. The amount of Pd(PPh3)4 added was 1 mol% of M1.

[0126] 100 mmol of M2, 100 mmol of pinacol diborate, 41.4 g of potassium carbonate (300 mmol), and 800 mL of xylene were added to a reaction flask, along with 1 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 100 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, M3. The amount of Pd(PPh3)4 added was 1 mol% of M2.

[0127] 100 mmol of M3, 100 mmol of 2,4-dichloro-6-phenyl-1,3,5-triazine, 41.4 g of potassium carbonate (300 mmol), 800 mL of tetrahydrofuran (THF), and 200 mL of water were added to a reaction flask, along with 1 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 60 °C for 12 h. After the reaction was completed, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, M4. The amount of Pd(PPh3)4 added was 1 mol% of M3.

[0128] 100 mmol of M4, 100 mmol of 9,9-dimethyl-2-fluorenboric 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, along with 1 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 60 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder A8. The amount of Pd(PPh3)4 added was 1 mol% of M4.

[0129] 1 H NMR (400MHz, Chloroform)9.24(s,1H),8.98(d,J=10.0Hz,2H),8.84(s,1H),8.76(d,J=8.0Hz,2H),8.54–8.28(m,3H),8.1 7(d,J=8.4Hz,2H),7.91(d,J=10.0Hz,2H),7.79–7.59(m,5H),7.48(d,J=10.0Hz,4H),7.25(d,J=7.6Hz,4H),1.69(s,6H).

[0130] Synthesis of compound A11:

[0131]

[0132] 100 mmol of 4-biphenylboronic acid, 100 mmol of 2,4-dichloro-6-phenyl-1,3,5-triazine, 41.4 g of potassium carbonate (300 mmol), 800 mL of tetrahydrofuran (THF), and 200 mL of water were added to a reaction flask, along with 1 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 60 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder M1. The amount of Pd(PPh3)4 added was 1 mol% of 4-biphenylboronic acid.

[0133] 100 mmol of 1-naphthoboric acid, 100 mmol of 2,6-dibromonaphthalene, 41.4 g of potassium carbonate (300 mmol), 800 mL of tetrahydrofuran (THF), and 200 mL of water were added to a reaction flask, along with 1 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 60 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder M2. The amount of Pd(PPh3)4 added was 1 mol% of 1-naphthoboric acid.

[0134] Under nitrogen protection, M2 (100 mmol, 1 eq.) and 1 L of tetrahydrofuran were added to a 3 L three-necked flask equipped with a mechanical stirrer and a cryostat. The flask was cooled to -90°C to -80°C with liquid nitrogen, and n-butyllithium (120 mmol, 1.2 eq.) was added dropwise. After the addition was complete, the flask was kept at -90°C to -80°C for 30 min. Then, tri-tert-butyl borate (120 mmol, 1.2 eq.) was added. After the addition was complete, the flask was allowed to naturally warm to 0°C and stirred for 8 hours. After the reaction was complete, 1000 mL of 10 wt% ammonium chloride aqueous solution was added. The mixture was separated, and the organic phase was washed with 300 mL of 10 wt% ammonium chloride aqueous solution each time. The filtrate was concentrated to obtain a black solid, which was then crystallized from toluene to obtain a pale yellow granular solid M3.

[0135] 100 mmol of M1, 100 mmol of M3, 41.4 g of potassium carbonate (300 mmol), 800 mL of tetrahydrofuran (THF), and 200 mL of water were added to a reaction flask, along with 1 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 60 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, Al1. The amount of Pd(PPh3)4 added was 1 mol% of M1.

[0136] 1 H NMR(400MHz,Chloroform)9.15(s,1H),8.95(s,1H),8.51(d,J=8.0Hz,4H),8.12–7.96(m,3 H),7.78(d,J=8.0Hz,3H),7.77(t,J=7.6Hz,4H),7.52–7.41(m,7H),7.39(d,J=10.0Hz,4H).

[0137] Synthesis of compound A16:

[0138]

[0139] Under nitrogen protection, 1-bromonaphthalene (100 mmol, 1 eq.) and 1 L of tetrahydrofuran were added to a 3 L three-necked flask equipped with a mechanical stirrer and a cryostat. The flask was cooled to -90°C to -80°C with liquid nitrogen, and n-butyllithium (120 mmol, 1.2 eq.) was added dropwise. After the addition was complete, the flask was kept at -90°C to -80°C for 30 min. After the addition was complete, the flask was allowed to cool naturally to 0°C, and cyanuric chloride (100 mmol, 1.0 eq.) was added. The mixture was stirred for 8 hours. After the reaction was complete, 1000 mL of 10 wt% ammonium chloride aqueous solution was added. The mixture was separated, and the organic phase was washed with 300 mL of 10 wt% ammonium chloride aqueous solution each time. The filtrate was concentrated to obtain a white solid, which was then crystallized from toluene to obtain a pale yellow granular solid M1.

[0140] 100 mmol of phenylboronic acid, 100 mmol of 2-bromo-5-chloropyridine, 41.4 g of potassium carbonate (300 mmol), 800 mL of tetrahydrofuran (THF), and 200 mL of water were added to a reaction flask, along with 1 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 60 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder M2. The amount of Pd(PPh3)4 added was 1 mol% of the amount of phenylboronic acid.

[0141] 100 mmol of M2, 100 mmol of p-chlorophenylboronic acid, 41.4 g of potassium carbonate (300 mmol), 800 mL of tetrahydrofuran (THF), and 200 mL of water were added to a reaction flask, along with 1 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 60 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, M3. The amount of Pd(PPh3)4 added was 1 mol% of M2.

[0142] 100 mmol of M3, 100 mmol of pinacol diborate, 41.4 g of potassium carbonate (300 mmol), and 800 mL of xylene were added to a reaction flask, along with 1 mol% of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 100 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, M4. The amount of Pd(PPh3)4 added was 1 mol% of M3.

[0143] 100 mmol of M1, 100 mmol of M4, 41.4 g of potassium carbonate (300 mmol), 800 mL of tetrahydrofuran (THF), and 200 mL of water were added to a reaction flask, along with 1 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 60 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, A16. The amount of Pd(PPh3)4 added was 1 mol% of M1.

[0144] 1 H NMR(400MHz,Chloroform)δ8.95(d,J=8.8Hz,1H),8.35(d,J=10.0Hz,2H),8.01(d,J=8.0Hz,2H),7. 94(t,J=7.6Hz,2H),7.83(d,J=10.0Hz,4H),7.65(s,1H),7.58–7.45(m,8H),7.25(d,J=10.0Hz,4H).

[0145] Synthesis of compound A22:

[0146]

[0147] 100 mmol of 1,4-dibromonaphthalene, 100 mmol of 3-pyridineboronic 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, along with 1 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 60 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder M1. The amount of Pd(PPh3)4 added was 1 mol% of p-bromoiodobenzene.

[0148] Under nitrogen protection, M1 (100 mmol, 1 eq.) and 1 L of tetrahydrofuran were added to a 3 L three-necked flask equipped with a mechanical stirrer and a cryostat. The flask was cooled to -90°C to -80°C with liquid nitrogen, and n-butyllithium (120 mmol, 1.2 eq.) was added dropwise. After the addition was complete, the flask was kept at -90°C to -80°C for 30 min. Then, tert-butyl borate (120 mmol, 1.2 eq.) was added. After the addition was complete, the flask was allowed to cool naturally to 0°C and stirred for 8 hours. After the reaction was complete, 1000 mL of 10 wt% ammonium chloride aqueous solution was added. The mixture was separated, and the organic phase was washed with 300 mL of 10 wt% ammonium chloride aqueous solution each time. The filtrate was concentrated to obtain a black solid, which was then crystallized from toluene to obtain a pale yellow granular solid M2.

[0149] 200 mmol of M2, 100 mmol of glufosinate, 41.4 g of potassium carbonate (300 mmol), 800 mL of tetrahydrofuran (THF), and 200 mL of water were added to a reaction flask, along with 2 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 60 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, A22. The amount of Pd(PPh3)4 added was 2 mol% of M2.

[0150] 1 H NMR (400MHz, Chloroform) δ9.24 (s, 2H), 8.97-8.70 (m, 4H), 8.34 (d, J = 10.0Hz, 4H), 8.23-8.01 (m, 6H), 7.67 (d, J = 11.2Hz, 4H), 7.48 (d, J = 11.2Hz, 6H).

[0151] Synthesis of compound A26:

[0152]

[0153] 100 mmol of 4-cyanobenzoic acid, 100 mmol of 1,4-dibromonaphthalene, 41.4 g of potassium carbonate (300 mmol), 800 mL of tetrahydrofuran (THF), and 200 mL of water were added to a reaction flask, along with 1 mol% tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 60 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder M1. The amount of Pd(PPh3)4 added was 1 mol% of 4-cyanobenzoic acid.

[0154] 100 mmol of M1, 100 mmol of p-chlorophenylboronic acid, 41.4 g of potassium carbonate (300 mmol), 800 mL of tetrahydrofuran (THF), and 200 mL of water were added to a reaction flask, along with 1 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 60 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, M2. The amount of Pd(PPh3)4 added was 1 mol% of M1.

[0155] 100 mmol of M2, 100 mmol of pinacol diborate, 41.4 g of potassium carbonate (300 mmol), and 800 mL of xylene were added to a reaction flask, along with 1 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 100 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, M3. The amount of Pd(PPh3)4 added was 1 mol% of M2.

[0156] 100 mmol of 9,9'-spirodifluorene-2-boric acid, 100 mmol of 2,4-dichloro-6-phenyl-1,3,5-triazine, 41.4 g of potassium carbonate (300 mmol), 800 mL of tetrahydrofuran (THF), and 200 mL of water were added to a reaction flask, along with 1 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 60 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder M4. The amount of Pd(PPh3)4 added was 1 mol% of 9,9'-spirodifluorene-2-boric acid.

[0157] 100 mmol of M3, 100 mmol of M4, 41.4 g of potassium carbonate (300 mmol), 800 mL of tetrahydrofuran (THF), and 200 mL of water were added to a reaction flask, along with 1 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 60 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, A26. The amount of Pd(PPh3)4 added was 1 mol% of M3.

[0158] 1 H NMR(400MHz,Chloroform)9.00(s,1H),8.95(s,1H),8.14(d,J=10.4Hz,2H),7.98–7.76(m,5H),7. 68(s,1H),7.63(d,J=8.8Hz,4H),7.56-7.40(m,8H),7.34(d,J=8.4Hz,4H),7.24(d,J=8.0Hz,4H).

[0159] Synthesis of compound A27

[0160]

[0161] 100 mmol of 2-bromoquinoline, 100 mmol of p-chlorophenylboronic acid, 41.4 g of potassium carbonate (300 mmol), 800 mL of tetrahydrofuran (THF), and 200 mL of water were added to a reaction flask, along with 1 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 60 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder M1. The amount of Pd(PPh3)4 added was 1 mol% of 2-bromoquinoline.

[0162] 100 mmol of M1, 100 mmol of pinacol diborate, 41.4 g of potassium carbonate (300 mmol), and 800 mL of xylene were added to a reaction flask, along with 1 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 100 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, M2. The amount of Pd(PPh3)4 added was 1 mol% of M1.

[0163] 100 mmol of M2, 100 mmol of 2,4-dichloro-6-phenyl-1,3,5-triazine, 41.4 g of potassium carbonate (300 mmol), 800 mL of tetrahydrofuran (THF), and 200 mL of water were added to a reaction flask, along with 1 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 60 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, M3. The amount of Pd(PPh3)4 added was 1 mol% of M2.

[0164] Under nitrogen protection, 1-bromonaphthalene-D7 (100 mmol, 1 eq.) and 1 L of tetrahydrofuran were added to a 3 L three-necked flask equipped with a mechanical stirrer and a cryostat. The flask was cooled to -90°C to -80°C with liquid nitrogen, and n-butyllithium (120 mmol, 1.2 eq.) was added dropwise. After the addition was complete, the flask was kept at -90°C to -80°C for 30 min. Then, tri-tert-butyl borate (120 mmol, 1.2 eq.) was added. After the addition was complete, the flask was allowed to cool naturally to 0°C and stirred for 8 hours. After the reaction was complete, 1000 mL of 10 wt% ammonium chloride aqueous solution was added. The mixture was separated, and the organic phase was washed with 300 mL of 10 wt% ammonium chloride aqueous solution each time. The filtrate was concentrated to obtain a black solid, which was then crystallized from toluene to obtain a pale yellow granular solid M4.

[0165] 100 mmol of M3, 100 mmol of M4, 41.4 g of potassium carbonate (300 mmol), 800 mL of tetrahydrofuran (THF), and 200 mL of water were added to a reaction flask, along with 1 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 60 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, A27. The amount of Pd(PPh3)4 added was 1 mol% of M3.

[0166] 1 H NMR (400MHz, Chloroform)8.69(s,1H),8.38(d,J=10.0Hz,2H),7.99(t,J=8.4Hz,2H),7.89(d,J=8.0Hz,3H),7.74-7.55(m,3H),7.43-7.34(m,4H).

[0167] Synthesis of compound A28

[0168]

[0169] 100 mmol of 1-bromonaphthalene, 100 mmol of p-chlorophenylboronic acid, 41.4 g of potassium carbonate (300 mmol), 800 mL of tetrahydrofuran (THF), and 200 mL of water were added to a reaction flask, along with 1 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 60 °C for 12 h. After the reaction was completed, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder M1. The amount of Pd(PPh3)4 added was 1 mol% of the 1-bromonaphthalene.

[0170] 100 mmol of M1, 100 mmol of pinacol diborate, 41.4 g of potassium carbonate (300 mmol), and 800 mL of xylene were added to a reaction flask, along with 1 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 100 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, M2. The amount of Pd(PPh3)4 added was 1 mol% of M1.

[0171] 100 mmol of M2, 100 mmol of 2,4-dichloro-6-phenyl-1,3,5-triazine, 41.4 g of potassium carbonate (300 mmol), 800 mL of tetrahydrofuran (THF), and 200 mL of water were added to a reaction flask, along with 1 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 60 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, M3. The amount of Pd(PPh3)4 added was 1 mol% of M2.

[0172] 100 mmol of M3, 100 mmol of dibenzothiophene-2-boric 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, along with 1 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 60 °C for 12 h. After the reaction was completed, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, A28. The amount of Pd(PPh3)4 added was 1 mol% of M3.

[0173] 1 H NMR(400MHz,Chloroform)8.95(s,1H),8.61(s,1H),8.47(d,J=8.0Hz,2H),8.36( s,1H),7.99–7.77(m,5H),7.67-7.56(m,6H),7.50(s,1H),7.33(d,J=10.0Hz,6H).

[0174] Synthesis of compound A29

[0175]

[0176] 100 mmol of 1-naphthoboric acid, 100 mmol of 2-iodo-5-bromopyridine, 41.4 g of potassium carbonate (300 mmol), 800 mL of tetrahydrofuran (THF), and 200 mL of water were added to a reaction flask, along with 1 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 60 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder M1. The amount of Pd(PPh3)4 added was 1 mol% of 1-naphthoboric acid.

[0177] 100 mmol of M1, 100 mmol of p-chlorophenylboronic acid, 41.4 g of potassium carbonate (300 mmol), 800 mL of tetrahydrofuran (THF), and 200 mL of water were added to a reaction flask, along with 1 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 60 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, M2. The amount of Pd(PPh3)4 added was 1 mol% of M1.

[0178] 100 mmol of M2, 100 mmol of pinacol diborate, 41.4 g of potassium carbonate (300 mmol), and 800 mL of xylene were added to a reaction flask, along with 1 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 100 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, M3. The amount of Pd(PPh3)4 added was 1 mol% of M2.

[0179] 100 mmol of M3, 100 mmol of 2,4-dichloro-6-phenyl-1,3,5-triazine, 41.4 g of potassium carbonate (300 mmol), 800 mL of tetrahydrofuran (THF), and 200 mL of water were added to a reaction flask, along with 1 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 60 °C for 12 h. After the reaction was completed, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, M4. The amount of Pd(PPh3)4 added was 1 mol% of M3.

[0180] 100 mmol of M4, 100 mmol of 9,9-dimethylfluorene-2-boric 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, along with 1 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 60 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, A29. The amount of Pd(PPh3)4 added was 1 mol% of M4.

[0181] 1H NMR(400MHz,Chloroform)8.51–8.38(m,2H),8.36(s,1H),8.27(t,J=8.4Hz,2H),8.01– 7.92(m,5H),7.71–7.59(m,6H),7.48(d,J=10.0Hz,4H),7.37–7.16(m,6H),1.69(s,6H).

[0182] Synthesis of compound A30

[0183]

[0184] 100 mmol of 4-bromoquinoline, 100 mmol of p-chlorophenylboronic acid, 41.4 g of potassium carbonate (300 mmol), 800 mL of tetrahydrofuran (THF), and 200 mL of water were added to a reaction flask, along with 1 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 60 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder M1. The amount of Pd(PPh3)4 added was 1 mol% of 4-bromoquinoline.

[0185] 100 mmol of M1, 100 mmol of pinacol diborate, 41.4 g of potassium carbonate (300 mmol), and 800 mL of xylene were added to a reaction flask, along with 1 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 100 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, M2. The amount of Pd(PPh3)4 added was 1 mol% of M1.

[0186] 100 mmol of M2, 100 mmol of 2,4-dichloro-6-phenyl-1,3,5-triazine, 41.4 g of potassium carbonate (300 mmol), 800 mL of tetrahydrofuran (THF), and 200 mL of water were added to a reaction flask, along with 1 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 60 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, M3. The amount of Pd(PPh3)4 added was 1 mol% of M2.

[0187] 100 mmol of 3,7-dibromodibenzofuran, 100 mmol of 1-naphthylboronic 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, along with 1 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 60 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder M4. The amount of Pd(PPh3)4 added was 1 mol% of 3,7-dibromodibenzofuran.

[0188] 100 mmol of M4, 100 mmol of pinacol diborate, 41.4 g of potassium carbonate (300 mmol), and 800 mL of xylene were added to a reaction flask, along with 1 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 100 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, M5. The amount of Pd(PPh3)4 added was 1 mol% of M4.

[0189] 100 mmol of M3, 100 mmol of M5, 41.4 g of potassium carbonate (300 mmol), 800 mL of tetrahydrofuran (THF), and 200 mL of water were added to a reaction flask, along with 1 mol% of tetra(triphenylphosphine)palladium (Pd(PPh3)4). The reaction was carried out at 60 °C for 12 h. After the reaction was complete, the reaction was stopped, and the reactants were cooled to room temperature. Water was added, the mixture was filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to obtain a white powder, A30. The amount of Pd(PPh3)4 added was 1 mol% of M3.

[0190] 1 H NMR(400MHz,Chloroform)8.87(s,1H),8.50(s,1H),8.36(s,1H),8.20(d,J=10.0Hz,2H),7.99 –7.89(m,4H),7.86–7.74(m,5H),7.62–7.48(m,7H),7.40(d,J=8.8Hz,4H),7.34-7.25(m,3H).

[0191] Other compounds in this application can be synthesized by selecting suitable raw materials in accordance with the above-mentioned synthetic ideas of compounds A1, A3, A5, A6, A8, A11, A16, A22, A26, A27, A28, A29 or A30, or by selecting any other suitable method and raw materials.

[0192] Example 1

[0193] 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 until all moisture was removed, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam.

[0194] Then, the glass substrate with the anode was placed in a vacuum chamber and evacuated to a vacuum level of less than 10. -5 A hole injection layer is vacuum-deposited on the aforementioned anolyte film. The hole injection layer material comprises hole injection layer material HT-11 and p-type dopant p-1. The deposition is performed using a multi-source co-evaporation method. The deposition rate of hole injection layer material HT-11 is adjusted to 0.1 nm / s, and the deposition rate of p-type dopant p-1 is 3% of the deposition rate of hole injection layer material HT-11. The deposited film thickness is 10 nm. The hole injection layer material HT-11 and p-type dopant p-1 are as follows:

[0195]

[0196] Then, hole transport material HT-5 was vacuum-deposited on the hole injection layer as a hole transport layer, wherein the deposition rate was 0.1 nm / s and the deposition film thickness was 80 nm. The hole transport material HT-5 is as follows:

[0197]

[0198] Then, a light-emitting layer is vacuum-deposited on top of the hole transport layer. The light-emitting layer comprises a host material BH-2 and a fluorescent dopant BD-1, and is deposited using a multi-source co-evaporation method. The deposition rate of the host material BH-2 is adjusted to 0.1 nm / s, and the deposition rate of the fluorescent dopant BD-1 is 3% of the deposition rate of the host material BH-2. The deposited film thickness is 30 nm. The host material BH-2 and the fluorescent dopant BD-1 are as follows:

[0199]

[0200] Then, an electron transport layer is vacuum-deposited on top of the light-emitting layer. The electron transport material is compound A1, with a deposition rate of 0.1 nm / s and a film thickness of 30 nm. The electron transport material A1 is as follows:

[0201]

[0202] Then, a 0.5 nm thick LiF layer was vacuum-deposited on the electron transport layer as an electron injection layer, with a deposition rate of 0.1 nm / s.

[0203] Finally, an Al layer with a thickness of 150 nm was vacuum-deposited on the electron injection layer as the cathode electrode of the organic electroluminescent device, wherein the deposition rate was 0.1 nm / s.

[0204] Example 2-13

[0205] Except that the electron transport material is replaced by A3, A5, A6, A8, A11, A16, A22, A26, A27, A28, A29 or A30 instead of A1, the rest is the same as in Example 1. See Table 1 for details.

[0206] Comparative Example 1

[0207] Except for the use of ET-6 as the electron transport material, everything else is the same as in Example 1; ET-6 is as follows:

[0208]

[0209] The organic electroluminescent devices prepared by the above process were subjected to the following performance measurements:

[0210] Under the same brightness, the driving voltage, current efficiency, and lifetime of the organic electroluminescent devices prepared in Examples 1-13 and Comparative Example 1 were measured using a digital source meter and a luminance meter. Specifically, the voltage was increased at a rate of 0.1V per second, and the measurement was performed when the brightness of the organic electroluminescent device reached 1000 cd / m². 2 The voltage at that time is the driving voltage, and the current density at that time is measured simultaneously; the ratio of brightness to current density is the current efficiency; the life test of LT95 is as follows: using a luminance meter at 1000 cd / m² 2 At a constant current, the brightness of the organic electroluminescent device decreased to 950 cd / m² under the specified brightness. 2 The time is expressed in hours. The results are shown in Table 1.

[0211] Table 1 Performance results of organic electroluminescent devices

[0212]

[0213] As can be seen from Table 1, the compounds A1, A3, A5, A6, A8, A11, A16, A22, A26, A27, A28, A29, and A30 obtained in this application, when used as electron transport materials in organic electroluminescent devices, can effectively reduce driving voltage, improve current efficiency, and extend device lifespan, making them high-performance electron transport materials.

[0214] The above description is merely a preferred embodiment of this application and is not intended to limit the scope of protection of this application. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application are included within the scope of protection of this application.

Claims

1. A compound, wherein, The compound is selected from the compounds shown in A6, A16, A26, A27, and A29 below: .

2. An electron transport material comprising at least one of the compounds of claim 1.

3. An organic electroluminescent device comprising at least one of the electron transport materials of claim 2.

4. A display device comprising the organic electroluminescent device of claim 3.

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