An anthracene compound

Abstract

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

Description

Technical Field

[0001] The present application relates to the technical field of organic light-emitting display, and in particular to an anthracene compound. Background Art

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

[0003] With the continuous advancement of OLED technology in the two major fields of lighting and display, people 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.

[0004] Compared with inorganic light-emitting materials, organic electroluminescent materials have many advantages, such as good processing performance, can be formed into films 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, etc., and there is a lot of room for material selection. In the most common OLED device structure, the following types of organic materials are usually included: hole injection materials, hole transport materials, electron transport materials, and luminescent materials (including host materials and guest materials). At present, 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. The low mobility of commercial electron transport materials is an important limiting factor in the development of device performance. It is worth doing more exploration to develop materials with higher mobility. Summary of the invention

[0005] The purpose of the present application is to provide an anthracene compound, which, when used as an electron transport material, can improve the working efficiency and extend the service life of an organic electroluminescent device.

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

[0007]

[0008] in,

[0009] L 1 and L 2 Each independently selected from a chemical bond, unsubstituted or Rc-substituted C 6 -C 30 Arylene, unsubstituted or Rc-substituted C 3 -C 30 heteroarylene;

[0010] R 1 -R 8 are each independently selected from hydrogen, deuterium, C 1 -C 10 Alkyl, unsubstituted or substituted by Rc C 6 -C 30 Aryl, unsubstituted or Rc substituted C 3 -C 30 Heteroaryl, R 1 -R 8 Two adjacent groups in the can be connected to form a ring;

[0011] X is each independently selected from O or S;

[0012] Y 1 -Y 8 are each independently selected from hydrogen, C unsubstituted or substituted by Rc 6 -C 30 Aryl, unsubstituted or Rc substituted C 3 -C 30 Heteroaryl, Y 1 -Y 8 Two adjacent groups in the can be connected to form a ring;

[0013] The heteroatoms on the heteroaryl or the heteroarylene are each independently selected from O, S or N;

[0014] The substituents Rc of each group are independently selected from deuterium, halogen, nitro, cyano, C 1 -C 4 Alkyl, phenyl, biphenyl, terphenyl or naphthyl.

[0015] The second aspect of the present application provides an electron transport material, which comprises at least one of the compounds provided in the first aspect of the present application.

[0016] The third aspect of the present application provides an organic electroluminescent device, which comprises at least one of the electron transport materials provided in the second aspect of the present application.

[0017] A fourth aspect of the present application provides a display device, which includes the organic electroluminescent device provided by the third aspect of the present application.

[0018] The compound provided by the present application has the parent structure of anthracene biphenyl azole, high bond energy between atoms, good thermal stability, and is conducive to solid-state stacking between molecules. When used as an electron transport material, it has a suitable energy level between adjacent layers, which is conducive to the injection and migration of excitons, can effectively reduce the driving voltage, and has a high electron migration rate, and can achieve good luminous efficiency and service life in organic electroluminescent devices. The compound of the present application has a larger conjugated plane, which is conducive to molecular stacking, shows good thermodynamic stability, and is manifested as a long life in the device. The organic electroluminescent device of the present application contains 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 service life of the organic electroluminescent device. The display device provided by the present application has an excellent display effect.

[0019] 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

[0020] In order to more clearly illustrate the technical solutions in the present application or the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application, and for ordinary technicians in this field, other embodiments can also be obtained based on these drawings.

[0021] Figure 1 A schematic diagram of the structure of a typical organic electroluminescent device. DETAILED DESCRIPTION

[0022] The following will be combined with the drawings in this application to clearly and completely describe the technical solutions in this application. Obviously, the described embodiments are only part of the embodiments of this application, not all of the embodiments. Based on the embodiments in this application, all other embodiments obtained by ordinary technicians in this field based on this application belong to the scope of protection of this application.

[0023] In a first aspect, the present application provides a compound of formula (I):

[0024]

[0025] in,

[0026] L 1 and L 2 Each independently selected from a chemical bond, unsubstituted or Rc-substituted C 6 -C 30 Arylene, unsubstituted or Rc-substituted C 3 -C 30heteroarylene;

[0027] R 1 -R 8 are each independently selected from hydrogen, deuterium, C 1 -C 10 Alkyl, unsubstituted or substituted by Rc C 6 -C 30 Aryl, unsubstituted or Rc substituted C 3 -C 30 Heteroaryl, R 1 -R 8 Two adjacent groups in the can be connected to form a ring;

[0028] X is each independently selected from O or S;

[0029] Y 1 -Y 8 are each independently selected from hydrogen, C unsubstituted or substituted by Rc 6 -C 30 Aryl, unsubstituted or Rc substituted C 3 -C 30 Heteroaryl, Y 1 -Y 8 Two adjacent groups in the can be connected to form a ring;

[0030] The heteroatoms on the heteroaryl or the heteroarylene are each independently selected from O, S or N;

[0031] The substituents Rc of each group are independently selected from deuterium, halogen, nitro, cyano, C 1 -C 4 Alkyl, phenyl, biphenyl, terphenyl or naphthyl.

[0032] Preferably, L 1 and L 2 Each independently selected from a chemical bond, unsubstituted or Rc-substituted C 6 -C 18 Arylene, unsubstituted or Rc-substituted C 3 -C 18 Heteroarylene.

[0033] More preferably, the L 1 and L 2 The subunits are each independently selected from the following compounds which are chemically bonded, unsubstituted or substituted with Rc: benzene, biphenyl, terphenyl, naphthalene, phenanthrene, triphenylene, fluorene, pyridine, pyridazine, pyrimidine, pyrazine, quinoline, isoquinoline, quinazoline, quinoxaline, cinnoline, naphthyridine, triazine, pyridopyrazine, furan, benzofuran, dibenzofuran, aza-dibenzofuran, thiophene, benzothiophene, dibenzothiophene, aza-dibenzothiophene, 9,9-dimethylfluorene, and spirofluorene.

[0034] For example, the compound of formula (I) can be selected from the following compounds A1 to A25:

[0035]

[0036]

[0037] The compound of formula (I) provided in the present application has high bond energy between atoms, good thermal stability, and is conducive to solid-state stacking between molecules. In addition, the preparation process of the compound of formula (I) provided in the present application is simple and easy, and the raw materials are easily available, which is suitable for industrial production.

[0038] The second aspect of the present application provides an electron transport material, which comprises at least one of the compounds provided in the first aspect of the present application.

[0039] When the compound of the present application is used as an electron transport material, it has a matching energy level between adjacent layers, which is conducive to the injection and migration of electrons and can effectively reduce the driving voltage. At the same time, it has a high electron migration rate and can achieve good luminous efficiency and service life in an organic electroluminescent device. It also has a large conjugated plane, which is conducive to molecular stacking and shows good thermodynamic stability. Use in an organic electroluminescent device can extend its service life.

[0040] The third aspect of the present application provides an organic electroluminescent device, which comprises at least one of the electron transport materials provided in the second aspect of the present application. Therefore, the organic electroluminescent device provided in the present application has low driving voltage, high luminous efficiency and long service life.

[0041] In the present application, there is no particular limitation on the type and structure of the organic electroluminescent device, and it can be any organic electroluminescent device of different types and structures known in the art, as long as the electron transport material provided in the present application can be used.

[0042] 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.

[0043] The organic electroluminescent device of the present application may also be a light-emitting device with a bottom emission 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.

[0044] 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.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] In the present application, the substrate 1 is not particularly limited, and conventional substrates used in organic electroluminescent devices in the prior art may be used, such as glass, polymer materials, and glass and polymer materials with thin film transistor (TFT) components.

[0050] In the present application, the reflective anode material 2 is not particularly limited and can be selected from indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO 2), zinc oxide (ZnO) and other transparent conductive materials, and can also be selected from metal materials such as silver and its alloys, aluminum and its alloys, and can also be selected from organic conductive materials such as poly 3,4-ethylenedioxythiophene (PEDOT), or a multilayer structure of the above materials.

[0051] In the present application, the material of the hole injection layer 3 is not particularly limited, and can be made of hole injection layer materials known in the art. For example, at least one of the known hole transport materials (HTM) is selected as the hole injection material.

[0052] In the present application, the hole injection layer 3 may further include a p-type dopant, and the type of the p-type dopant is not particularly limited, and various p-type dopants known in the art may be used. For example, the p-type dopant may be selected from but not limited to at least one of the following p-1 to p-3 compounds:

[0053]

[0054] 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.

[0055] In the present 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 can meet the purpose of the present application, for example, 1 layer, 2 layers, 3 layers, 4 layers or more layers.

[0056] For example, the HTM for the hole injection layer material and the HTM for the hole transport layer material may be selected from, but not limited to, at least one of the following HT-1 to HT-31 compounds:

[0057]

[0058]

[0059] In the present application, the light-emitting layer 5 may include a blue light-emitting layer, a green light-emitting layer or a red light-emitting layer. The light-emitting material in the light-emitting layer 5 is not particularly limited, and various light-emitting materials known to those skilled in the art may be used. For example, the material of the light-emitting layer 5 may include a host material and a guest material.

[0060] In the present application, the host material may be selected from but not limited to at least one of the following BH-1 to BH-10 compounds:

[0061]

[0062] In the present application, the guest material is not particularly limited, and at least one of the light-emitting layer guest materials known in the art can be used. For example, the light-emitting layer guest material can be selected from but not limited to at least one of the following BD-1 to BD-9 compounds:

[0063]

[0064] In the present application, the amount of the guest material in the light-emitting layer is not particularly limited and can be an amount known to those skilled in the art.

[0065] In the present application, the electron transport layer 6 comprises at least one of the electron transport materials of the present application, and the electron transport layer 6 may also comprise a combination of at least one of the electron transport materials of the present application and at least one of the known electron transport materials. The number of layers of the electron transport layer 6 is not particularly limited and can be adjusted according to actual needs, as long as the purpose of the present application can be met, for example, 1 layer, 2 layers, 3 layers, 4 layers or more layers.

[0066] 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:

[0067]

[0068]

[0069]

[0070]

[0071] 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:

[0072]

[0073] 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.

[0074] In the present application, the material of the electron injection layer 7 is not particularly limited, and electron injection materials known in the art can be used, for example, including but not limited to LiQ, LiF, NaCl, CsF, Li 2 O、Cs 2 CO 3 , BaO, Na, Li, Ca and other materials.

[0075] 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, LiF / Al, ITO, Al and other metals, metal mixtures, oxides and the like.

[0076] The fourth aspect of the present application provides a display device, which includes the organic electroluminescent device provided in the third aspect of the present application. The display device includes but is not limited to a display, a television, a tablet computer, a mobile communication terminal, etc.

[0077] 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:

[0078] (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;

[0079] (2) vacuum evaporating a hole injection material on the reflective anode electrode 2 to form a hole injection layer 3;

[0080] (3) vacuum evaporating a hole transport material on the hole injection layer 3 to form a hole transport layer 4;

[0081] (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;

[0082] (5) vacuum evaporating an electron transport material on the light emitting layer 5 to form an electron transport layer 6;

[0083] (6) vacuum evaporating an electron injection material on the electron transport layer 6 to form an electron injection layer 7;

[0084] (7) A cathode material is vacuum-deposited on the electron injection layer 7 to form a cathode electrode 8 .

[0085] 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.

[0086] The synthesis method of the compound of the present application is not particularly limited, and any method known to those skilled in the art can be used for synthesis. The following examples illustrate the synthesis process of the compound of the present application.

[0087] Synthesis Example 1: Synthesis of Compound A1:

[0088]

[0089] In a reaction flask, 100 mmol of p-bromophenylboronic acid, 100 mmol of 2-chlorobenzoxazole, 41.4 g of potassium carbonate (300 mmol), 800 ml of tetrahydrofuran (THF) and 200 ml of water were added, and 1 mol% of tetrakis(triphenylphosphine)palladium (Pd(PPh 3 ) 4 ), react at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain white powder M1. 3 ) 4 The amount of addition is 1 mol% of p-bromophenylboric acid.

[0090] N 2 Under protection, M1 (250mmol, 2.5eq.) and 1L of tetrahydrofuran were added to a 10L three-necked flask equipped with a mechanical stirrer and a low-temperature thermometer, and the temperature was cooled to -90°C to -80°C with liquid nitrogen, and n-butyl lithium (250mmol, 2.5eq.) was added dropwise. After the addition was completed, the temperature was kept at (-90°C to -80°C) for 30min, and 9,10-dianthraquinone (100mmol, 1eq.) was added. After the addition was completed, the temperature was naturally raised to zero degrees and stirring was continued for 8 hours. After the reaction was completed, 1000mL of 10wt% ammonium chloride aqueous solution was added, and the liquid was separated. The organic phase was washed with 300mL of 10wt% ammonium chloride aqueous solution each time, and the filtrate was concentrated to obtain a black solid, which was crystallized from toluene to obtain a light yellow sandy solid M2.

[0091] N 2 Under protection, add 1L of acetic acid to the reactor, start stirring and heating, and when the reaction liquid is heated to about 60°C, add 100mmol of intermediate M1, 300mmol of KI, and NaHPO 2 ·H 2 O 300mmol, reflux (about 120℃) for 5 hours, stop heating, cool down, filter, rinse with acetic acid and anhydrous ethanol in turn and drain, then rinse with water repeatedly, and finally rinse with acetone and drain to obtain yellow solid compound A1.

[0092] 1 H NMR (400MHz, Chloroform) 8.21 (s, 2H), 7.96-7.74 (m, 8H), 7.52 (d, J = 10.0Hz, 8H), 7.43-7.25 (m, 6H).

[0093] Synthesis Example 2: Synthesis of Compound A2:

[0094]

[0095] 100 mmol of 2-bromo-5-iodopyridine, 100 mmol of biboric acid pinacol ester, 41.4 g of potassium carbonate (300 mmol) and 800 ml of toluene were added to the reaction flask, and 1 mol% of tris(dibenzylideneacetone)dipalladium (Pd 2 (dba) 3 ), react at 100°C for 12h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain white powder M1. 2 (dba) 3 The amount of addition was 1 mol% of 2-bromo-5-iodopyridine.

[0096] 100 mmol of M1, 100 mmol of 2-chlorobenzoxazole, 41.4 g of potassium carbonate (300 mmol), 800 ml of tetrahydrofuran (THF) and 200 ml of water were added to the reaction flask, and 1 mol% of tetrakis(triphenylphosphine)palladium (Pd(PPh 3 ) 4 ), react at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain white powder M2. 3 ) 4 The added amount is 1 mol% of M1.

[0097] N 2 Under protection, add M2 (250mmol, 2.5eq.) and 1L of tetrahydrofuran to a 10L three-necked flask equipped with mechanical stirring and a low-temperature thermometer, cool the temperature to -90℃ to -80℃ with liquid nitrogen, add n-butyl lithium (250mmol, 2.5eq.) dropwise, keep warm (-90℃ to -80℃) for 30min after the addition is complete, add 9,10-dianthraquinone (100mmol, 1eq.), naturally heat to zero after the addition is complete, and continue stirring for 8 hours. After the reaction is completed, add 1000mL of 10wt% ammonium chloride aqueous solution, separate the liquids, wash the organic phase with 300mL of 10wt% ammonium chloride aqueous solution each time, concentrate the filtrate to obtain a black solid, and crystallize with toluene to obtain a light yellow sandy solid M3.

[0098] N 2 Under protection, add 1L of acetic acid to the reactor, start stirring and heating, and when the reaction liquid is heated to about 60°C, add 100mmol of intermediate M3, 300mmol of KI, and NaHPO 2 ·H 2O 300mmol, reflux (about 120℃) for 5 hours, stop heating, cool down, filter, rinse with acetic acid and anhydrous ethanol in turn and drain, then rinse with water repeatedly, and finally rinse with acetone and drain to obtain yellow solid compound A2.

[0099] 1 H NMR (400MHz, Chloroform) 9.11 (s, 2H), 8.28 (s, 2H), 8.19 (d, J = 8.0Hz, 4H), 7.74 (s, -7.53 (m, 8H), 7.38-7.23 (m, 6H).

[0100] Synthesis Example 3: Synthesis of Compound A3:

[0101]

[0102] 100 mmol of p-bromophenylboronic acid, 100 mmol of 2-chlorobenzothiazole, 41.4 g of potassium carbonate (300 mmol), 800 ml of tetrahydrofuran (THF) and 200 ml of water were added to the reaction flask, and 1 mol% of tetrakis(triphenylphosphine)palladium (Pd(PPh 3 ) 4 ), react at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain white powder M1. 3 ) 4 The amount of addition is 1 mol% of p-bromophenylboric acid.

[0103] N 2 Under protection, M1 (250mmol, 2.5eq.) and 1L of tetrahydrofuran were added to a 10L three-necked flask equipped with a mechanical stirrer and a low-temperature thermometer, and the temperature was cooled to -90°C to -80°C with liquid nitrogen, and n-butyl lithium (250mmol, 2.5eq.) was added dropwise. After the addition was completed, the temperature was kept at (-90°C to -80°C) for 30min, and 9,10-dianthraquinone (100mmol, 1eq.) was added. After the addition was completed, the temperature was naturally raised to zero degrees and stirring was continued for 8 hours. After the reaction was completed, 1000mL of 10wt% ammonium chloride aqueous solution was added, and the liquid was separated. The organic phase was washed with 300mL of 10wt% ammonium chloride aqueous solution each time, and the filtrate was concentrated to obtain a black solid, which was crystallized from toluene to obtain a light yellow sandy solid M2.

[0104] N 2 Under protection, add 1L of acetic acid to the reactor, start stirring and heating, and when the reaction liquid is heated to about 60°C, add 100mmol of intermediate M1, 300mmol of KI, and NaHPO 2 ·H2 O 300mmol, reflux (about 120℃) for 5 hours, stop heating, cool down, filter, rinse with acetic acid and anhydrous ethanol in turn and drain, then rinse with water repeatedly, and finally rinse with acetone and drain to obtain yellow solid compound A3.

[0105] 1 H NMR (400MHz, Chloroform)8.20(d,J=12.0Hz,4H),8.04(t,J=7.2Hz,4H),7.99(d,J=10.0Hz,8H),7.52(d,J=10.0Hz,4H),7.43-7.25(m,4H).

[0106] Synthesis Example 4: Synthesis of Compound A4:

[0107]

[0108] Add 100 mmol of 2-phenylanthracene and 500 ml of dichloromethane to a single-mouth bottle, cool to 0°C, add 200 mmol of N-bromosuccinimide (NBS) in batches, keep at 0°C for 1 hour, react for 3 hours, and monitor the disappearance of the raw material by thin layer chromatography (TLC). Add water to the reaction solution, extract with ethyl acetate, and concentrate the organic phase to obtain a brown solid M1.

[0109] 100 mmol of M1, 200 mmol of biboric acid pinacol ester, 41.4 g of potassium carbonate (300 mmol) and 800 ml of toluene were added to the reaction flask, and 2 mol% of tris(dibenzylideneacetone)dipalladium (Pd 2 (dba) 3 ), react at 100°C for 12h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain white powder M2. 2 (dba) 3 The added amount is 2 mol% of M1.

[0110] 100 mmol of 2-chlorobenzoxazole, 100 mmol of p-bromophenylboronic acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of THF and 200 ml of water were added to the reaction flask, and 1 mol% of tetrakis(triphenylphosphine)palladium (Pd(PPh 3 ) 4 ), reacted at 60°C for 12h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder M3. Among them, Pd(PPh 3 ) 4The amount of addition was 1 mol% of 2-chlorobenzoxazole.

[0111] 100 mmol of M2, 200 mmol of M3, 41.4 g of potassium carbonate (300 mmol), 800 ml of tetrahydrofuran (THF) and 200 ml of water were added to the reaction flask, and 1 mol% of Pd (PPh 3 ) 4 , react at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain yellow powder compound A4. 3 ) 4 The amount added is 2 mol% of M2.

[0112] 1 H NMR(400MHz,Chloroform)8.96(s,1H),8.34(s,1H),7.96-7.82(m,4H),7.74( d,J=8.0Hz,4H),7.62-7.49(m,6H),7.39(d,J=12.0Hz,6H),7.33-7.15(m,6H).

[0113] Synthesis Example 5: Synthesis of Compound A5:

[0114]

[0115] 100 mmol of 2,6-dibromoanthracene, 200 mmol of phenylboric acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of tetrahydrofuran (THF) and 200 ml of water were added to the reaction flask, and 1 mol% of tetrakis(triphenylphosphine)palladium (Pd(PPh 3 ) 4 ), react at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain white powder M1. 3 ) 4 The added amount was 1 mol% of 2,6-dibromoanthracene.

[0116] Add 100 mmol of M1 and 500 ml of dichloromethane to a single-necked bottle, cool to 0°C, add 200 mmol of N-bromosuccinimide (NBS) in batches, keep at 0°C for 1 hour, react for 3 hours, and monitor the disappearance of the raw material by thin layer chromatography (TLC). Add water to the reaction solution, extract with ethyl acetate, and concentrate the organic phase to obtain a brown solid M2.

[0117] 100 mmol of M2, 200 mmol of biboric acid pinacol ester, 41.4 g of potassium carbonate (300 mmol) and 800 ml of toluene were added to the reaction flask, and 2 mol% of tris(dibenzylideneacetone)dipalladium (Pd 2 (dba) 3 ), reacted at 100°C for 12h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain a white powder M3. 2 (dba) 3 The amount added is 2 mol% of M2.

[0118] 100 mmol of 2-chlorobenzoxazole, 100 mmol of p-bromophenylboronic acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of THF and 200 ml of water were added to the reaction flask, and 1 mol% of Pd(PPh 3 ) 4 , react at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain white powder M4. 3 ) 4 The amount of addition was 1 mol% of 2-chlorobenzoxazole.

[0119] 100 mmol of M3, 200 mmol of M4, 41.4 g of potassium carbonate (300 mmol), 800 ml of THF and 200 ml of water were added to the reaction flask, and 1 mol% of Pd(PPh 3 ) 4 , react at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain yellow powder compound A5. 3 ) 4 The amount added is 2 mol% of M2.

[0120] 1 H NMR (400MHz, Chloroform)8.97(s,2H),8.35(s,2H),7.74(d,J=8.0Hz,8H),7.50(d,J=12.0Hz,6H),7.39(d,J=10.0Hz,12H),7.25(s,2H).

[0121] Synthesis Example 6: Synthesis of Compound A7:

[0122]

[0123] 100 mmol of 2-chlorobenzoxazole, 100 mmol of p-bromophenylboronic acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of tetrahydrofuran (THF) and 200 ml of water were added to the reaction flask, and 1 mol% of tetrakis(triphenylphosphine)palladium (Pd(PPh 3 ) 4 ), react at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain white powder M1. 3 ) 4 The amount of addition was 1 mol% of 2-chlorobenzoxazole.

[0124] 100 mmol of M1, 100 mmol of 9-anthraceneboric acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of THF and 200 ml of water were added to the reaction flask, and 1 mol% of Pd(PPh 3 ) 4 , react at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain white powder M2. 3 ) 4 The added amount is 1 mol% of M1.

[0125] Add 100 mmol of M2 and 500 ml of dichloromethane to a single-necked bottle, cool to 0°C, add 200 mmol of N-bromosuccinimide (NBS) in batches, keep at 0°C for 1 hour, react for 3 hours, and monitor the disappearance of the raw material by thin layer chromatography (TLC). Add water to the reaction solution, extract with ethyl acetate, and concentrate the organic phase to obtain a brown solid M3.

[0126] 100 mmol of 2-chlorobenzoxazole, 100 mmol of m-bromophenylboronic acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of tetrahydrofuran (THF) and 200 ml of water were added to the reaction flask, and 1 mol% of tetrakis(triphenylphosphine)palladium (Pd(PPh 3 ) 4 ), reacted at 60°C for 12h. After the reaction was completed, the reaction was stopped, and the reactant was cooled to room temperature, added with water, filtered, washed with water, and the obtained solid was recrystallized and purified with toluene to obtain white powder M4. Among them, Pd(PPh 3 ) 4 The amount of addition was 1 mol% of 2-chlorobenzoxazole.

[0127] Add 100 mmol of M4, 100 mmol of biboric acid pinacol ester, 29.4 g of potassium carbonate (300 mmol), 800 ml of dioxane, and 1 mol% of palladium acetate to the reaction flask, and react at 100°C for 12 hours. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain a yellow powder compound M5. The amount of palladium acetate added is 2 mol% of M4.

[0128] 100 mmol of M3, 100 mmol of M5, 41.4 g of potassium carbonate (300 mmol), 800 ml of THF and 200 ml of water were added to the reaction flask, and 1 mol% of Pd(PPh 3 ) 4 , react at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain yellow powder compound A7. 3 ) 4 The added amount is 2 mol% of M3.

[0129] 1 H NMR (400MHz, Chloroform)8.22(d,J=8.0Hz,2H),8.15-7.96(m,4H),7.72(d,J=10.0Hz,4H),7.69(s,1H),7.61-7.43(m,7H),7.38-7.25(m,6H).

[0130] Synthesis Example 7: Synthesis of Compound A15:

[0131]

[0132] 100 mmol of 2-chlorobenzoxazole, 100 mmol of p-bromophenylboronic acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of tetrahydrofuran (THF) and 200 ml of water were added to the reaction flask, and 1 mol% of tetrakis(triphenylphosphine)palladium (Pd(PPh 3 ) 4 ), react at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain white powder M1. 3 ) 4 The amount of addition was 1 mol% of 2-chlorobenzoxazole.

[0133] 100 mmol of M1, 100 mmol of 9-anthraceneboric acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of THF and 200 ml of water were added to the reaction flask, and 1 mol% of Pd(PPh 3 ) 4 , react at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain white powder M2. 3 ) 4 The added amount is 1 mol% of M1.

[0134] Add 100 mmol of M2 and 500 ml of dichloromethane to a single-necked bottle, cool to 0°C, add 200 mmol of N-bromosuccinimide (NBS) in batches, keep at 0°C for 1 hour, react for 3 hours, and monitor the disappearance of the raw material by thin layer chromatography (TLC). Add water to the reaction solution, extract with ethyl acetate, and concentrate the organic phase to obtain a brown solid M3.

[0135] 100 mmol of 3-bromo-5-chloroiodobenzene, 100 mmol of 4-cyanophenylboronic acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of THF and 200 ml of water were added to the reaction flask, and 1 mol% of Pd(PPh 3 ) 4 , react at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain white powder M4. 3 ) 4 The amount of addition was 1 mol% of 3-bromo-5-chloroiodobenzene.

[0136] Add 100 mmol of M4, 100 mmol of biboric acid pinacol ester, 29.4 g of potassium carbonate (300 mmol), 800 ml of dioxane, and 1 mol% of palladium acetate to the reaction flask, and react at 100°C for 12 hours. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain a yellow powder compound M5. The amount of palladium acetate added is 2 mol% of M4.

[0137] 100 mmol of M5, 100 mmol of 2-chlorobenzoxazole, 41.4 g of potassium carbonate (300 mmol), 800 ml of THF and 200 ml of water were added to the reaction flask, and 1 mol% of Pd(PPh 3 ) 4, react at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain white powder M6. 3 ) 4 The added amount is 1 mol% of M5.

[0138] Add 100 mmol of M6, 100 mmol of biboric acid pinacol ester, 29.4 g of potassium carbonate (300 mmol), 800 ml of dioxane, and 1 mol% of palladium acetate to the reaction flask, and react at 100°C for 12 hours. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain a yellow powder compound M7. The amount of palladium acetate added is 2 mol% of M6.

[0139] 100 mmol of M3, 200 mmol of M7, 41.4 g of potassium carbonate (300 mmol), 800 ml of THF and 200 ml of water were added to the reaction flask, and 1 mol% of Pd(PPh 3 ) 4 , react at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain yellow powder compound A15. 3 ) 4 The added amount is 2 mol% of M3.

[0140] 1 H NMR(400MHz,Chloroform)8.34(d,J=8.8Hz,4H),8.26(s,1H),8.09–7.81(m,5H),7 .74-7.56(m,4H),7.46(d,J=6.8Hz,4H),7.43-7.32(m,5H),7.21(t,J=10.0Hz,4H).

[0141] Synthesis Example 8: Synthesis of Compound A24:

[0142]

[0143] 100 mmol of 2,5-dichlorobenzoxazole, 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 the reaction flask, and 1 mol% of tetrakis(triphenylphosphine)palladium (Pd(PPh 3 ) 4), react at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain white powder M1. 3 ) 4 The amount of addition was 1 mol% of 2,5-dichlorobenzoxazole.

[0144] In a reaction flask, 100 mmol of M1, 100 mmol of 4-pyridine boronic acid, 41.4 g of potassium carbonate (300 mmol), 800 ml of THF and 200 ml of water were added, and 1 mol% of Pd(PPh 3 ) 4 , react at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain white powder M2. 3 ) 4 The added amount is 1 mol% of M1.

[0145] Add 100 mmol of M2, 100 mmol of biboric acid pinacol ester, 29.4 g of potassium carbonate (300 mmol), 800 ml of dioxane, and 1 mol% of palladium acetate to the reaction flask, and react at 100°C for 12 hours. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and recrystallize and purify the obtained solid with toluene to obtain a yellow powder compound M3. The amount of palladium acetate added is 2 mol% of M2.

[0146] 200 mmol of M3, 100 mmol of 9,10-dibromoanthracene, 41.4 g of potassium carbonate (300 mmol), 800 ml of THF and 200 ml of water were added to the reaction flask, and 1 mol% of Pd(PPh 3 ) 4 , react at 60°C for 12h. After the reaction is completed, stop the reaction, cool the reactant to room temperature, add water, filter, wash with water, and purify the obtained solid by recrystallization with toluene to obtain yellow powder compound A24. 3 ) 4 The added amount is 1 mol% of M3.

[0147] 1 H NMR (400MHz, Chloroform)8.71(s,2H),8.21(s,2H),7.93(d,J=10.0Hz,4H),7.85(s,2H),7.79(d,J=10.0Hz,6H),7.43-7.25(m,14H).

[0148] Other compounds of the present application can be synthesized by selecting suitable raw materials according to the ideas of the above-mentioned synthesis examples 1-8, or by selecting any other suitable method and raw materials for synthesis.

[0149] Example 1

[0150] 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;

[0151] 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 includes hole injection layer material HT-11 and p-type dopant p-1. The deposition is performed by a multi-source co-evaporation method. The deposition rate of the hole injection layer material HT-11 is adjusted to 0.1 nm / s, the deposition rate of the p-type dopant p-1 is adjusted to 3% of the deposition rate of the hole injection layer material HT-11, and the deposition film thickness is 10 nm. The hole injection layer material HT-11 and the p-type dopant p-1 are as follows:

[0152]

[0153] Then, a hole transport material HT-5 was vacuum-deposited on the hole injection layer as a hole transport layer, wherein the evaporation rate was 0.1 nm / s, the evaporation film thickness was 80 nm, and the hole transport material HT-5 was as follows:

[0154]

[0155] Then, a light-emitting layer is vacuum-deposited on the hole transport layer. The light-emitting layer includes a main material BH-2 and a fluorescent dopant BD-1. The deposition is performed by a multi-source co-evaporation method. The deposition rate of the main material BH-2 is adjusted to 0.1 nm / s, the deposition rate of the fluorescent dopant BD-1 is adjusted to 3% of the deposition rate of the main material BH-2, and the deposition film thickness is 30 nm. The main material BH-2 and the fluorescent dopant BD-1 are as follows:

[0156]

[0157] Then, an electron transport layer is vacuum evaporated on the light-emitting layer, and the electron transport material is compound A1, wherein the evaporation rate is 0.1 nm / s and the evaporation film thickness is 30 nm; the electron transport material A1 is as follows:

[0158]

[0159] 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;

[0160] Finally, an Al 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 0.1 nm / s.

[0161] Embodiment 2-8

[0162] Except that the electron transport material is replaced by A2, A3, A4, A5, A6, A10 or A13 respectively, the rest is the same as Example 1. See Table 1 for details.

[0163] Comparative Example 1

[0164] Except that ET-32 is selected as the electron transport material, the rest is the same as Example 1; ET-32 is as follows:

[0165]

[0166] The organic electroluminescent device prepared by the above process was subjected to the following performance tests:

[0167] At the same brightness, the driving voltage, current efficiency and device life of the organic electroluminescent devices prepared in Examples 1-8 and Comparative Example 1 were measured using a digital source meter and a brightness meter. Specifically, the voltage was increased at a rate of 0.1 V per second, and the brightness of the organic electroluminescent device was measured when it reached 1000 cd / m 2 The voltage at which the light is on is the driving voltage, and the current density at this time is measured at the same time; the ratio of brightness to current density is the current efficiency; the life test of LT95 is as follows: use a brightness meter at 1000cd / m 2 At the same brightness, the current is kept constant and the brightness of the organic electroluminescent device is measured to drop to 950cd / m 2 The time is in hours. The results are shown in Table 1.

[0168] Table 1 Performance results of organic electroluminescent devices

[0169]

[0170] As can be seen from Table 1, compounds A1, A2, A3, A4, A5, A7, A15, and A24 prepared in the present application are used as electron transport materials in organic electroluminescent devices, which can effectively reduce the driving voltage, improve the current efficiency, and extend the service life of the device, and are electron transport materials with good performance.

[0171] 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, wherein The compound is selected from the following compounds A2, A4, A5, A7, A15, A24: 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 . A display device comprising the organic electroluminescent device according to claim 3.

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