CN113264911A - Compound, organic light-emitting material and organic electroluminescent device - Google Patents

Compound, organic light-emitting material and organic electroluminescent device Download PDF

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CN113264911A
CN113264911A CN202110485521.0A CN202110485521A CN113264911A CN 113264911 A CN113264911 A CN 113264911A CN 202110485521 A CN202110485521 A CN 202110485521A CN 113264911 A CN113264911 A CN 113264911A
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邢其锋
丰佩川
单鸿斌
马艳
胡灵峰
陈跃
陈义丽
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Yantai Xianhua Chem Tech Co ltd
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Abstract

The present application provides aThe compound of the general formula (I) has a parent structure of s-triphenyl substituted anthracene, has high bond energy among atoms, good thermal stability, is favorable for intermolecular solid-state accumulation, has large bandwidth, has a light-emitting region in a blue light region, high light-emitting intensity, has a proper energy level with an adjacent layer, and is favorable for exciton injection and transfer. When the blue light host material is used as a blue light host material in a light-emitting layer, the driving voltage of an organic electroluminescent device can be effectively reduced, the light-emitting efficiency is improved, and the service life is prolonged. The present application also provides an organic electroluminescent device and a display device comprising the compound of formula (I).
Figure DDA0003050504930000011

Description

Compound, organic light-emitting material and organic electroluminescent device
Technical Field
The application relates to the technical field of organic light-emitting display, in particular to a compound, an organic light-emitting material and an organic electroluminescent device.
Background
Electroluminescence (EL) refers to a phenomenon in which a light emitting material emits light when excited by current and voltage under the action of an electric field, and is a light emitting process in which electric energy is directly converted into light energy. The organic electroluminescent display (hereinafter referred to as OLED) has a series of advantages of self-luminescence, low-voltage dc driving, full curing, wide viewing angle, light weight, simple composition and process, etc., and compared with the liquid crystal display, the organic electroluminescent display does not need a backlight source, and has a large viewing angle, low power, a response speed 1000 times that of the liquid crystal display, and a manufacturing cost lower than that of the liquid crystal display with the same resolution. Therefore, the organic electroluminescent device has very wide application prospect.
With the continuous advance of the OLED technology in the two fields of lighting and display, people pay more attention to the research on efficient organic materials affecting the performance of OLED devices, and an organic electroluminescent device with good efficiency and long service life is generally the result of the optimized matching of device structures and various organic materials, which provides great opportunities and challenges for chemists to design and develop functional materials with various structures.
Organic electroluminescent materials have many advantages over inorganic luminescent materials, such as: the processing performance is good, a film can be formed on any substrate by an evaporation or spin coating method, flexible display and large-area display can be realized, the optical performance, the electrical performance, the stability and the like of the material can be adjusted by changing the structure of molecules, and the selection of the material has a large space. In the most common OLED device structures, the following classes of organic materials are typically included: hole injection materials, hole transport materials, electron transport materials, and light emitting materials (including host materials and guest materials), etc., and the most important factor determining the light emitting efficiency of the OLED is the light emitting material.
Disclosure of Invention
In view of the above problems of the prior art, it is an object of the present application to provide a blue organic light emitting material.
A first aspect of the present application provides a compound of general formula (I):
Figure BDA0003050504910000021
wherein the content of the first and second substances,
ar is selected from C unsubstituted or substituted by Rc6-C30Aryl, C unsubstituted or substituted by Rc3-C30A heteroaryl group;
x is O, S or CRaRb, Ra and Rb are independently selected from C1-C10Alkyl radical, C3-C6Cycloalkyl, C unsubstituted or substituted by Rc6-C30Aryl, C unsubstituted or substituted by Rc3-C30Heteroaryl, unsubstituted or substituted by RcSubstituted amino, and adjacent Ra and Rb can be connected to form a ring;
R1-R5are identical or different from each other and are independently selected from hydrogen, deuterium, C1-C10Alkyl radical, C3-C6Cycloalkyl, C unsubstituted or substituted by Rc6-C30Aryl, C unsubstituted or substituted by Rc3-C30Heteroaryl, amino unsubstituted or substituted by Rc, and adjacent R1-R5Can be connected into a ring;
R6-R13are identical or different from each other and are independently selected from hydrogen, deuterium, C1-C10Alkyl radical, C3-C6Cycloalkyl radical, C1-C6Heteroalkyl, C unsubstituted or substituted by Rc6-C30Aryl, C unsubstituted or substituted by Rc3-C30Heteroaryl, amino unsubstituted or substituted by Rc, and adjacent R6-R13Can be connected into a ring;
Y1-Y8equal to or different from each other and independently from each other selected from CR or N, R is selected from hydrogen, deuterium, C1-C10Alkyl radical, C3-C6Cycloalkyl, C unsubstituted or substituted by Rc6-C30Aryl, C unsubstituted or substituted by Rc3-C30Heteroaryl, amino unsubstituted or substituted by Rc, and adjacent R can be connected to form a ring;
the heteroatoms on the heteroaryl and the heteroalkyl are each independently selected from O, S or N;
the substituents Rc of the various radicals may be identical or different and are each independently selected from deuterium, halogen, nitro, cyano, C1-C4Alkyl, phenyl, biphenyl, terphenyl, or naphthyl.
A second aspect of the present application provides an organic light emitting material comprising at least one of the compounds provided herein.
A third aspect of the present application provides an organic electroluminescent device comprising at least one of the organic light-emitting materials provided herein.
A fourth aspect of the present application provides a display apparatus comprising an organic electroluminescent device as provided herein.
The compound provided by the application has a parent structure of s-triphenyl substituted anthracene, has high bond energy among atoms, good thermal stability, is favorable for intermolecular solid-state accumulation, and simultaneously has large bandwidth, a light-emitting region is positioned in a blue light region, and the light-emitting intensity is high. When the blue light host material is used as a blue light host material and applied to a light emitting layer, the blue light host material has a proper energy level with the adjacent layers, is favorable for the injection and the migration of excitons, can effectively reduce the driving voltage, has a high exciton migration rate, and can realize good light emitting efficiency and service life in an organic electroluminescent device. The compound has a large conjugated plane, is beneficial to molecular accumulation, shows good thermodynamic stability and shows long service life in a device. The organic electroluminescent device comprises the compound as a blue luminescent material, so that the driving voltage can be effectively reduced, the luminous efficiency is improved, and the service life of the organic electroluminescent device is prolonged. The display device provided by the application has an excellent display effect.
Meanwhile, the preparation process of the compound is simple and feasible, the raw materials are easy to obtain, and the compound is suitable for industrial production.
Of course, not all advantages described above need to be achieved at the same time in the practice of any one product or method of the present application.
Drawings
Fig. 1 is a schematic structural view of a typical organic electroluminescent device.
Detailed Description
The technical solutions in the present application will be described clearly and completely with reference to the accompanying drawings, and it is to be understood that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments in this application are within the scope of protection of this application.
A first aspect of the present application provides a compound of general formula (I):
Figure BDA0003050504910000041
wherein the content of the first and second substances,
ar is selected from C unsubstituted or substituted by Rc6-C30Aryl, C unsubstituted or substituted by Rc3-C30A heteroaryl group;
x is O, S or CRaRb, Ra and Rb are independently selected from C1-C10Alkyl radical, C3-C6Cycloalkyl, C unsubstituted or substituted by Rc6-C30Aryl, C unsubstituted or substituted by Rc3-C30Heteroaryl, amino unsubstituted or substituted by Rc, and adjacent Ra and Rb can be linked together to form a ring;
R1-R5are identical or different from each other and are independently selected from hydrogen, deuterium, C1-C10Alkyl radical, C3-C6Cycloalkyl, C unsubstituted or substituted by Rc6-C30Aryl, C unsubstituted or substituted by Rc3-C30Heteroaryl, amino unsubstituted or substituted by Rc, and adjacent R1-R5Can be connected into a ring;
R6-R13are identical or different from each other and are independently selected from hydrogen, deuterium, C1-C10Alkyl radical, C3-C6Cycloalkyl radical, C1-C6Heteroalkyl, C unsubstituted or substituted by Rc6-C30Aryl, C unsubstituted or substituted by Rc3-C30Heteroaryl, amino unsubstituted or substituted by Rc, and adjacent R6-R13Can be connected into a ring;
Y1-Y8equal to or different from each other and independently from each other selected from CR or N, R is selected from hydrogen, deuterium, C1-C10Alkyl radical, C3-C6Cycloalkyl, C unsubstituted or substituted by Rc6-C30Aryl, C unsubstituted or substituted by Rc3-C30Heteroaryl, amino unsubstituted or substituted by Rc, and between adjacent RCan be connected into a ring;
the heteroatoms on the heteroaryl and the heteroalkyl are each independently selected from O, S or N;
the substituents Rc of the various radicals may be identical or different and are each independently selected from deuterium, halogen, nitro, cyano, C1-C4Alkyl, phenyl, biphenyl, terphenyl, or naphthyl.
Preferably, Ar is selected from C unsubstituted or substituted by Rc6-C18Aryl, C unsubstituted or substituted by Rc3-C18A heteroaryl group;
preferably, Ra, Rb are independently of each other selected from C1-C6Alkyl radical, C3-C6Cycloalkyl, C unsubstituted or substituted by Rc6-C18Aryl, C unsubstituted or substituted by Rc3-C18Heteroaryl, amino unsubstituted or substituted by Rc, and adjacent Ra and Rb can be linked together to form a ring;
preferably, R1-R5Are identical or different from each other and are independently selected from hydrogen, deuterium, C1-C6Alkyl radical, C3-C6Cycloalkyl, C unsubstituted or substituted by Rc6-C18Aryl, C unsubstituted or substituted by Rc3-C18Heteroaryl, amino unsubstituted or substituted by Rc, and adjacent R1-R5Can be connected into a ring;
preferably, R6-R13Are identical or different from each other and are independently selected from hydrogen, deuterium, C1-C6Alkyl radical, C3-C6Cycloalkyl radical, C1-C3Heteroalkyl, C unsubstituted or substituted by Rc6-C18Aryl, C unsubstituted or substituted by Rc3-C18Heteroaryl, amino unsubstituted or substituted by Rc, and adjacent R6-R13Can be connected into a ring;
preferably, R is selected from hydrogen, deuterium, C1-C6Alkyl radical, C3-C6Cycloalkyl, C unsubstituted or substituted by Rc6-C18Aryl, unsubstituted or substituted by RcSubstituted C3-C18Heteroaryl, amino unsubstituted or substituted by Rc, and adjacent R can be linked to form a ring.
More preferably, R1-R5Independently of one another, from hydrogen, deuterium, methyl, ethyl, cyclopentyl, cyclohexyl, the following groups unsubstituted or substituted by Rc: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furyl, benzofuryl, dibenzofuryl, aza-dibenzofuryl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, spirofluorenyl, arylamino, carbazolyl.
More preferably, R6-R13Independently of one another, from hydrogen, deuterium, methyl, ethyl, cyclopentyl, cyclohexyl, the following groups unsubstituted or substituted by Rc: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furyl, benzofuryl, dibenzofuryl, aza-dibenzofuryl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, spirofluorenyl, arylamino, carbazolyl.
More preferably, R is selected from hydrogen, deuterium, methyl, ethyl, cyclopentyl, cyclohexyl, the following groups unsubstituted or substituted by Rc: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furyl, benzofuryl, dibenzofuryl, aza-dibenzofuryl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, spirofluorenyl, arylamino, carbazolyl.
More preferably, Ra, Rb are independently from each other selected from methyl, ethyl, cyclopentyl, cyclohexyl, the following groups unsubstituted or substituted by Rc: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furyl, benzofuryl, dibenzofuryl, aza-dibenzofuryl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, spirofluorenyl, arylamino, carbazolyl.
For example, the compound of formula (I) may be selected from the compounds represented by a1 to a35 below:
Figure BDA0003050504910000061
Figure BDA0003050504910000071
the compound of the general formula (I) provided by the application has high bond energy among atoms, has good thermal stability and is beneficial to solid-state accumulation among molecules. Meanwhile, the bandwidth is large, the light emitting area is located in a blue light area, and the light emitting intensity is high. In addition, the preparation process of the compound of the general formula (I) is simple and easy to implement, raw materials are easy to obtain, and the method is suitable for industrial production.
A second aspect of the present application provides an organic light emitting material comprising at least one of the compounds provided herein.
In the present application, the above-mentioned organic light emitting material may be used as a blue host material in an organic electroluminescent device.
When the organic luminescent material is used as a blue light main body material in a luminescent layer, the organic luminescent material has a proper energy level with an adjacent layer, so that exciton injection and transfer are facilitated, and driving voltage can be effectively reduced. Meanwhile, the organic electroluminescent device has higher exciton migration rate, and can realize good luminous efficiency and service life in the organic electroluminescent device. The organic electroluminescent material also has a larger conjugated plane, is beneficial to molecular accumulation, shows good thermodynamic stability, and can prolong the service life when being used in an organic electroluminescent device.
A third aspect of the present application provides an organic electroluminescent device comprising at least one of the organic light-emitting materials provided herein. Therefore, the organic electroluminescent device provided by the application has low driving voltage, high luminous efficiency and long service life.
In the present application, there is no particular limitation on the kind and structure of the organic electroluminescent device as long as the organic light emitting material provided herein can be used.
The organic electroluminescent device of the present application may be a light-emitting device having a top emission structure, and examples thereof include a light-emitting device comprising an anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a transparent or translucent cathode in this order on a substrate.
The organic electroluminescent device of the present application may be a light-emitting device having a bottom emission structure, and may include a structure in which a transparent or translucent anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a cathode are sequentially provided on a substrate.
The organic electroluminescent device of the present application may be a light-emitting device having a double-sided light-emitting structure, and may include a structure in which a transparent or translucent 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 translucent cathode are sequentially provided on a substrate.
In addition, an electron blocking layer may be provided between the hole transport layer and the light emitting layer, a hole blocking layer may be provided 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 outgoing side. However, the structure of the organic electroluminescent device of the present application is not limited to the above-described specific structure, and the above-described layers may be omitted or added if necessary. The thickness of each layer is not particularly limited as long as the object of the present invention 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 semitransparent cathode, and a light extraction layer (50nm to 90nm) in this order on a substrate.
Fig. 1 shows a schematic diagram of a typical organic electroluminescent device, in which a substrate 1, a reflective anode electrode 2, a hole injection layer 3, a hole transport layer 4, a light-emitting layer 5, an electron transport layer 6, an electron injection layer 7, and a cathode electrode 8 are sequentially disposed from bottom to top.
It is to be understood that fig. 1 only schematically illustrates the structure of a typical organic electroluminescent device, and the present application is not limited to this structure, and the organic luminescent material of the present application may be used in any type of organic electroluminescent device.
For convenience, the organic electroluminescent device of the present application is described below with reference to fig. 1, but this is not meant to limit the scope of the present application in any way. It is understood that all organic electroluminescent devices capable of using the organic light emitting material of the present application are within the scope of the present application.
In the present application, the substrate 1 is not particularly limited, and conventional substrates used in organic electroluminescent devices in the related art, such as glass, polymer materials, and glass and polymer materials with Thin Film Transistor (TFT) components, etc., may be used.
In the present application, the reflective anode material 2 is not particularly limited, and may be selected from Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), tin dioxide (SnO) known in the art2) The transparent conductive material such as zinc oxide (ZnO) may be selected from a metal material such as silver and an alloy thereof, aluminum and an alloy thereof, an organic conductive material such as poly-3, 4-ethylenedioxythiophene (PEDOT), a multilayer structure of the above materials, and the like.
In the present application, the material of the hole injection layer 3 is not particularly limited, and may be made of a hole injection layer material known in the art. For example, at least one of known Hole Transport Materials (HTM) is selected as the hole injection material.
In the present application, the hole injection layer 3 may further include a p-type dopant, the type of which 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 is not limited to, at least one of the following p-1 to p-3 compounds:
Figure BDA0003050504910000101
in the present application, the amount of the p-type dopant is not particularly limited and may be an amount well known to those skilled in the art.
In the present application, the material of the hole transport layer 4 is not particularly limited, and may be made using a Hole Transport Material (HTM) known in the art. The number of layers of the hole transport layer 4 is not particularly limited, and may be adjusted as needed as long as it satisfies the object of the present application, for example, 1 layer, 2 layers, 3 layers, 4 layers or more.
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:
Figure BDA0003050504910000102
Figure BDA0003050504910000111
in the present application, the material of the light emitting layer 5 may include a host material and a guest material.
In the present application, the host material may include at least one of the organic light emitting materials of the present application, and may also include a combination of at least one of the organic light emitting materials of the present application and at least one of the known host materials.
For example, known host materials may be selected from, but are not limited to, at least one of the following BH-1 to BH-10 compounds:
Figure BDA0003050504910000121
in the present application, the guest material is not particularly limited, and at least one of light-emitting layer guest materials known in the art may be used. For example, the light-emitting layer guest material may be selected from, but is not limited to, at least one of the following BD-1 to BD-9 compounds:
Figure BDA0003050504910000122
Figure BDA0003050504910000131
in the present application, the amount of the guest material of the light-emitting layer is not particularly limited and may be an amount well known to those skilled in the art.
In the present application, the material of the electron transport layer 6 is not particularly limited, and electron transport materials known in the art may be used. The number of the electron transport layers 6 is not particularly limited, and may be adjusted according to actual needs as long as the object of the present application is satisfied, for example, 1,2, 3,4 or more layers.
For example, known electron transport materials may be selected from, but are not limited to, at least one of the following ET-1 to ET-57 compounds:
Figure BDA0003050504910000132
Figure BDA0003050504910000141
Figure BDA0003050504910000151
Figure BDA0003050504910000161
in the present application, the electron transport layer 6 may further include an n-type dopant, the kind of the n-type dopant is not particularly limited, and various n-type dopants known in the art may be employed, for example, the following n-type dopants may be employed:
Figure BDA0003050504910000162
in the present application, the amount of the n-type dopant is not particularly limited and may be an amount well known to those skilled in the art.
In the present application, the material of the electron injection layer 7 is not particularly limited, and electron injection materials known in the art may be used, and for example, may include, but are not limited to, LiQ, LiF, NaCl, CsF, Li in the prior art2O、Cs2CO3At least one of BaO, Na, Li, Ca and the like.
In the present application, the material of the cathode electrode 8 is not particularly limited, and may be selected from, but not limited to, magnesium silver mixture, metal such as LiF/Al, ITO, Al, etc., metal mixture, oxide, etc.
A fourth aspect of the present application provides a display device comprising the organic electroluminescent device provided by the present application. The display device includes, but is not limited to, a display, a television, a tablet computer, a mobile communication terminal, etc.
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:
(1) cleaning a reflective anode electrode 2 on an OLED device substrate 1 for top emission, respectively carrying out steps of medicinal washing, water washing, hairbrush, high-pressure water washing, air knife and the like in a cleaning machine, and then carrying out heat treatment;
(2) vacuum evaporating a hole injection material on the reflective anode electrode 2 to form a hole injection layer 3;
(3) vacuum evaporating a hole transport material on the hole injection layer 3 to form a hole transport layer 4;
(4) a luminescent layer 5 is evaporated on the hole transport layer 4 in vacuum, wherein the luminescent layer 5 comprises a host material and a guest material;
(5) vacuum evaporating an electron transport material on the luminescent layer 5 to form an electron transport layer 6;
(6) vacuum evaporating an electron injection material on the electron transport layer 6 to form an electron injection layer 7;
(7) a cathode material is vacuum-deposited on the electron injection layer 7 as a cathode electrode 8.
The above description has been made only of the structure of a typical organic electroluminescent device and a method for manufacturing the same, and it should be understood that the present application is not limited to this structure. The organic light emitting material of the present application may be used for an organic electroluminescent device of any structure, and the organic electroluminescent device may be manufactured using any manufacturing method known in the art.
The method for synthesizing the compound of the present application is not particularly limited, and the synthesis can be carried out by any method known to those skilled in the art. The following illustrates the synthesis of the compounds of the present application.
Synthesis example 1 Synthesis of Compound A1
Figure BDA0003050504910000171
Into a reaction flask were charged 100mmol of 4- (3-dibenzofuran) bromobenzene, 100mmol of 9-anthraceneboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 1 mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) was added3)4) And reacting at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M1. Wherein, Pd (PPh)3)4Is added in an amount of 4- (3-diphenyl)And furan) 1 mol% of bromobenzene.
100mmol of M1 and 500ml of dichloromethane are added into a single-mouth bottle, the temperature is reduced to 0 ℃, 100mmol of N-bromosuccinimide (NBS) is added in batches, the temperature is kept at 0 ℃ for 1h, the reaction is carried out for 3h, and the disappearance of the raw materials is monitored by thin-layer chromatography (TLC). Water was added to the reaction solution, extracted with ethyl acetate, and the organic phase was concentrated to give brown solid M2.
Into a reaction flask were charged 100mmol of M2, 100mmol of pinacol diboron, 41.4g of potassium carbonate (300mmol) and 800ml of toluene, and 1 mol% of tris (dibenzylideneacetone) dipalladium (Pd)2(dba)3) And reacting at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M3. Wherein, Pd2(dba)3Was added in an amount of 1 mol% based on M2.
Into a reaction flask were charged 100mmol of 1-iodo-3-bromo-5-chlorobenzene, 100mmol of phenylboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4And reacting at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M4. Wherein, Pd (PPh)3)4The amount of the compound (A) added is 1 mol% of 1-iodo-3-bromo-5-chlorobenzene.
Into a reaction flask were charged 100mmol of M4, 100mmol of 2-dibenzofuranboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4And reacting at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M5. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M4.
Into a reaction flask were added 100mmol of M3, 100mmol of M5, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% Pd (PPh) was added3)4And reacting at 120 ℃ for 12 h. Stop after the reaction is finishedThe reaction was stopped, and the reaction was cooled to room temperature, water was added, filtered, washed with water, and the resulting solid was purified by recrystallization from toluene to give a white powder a 1. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M5.
1H NMR(400MHz,Chloroform)8.38–8.18(m,3H),7.99(d,J＝9.6Hz,4H),7.91–7.73(m,7H),7.66–7.53(m,5H),7.41(t,J＝10.0Hz,4H),7.36–7.28(m,8H),7.25(s,1H),7.11(s,1H).
Synthesis example 2 Synthesis of Compound A7
Figure BDA0003050504910000181
Into a reaction flask were added 100mmol of 4-bromo-9, 9-dimethylfluorene, 100mmol of 9-anthraceneboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4And reacting at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M1. Wherein, Pd (PPh)3)4The amount of (A) added was 1 mol% of 4-bromo-9, 9-dimethylfluorene.
100mmol of M1 and 500ml of dichloromethane are added into a single-mouth bottle, the temperature is reduced to 0 ℃, 100mmol of NBS is added in batches, the temperature is kept at 0 ℃ for 1h, the reaction is carried out for 3h, and the disappearance of the raw materials is monitored by TLC. Water was added to the reaction solution, extracted with ethyl acetate, and the organic phase was concentrated to give brown solid M2.
Into a reaction flask were charged 100mmol of M2, 100mmol of pinacol diboron, 41.4g of potassium carbonate (300mmol) and 800ml of toluene, and 1 mol% of Pd was added2(dba)3And reacting at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M3. Wherein, Pd2(dba)3Was added in an amount of 1 mol% based on M2.
100mmol of 1-iodo-3-bromo-5-chlorobenzene, 100mmol of phenylboronic acid and 41 were added to a reaction flask.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) are added3)4And reacting at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M4. Wherein, Pd (PPh)3)4The amount of the compound (A) added is 1 mol% of 1-iodo-3-bromo-5-chlorobenzene.
Into a reaction flask were charged 100mmol of M4, 100mmol of 2-dibenzofuranboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4And reacting at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M5. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M4.
Into a reaction flask were added 100mmol of M3, 100mmol of M5, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% Pd (PPh) was added3)4And reacting at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain a white powder a 7. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M5.
1H NMR(400MHz,Chloroform)8.34–8.21(m,4H),8.19(s,1H),7.98(s,1H),7.76(d,J＝12.0Hz,3H),7.69(s,1H),7.54(d,J＝8.0Hz,5H),7.52–7.31(m,6H),7.25–7.11(m,8H),7.04(s,1H),1.69(s,6H).
Synthesis example 3 Synthesis of Compound A9
Figure BDA0003050504910000201
Into a reaction flask were charged 100mmol of 1, 2-dibromonaphthalene, 100mmol of phenylboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4And reacting at 120 ℃ for 12 h. Inverse directionAfter completion of the reaction, the reaction was stopped and the reaction was cooled to room temperature, water was added, filtered, washed with water and the resulting solid was purified by recrystallization from toluene to give M1 as a white powder. Wherein, Pd (PPh)3)4The amount of (A) added is 1 mol% of 1, 2-dibromonaphthalene.
Into a reaction flask were charged 100mmol of M1, 100mmol of 9-anthraceneboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4And reacting at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M2. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M1.
100mmol of M2 and 500ml of dichloromethane are added into a single-mouth bottle, the temperature is reduced to 0 ℃, 100mmol of NBS is added in batches, the temperature is kept at 0 ℃ for 1h, the reaction is carried out for 3h, and the disappearance of the raw materials is monitored by TLC. Water was added to the reaction solution, extracted with ethyl acetate, and the organic phase was concentrated to give brown solid M3.
Into a reaction flask were charged 100mmol of M3, 100mmol of pinacol diboron, 41.4g of potassium carbonate (300mmol) and 800ml of toluene, and 1 mol% of Pd was added2(dba)3And reacting at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M4. Wherein, Pd2(dba)3Was added in an amount of 1 mol% based on M3.
Into a reaction flask were charged 100mmol of 1-iodo-3-bromo-5-chlorobenzene, 100mmol of 2-naphthylboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4And reacting at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M5. Wherein, Pd (PPh)3)4The amount of the compound (A) added is 1 mol% of 1-iodo-3-bromo-5-chlorobenzene.
100mmol of M5, 100mmol of 2-dibenzofuranboronic acid, and 41.4g of the mixture were charged in a reaction flaskPotassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) were added3)4And reacting at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M6. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M5.
Into a reaction flask were added 100mmol of M4, 100mmol of M6, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% Pd (PPh) was added3)4And reacting at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain a white powder a 9. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M6.
1H NMR(400MHz,Chloroform)8.93(s,1H),8.53(s,1H),8.33-8.21(m,4H),8.19–7.90(m,6H),7.69(s,1H),7.67–7.58(m,7H),7.55(d,J＝8.0Hz,6H),7.46–7.33(m,8H),7.31(s,1H).
Synthesis example 4 Synthesis of Compound A13
Figure BDA0003050504910000211
Into a reaction flask were charged 100mmol of bromobenzene, 100mmol of 9-anthraceneboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4And reacting at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M1. Wherein, Pd (PPh)3)4Is added in an amount of 1 mol% based on bromobenzene.
100mmol of M1 and 500ml of dichloromethane are added into a single-mouth bottle, the temperature is reduced to 0 ℃, 100mmol of NBS is added in batches, the temperature is kept at 0 ℃ for 1h, the reaction is carried out for 3h, and the disappearance of the raw materials is monitored by TLC. Water was added to the reaction solution, extracted with ethyl acetate, and the organic phase was concentrated to give brown solid M2.
Into a reaction flask were charged 100mmol of M2, 100mmol of pinacol diboron, 41.4g of potassium carbonate (300mmol) and 800ml of toluene, and 1 mol% of Pd was added2(dba)3And reacting at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M3. Wherein, Pd2(dba)3Was added in an amount of 1 mol% based on M2.
Into a reaction flask were charged 100mmol of 1-iodo-3-bromo-5-chlorobenzene, 100mmol of deuterated phenylboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4And reacting at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M4. Wherein, Pd (PPh)3)4The amount of the compound (A) added is 1 mol% of 1-iodo-3-bromo-5-chlorobenzene.
Into a reaction flask were charged 100mmol of M4, 100mmol of 2-dibenzofuranboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4And reacting at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M5. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M4.
Into a reaction flask were added 100mmol of M3, 100mmol of M5, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% Pd (PPh) was added3)4And reacting at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain a white powder a 13. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M5.
1H NMR(400MHz,Chloroform)8.37–8.19(m,4H),7.98(s,1H),7.69(s,1H),7.65(s,1H),7.54(dd,J＝12.8,7.6Hz,8H),7.40(d,J＝10.0Hz,6H),7.31(s,1H).
Synthesis example 5 Synthesis of Compound A17
Figure BDA0003050504910000221
Into a reaction flask were charged 100mmol of bromobenzene, 100mmol of 9-anthraceneboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4And reacting at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M1. Wherein, Pd (PPh)3)4Is added in an amount of 1 mol% based on bromobenzene.
100mmol of M1 and 500ml of dichloromethane are added into a single-mouth bottle, the temperature is reduced to 0 ℃, 100mmol of NBS is added in batches, the temperature is kept at 0 ℃ for 1h, the reaction is carried out for 3h, and the disappearance of the raw materials is monitored by TLC. Water was added to the reaction solution, extracted with ethyl acetate, and the organic phase was concentrated to give brown solid M2.
Into a reaction flask were charged 100mmol of M2, 100mmol of pinacol diboron, 41.4g of potassium carbonate (300mmol) and 800ml of toluene, and 1 mol% of Pd was added2(dba)3And reacting at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M3. Wherein, Pd2(dba)3Was added in an amount of 1 mol% based on M2.
Into a reaction flask were charged 100mmol of 1-iodo-3-bromo-5-chlorobenzene, 100mmol of 2- (9, 9-dimethylfluorene) boronic acid, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4And reacting at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M4. Wherein, Pd (PPh)3)4The amount of the compound (A) added is 1 mol% of 1-iodo-3-bromo-5-chlorobenzene.
Into a reaction flask were charged 100mmol of M4, 100mmol of 1-dibenzofuranboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4And reacting at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M5. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M4.
Into a reaction flask were added 100mmol of M3, 100mmol of M5, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% Pd (PPh) was added3)4And reacting at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain a white powder a 17. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M5.
1H NMR(400MHz,Chloroform)8.31(t,J＝7.6Hz,2H),8.21(s,1H),8.09(d,J＝8.8Hz,2H),7.98(s,1H),7.94(d,J＝10.0Hz,4H),7.78(s,1H),7.79–7.52(m,9H),7.41(t,J＝10.0Hz,6H),7.33(d,J＝8.4Hz,4H),7.24(s,1H),1.69(s,6H).
Synthesis example 6 Synthesis of Compound A21
Figure BDA0003050504910000241
Into a reaction flask were charged 100mmol of 2-bromo-9, 9-dimethylfluorene, 100mmol of 9-anthraceneboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4And reacting at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M1. Wherein, Pd (PPh)3)4The amount of (A) added was 1 mol% of 2-bromo-9, 9-dimethylfluorene.
100mmol of M1 and 500ml of dichloromethane are added into a single-mouth bottle, the temperature is reduced to 0 ℃, 100mmol of NBS is added in batches, the temperature is kept at 0 ℃ for 1h, the reaction is carried out for 3h, and the disappearance of the raw materials is monitored by TLC. Water was added to the reaction solution, extracted with ethyl acetate, and the organic phase was concentrated to give brown solid M2.
100mmol of M2, 100mmol of pinacol diborate, 41.4g of potassium carbonate (300mmol), 800ml of toluene and 1 mol% of Pd were charged in a reaction flask2(dba)3And reacting at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M3. Wherein, Pd2(dba)3Was added in an amount of 1 mol% based on M2.
Into a reaction flask were charged 100mmol of 1-iodo-3-bromo-5-chlorobenzene, 100mmol of 4- (3-pyridyl) phenylboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4And reacting at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M4. Wherein, Pd (PPh)3)4The amount of the compound (A) added is 1 mol% of 1-iodo-3-bromo-5-chlorobenzene.
Into a reaction flask were charged 100mmol of M4, 100mmol of 3-dibenzothiophene boronic acid, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4And reacting at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M5. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M4.
Into a reaction flask were added 100mmol of M3, 100mmol of M5, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% Pd (PPh) was added3)4And reacting at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain a white powder a 21. Wherein, Pd (PPh)3)4In an amount of M51mol％。
1H NMR(400MHz,Chloroform)9.24(s,1H),8.70(s,1H),8.46(d,J＝9.2Hz,2H),8.28–8.15(m,6H),8.08(d,J＝6.4Hz,2H),7.97(s,1H),7.86(s,1H),7.70(d,J＝14.4Hz,4H),7.60(d,J＝7.2Hz,4H),7.56(s,1H),7.47(s,1H),7.33(d,J＝8.4Hz,5H),7.25(d,J＝7.6Hz,4H),1.69(s,6H).
Synthesis example 7 Synthesis of Compound A22
Figure BDA0003050504910000251
Into a reaction flask were charged 100mmol of 4- (2-pyridyl) bromobenzene, 100mmol of 9-anthraceneboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4And reacting at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M1. Wherein, Pd (PPh)3)4The amount of (b) added was 1 mol% based on 4- (2-pyridyl) bromobenzene.
100mmol of M1 and 500ml of dichloromethane are added into a single-mouth bottle, the temperature is reduced to 0 ℃, 100mmol of NBS is added in batches, the temperature is kept at 0 ℃ for 1h, the reaction is carried out for 3h, and the disappearance of the raw materials is monitored by TLC. Water was added to the reaction solution, extracted with ethyl acetate, and the organic phase was concentrated to give brown solid M2.
Into a reaction flask were charged 100mmol of M2, 100mmol of pinacol diboron, 41.4g of potassium carbonate (300mmol) and 800ml of toluene, and 1 mol% of Pd was added2(dba)3And reacting at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M3. Wherein, Pd2(dba)3Was added in an amount of 1 mol% based on M2.
Into a reaction flask were charged 100mmol of 1-iodo-3-bromo-5-chlorobenzene, 100mmol of phenylboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4At 120 ℃ by reactionAnd the time is 12 hours. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M4. Wherein, Pd (PPh)3)4The amount of the compound (A) added is 1 mol% of 1-iodo-3-bromo-5-chlorobenzene.
Into a reaction flask were charged 100mmol of M4, 100mmol of 2-dibenzofuranboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4And reacting at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M5. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M4.
Into a reaction flask were added 100mmol of M3, 100mmol of M5, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% Pd (PPh) was added3)4And reacting at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain a white powder a 22. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M5.
1H NMR(400MHz,Chloroform)8.69(s,1H),8.39(d,J＝7.6Hz,2H),8.38–8.14(m,4H),8.18(s,4H),7.98(s,1H),7.75(s,1H),7.66(d,J＝10.0Hz,2H),7.54–7.45(m,6H),7.34–7.07(m,7H),6.90(s,1H).
Synthesis example 8 Synthesis of Compound A31
Figure BDA0003050504910000271
Into a reaction flask were charged 100mmol of 2-bromonaphthalene, 100mmol of 9-anthraceneboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4And reacting at 120 ℃ for 12 h. Stopping reaction after the reaction is finished, cooling the reactant to room temperature, adding water, filtering, washing with water, and carrying out the reaction on the obtained solid by using tolueneRecrystallization purification gave white powder M1. Wherein, Pd (PPh)3)4The amount of (B) added is 1 mol% of 2-bromonaphthalene.
100mmol of M1 and 500ml of dichloromethane are added into a single-mouth bottle, the temperature is reduced to 0 ℃, 100mmol of NBS is added in batches, the temperature is kept at 0 ℃ for 1h, the reaction is carried out for 3h, and the disappearance of the raw materials is monitored by TLC. Water was added to the reaction solution, extracted with ethyl acetate, and the organic phase was concentrated to give brown solid M2.
Into a reaction flask were charged 100mmol of M2, 100mmol of pinacol diboron, 41.4g of potassium carbonate (300mmol) and 800ml of toluene, and 1 mol% of Pd was added2(dba)3And reacting at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M3. Wherein, Pd2(dba)3Was added in an amount of 1 mol% based on M2.
Into a reaction flask were charged 100mmol of 1-iodo-3-bromo-5-chlorobenzene, 100mmol of phenylboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4And reacting at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M4. Wherein, Pd (PPh)3)4The amount of the compound (A) added is 1 mol% of 1-iodo-3-bromo-5-chlorobenzene.
Into a reaction flask were charged 100mmol of 2-fluoro-3-bromo-5-chloropyridine, 100mmol of 2-hydroxyphenylboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4And reacting at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M5. Wherein, Pd (PPh)3)4The amount of the compound (b) added is 1 mol% of 2-fluoro-3-bromo-5-chloropyridine.
100mmol of M5, 41.4g of potassium carbonate (300mmol) and 500ml of N, N-Dimethylformamide (DMF) were charged in a reaction flask and reacted at 120 ℃ for 12 hours. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M6.
Into a reaction flask were charged 100mmol of M6, 100mmol of pinacol diboron, 41.4g of potassium carbonate (300mmol) and 800ml of toluene, and 1 mol% of Pd was added2(dba)3And reacting at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M7. Wherein, Pd2(dba)3Was added in an amount of 1 mol% based on M6.
Into a reaction flask were added 100mmol of M4, 100mmol of M7, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% Pd (PPh) was added3)4And reacting at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M8. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M4.
Into a reaction flask were added 100mmol of M3, 100mmol of M8, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% Pd (PPh) was added3)4And reacting at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain a white powder a 31. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M8.
1H NMR(400MHz,Chloroform)9.24(s,1H),8.48(s,1H),8.26(dd,J＝13.6,9.2Hz,6H),8.08(d,J＝12.0Hz,2H),7.98(d,J＝8.0Hz,2H),7.63(s,1H),7.57(d,J＝12.0Hz,2H),7.49(d,J＝8.0Hz,5H),7.41(t,J＝12.4Hz,6H),7.30(d,J＝12.0Hz,4H).
Synthesis example 9 Synthesis of Compound A34
Figure BDA0003050504910000281
Into a reaction flask were charged 100mmol of 2-bromobiphenyl, 100mmol of 9-anthraceneboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4And reacting at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M1. Wherein, Pd (PPh)3)4Is added in an amount of 1 mol% based on the 2-bromobiphenyl.
100mmol of M1 and 500ml of dichloromethane are added into a single-mouth bottle, the temperature is reduced to 0 ℃, 100mmol of NBS is added in batches, the temperature is kept at 0 ℃ for 1h, the reaction is carried out for 3h, and the disappearance of the raw materials is monitored by TLC. Water was added to the reaction solution, extracted with ethyl acetate, and the organic phase was concentrated to give brown solid M2.
Into a reaction flask were charged 100mmol of M2, 100mmol of pinacol diboron, 41.4g of potassium carbonate (300mmol) and 800ml of toluene, and 1 mol% of Pd was added2(dba)3And reacting at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M3. Wherein, Pd2(dba)3Was added in an amount of 1 mol% based on M2.
Into a reaction flask were charged 100mmol of 1-iodo-3-bromo-5-chlorobenzene, 100mmol of phenylboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4And reacting at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M4. Wherein, Pd (PPh)3)4The amount of the compound (A) added is 1 mol% of 1-iodo-3-bromo-5-chlorobenzene.
Into a reaction flask were charged 100mmol of M4, 100mmol of 9, 9-spirobifluorene-2-boronic acid, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4And reacting at 120 ℃ for 12 h. Stopping reaction after the reaction is finished, cooling the reactant to room temperature, adding water, filtering, washing with water to obtainThe solid of (2) was purified by recrystallization from toluene to give M5 as a white powder. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M4.
Into a reaction flask were added 100mmol of M3, 100mmol of M5, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% Pd (PPh) was added3)4And reacting at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain a white powder a 34. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M5.
1H NMR(400MHz,Chloroform)8.97(s,1H),8.27(s,1H),8.21(dd,J＝13.2,8.8Hz,6H),8.19–8.07(m,3H),7.96(s,1H),7.95–7.92(m,4H),7.85–7.64(m,9H),7.60(s,1H),7.45(dd,J＝12.8,8.4Hz,6H),7.24(d,J＝8.0Hz,8H).
Other compounds of the present application can be synthesized by selecting suitable starting materials according to the above-mentioned concept of synthetic examples 1 to 9, and also by selecting any other suitable methods and starting materials.
Example 1
Carrying out ultrasonic treatment on the glass plate coated with the ITO transparent conductive layer in a commercial cleaning agent, washing in deionized water, carrying out ultrasonic oil removal in an acetone-ethanol mixed solvent, baking in a clean environment until the water is completely removed, cleaning by using ultraviolet light and ozone, and bombarding the surface by using low-energy solar beams;
then, the glass substrate with the anode is placed in a vacuum chamber and is vacuumized to be less than 10 DEG-5In the torr state, a hole injection layer is evaporated on the anode layer film in vacuum, the material of the hole injection layer comprises a hole injection layer material HT-11 and a p-type dopant p-1, and evaporation is carried out by utilizing a multi-source co-evaporation method, wherein the evaporation rate of the hole injection layer material HT-11 is adjusted to be 0.1nm/s, the evaporation rate of the p-type dopant p-1 is 3 percent of the evaporation rate of the hole injection layer material HT-11, and the thickness of the evaporation film is 10 nm;
then, vacuum evaporating a hole transport material HT-5 on the hole injection layer to be used as a hole transport layer, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 80 nm;
then, a luminescent layer is evaporated on the hole transport layer in vacuum, the luminescent layer comprises a host material A1 and a guest material BD-1, evaporation is carried out by a multi-source co-evaporation method, wherein the evaporation rate of the host material A1 is adjusted to be 0.1nm/s, the evaporation rate of the guest material BD-1 is 3% of the evaporation rate of the host material A1, and the thickness of the evaporation film is 30 nm;
then, an electron transport layer is vacuum-evaporated on the light emitting layer, wherein the electron transport material is ET-42, the evaporation rate is 0.1nm/s, and the evaporation film thickness is 30 nm;
then, carrying out vacuum evaporation on the LiF with the thickness of 0.5nm on the electron transport layer to serve as an electron injection layer, wherein the evaporation rate is 0.1 nm/s;
and finally, performing vacuum evaporation on the electron injection layer to form an Al layer with the thickness of 150nm as a cathode electrode of the organic electroluminescent device, wherein the evaporation rate is 0.1 nm/s.
Example 2
The same as example 1 except that A7 was used as a host material for a light-emitting layer.
Example 3
The same as example 1 except that A9 was used as a host material for a light-emitting layer.
Example 4
The same as example 1 except that A13 was used as a host material for a light-emitting layer.
Example 5
The same as example 1 except that A17 was used as a host material for a light-emitting layer.
Example 6
The same as example 1 except that A21 was used as a host material for a light-emitting layer.
Example 7
The same as example 1 except that A22 was used as a host material for a light-emitting layer.
Example 8
The same as example 1 except that A31 was used as a host material for a light-emitting layer.
Example 9
The same as example 1 except that A34 was used as a host material for a light-emitting layer.
Comparative example 1
The same as example 1 except that BH-1 was used as the light-emitting layer host material.
The organic electroluminescent device prepared by the above process was subjected to the following performance measurement:
the organic electroluminescent devices prepared in examples 1 to 9 and comparative example 1 were measured for driving voltage, current efficiency and lifetime at the same luminance using a digital source meter and a luminance meter, and specifically, the luminance of the organic electroluminescent device was measured to reach 1000cd/m at a rate of 0.1V/sec by increasing the voltage2The current density is measured at the same time as the driving voltage; the ratio of the brightness to the current density is the current efficiency; the life test of LT95 is as follows: using a luminance meter at 1000cd/m2The luminance drop of the organic electroluminescent device was measured to 950cd/m by maintaining a constant current at luminance2Time in hours. The results are shown in Table 1.
Table 1 organic electroluminescent device performance results
Figure BDA0003050504910000321
As can be seen from table 1, the compounds a1, a7, a9, a13, a17, a21, a22, a31, and a34 prepared by the present invention are blue host materials with good performance, which can effectively reduce driving voltage, improve current efficiency, and prolong the service life of the device, when used as host materials of light emitting layers in organic electroluminescent devices.
The above description is only for the preferred embodiment of the present application and is not intended to limit the scope of the present application. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application are included in the protection scope of the present application.

Claims (11)

1. A compound of the general formula (I):
Figure FDA0003050504900000011
wherein the content of the first and second substances,
ar is selected from C unsubstituted or substituted by Rc6-C30Aryl, C unsubstituted or substituted by Rc3-C30A heteroaryl group;
x is O, S or CRaRb, Ra and Rb are independently selected from C1-C10Alkyl radical, C3-C6Cycloalkyl, C unsubstituted or substituted by Rc6-C30Aryl, C unsubstituted or substituted by Rc3-C30Heteroaryl, amino unsubstituted or substituted by Rc, and adjacent Ra and Rb can be linked together to form a ring;
R1-R5are identical or different from each other and are independently selected from hydrogen, deuterium, C1-C10Alkyl radical, C3-C6Cycloalkyl, C unsubstituted or substituted by Rc6-C30Aryl, C unsubstituted or substituted by Rc3-C30Heteroaryl, amino unsubstituted or substituted by Rc, and adjacent R1-R5Can be connected into a ring;
R6-R13are identical or different from each other and are independently selected from hydrogen, deuterium, C1-C10Alkyl radical, C3-C6Cycloalkyl radical, C1-C6Heteroalkyl, C unsubstituted or substituted by Rc6-C30Aryl, C unsubstituted or substituted by Rc3-C30Heteroaryl, amino unsubstituted or substituted by Rc, and adjacent R6-R13Can be connected into a ring;
Y1-Y8equal to or different from each other and independently from each other selected from CR or N, R is selected from hydrogen, deuterium, C1-C10Alkyl radical, C3-C6Cycloalkyl, C unsubstituted or substituted by Rc6-C30Aryl, C unsubstituted or substituted by Rc3-C30Heteroaryl, amino unsubstituted or substituted by Rc, and adjacent R can be connected to form a ring;
the heteroatoms on the heteroaryl and the heteroalkyl are each independently selected from O, S or N;
the substituents Rc of the various radicals may be identical or different and are each independently selected from deuterium, halogen, nitro, cyano, C1-C4Alkyl, phenyl, biphenyl, terphenyl, or naphthyl.
2. The compound of claim 1, wherein,
ar is selected from C unsubstituted or substituted by Rc6-C18Aryl, C unsubstituted or substituted by Rc3-C18A heteroaryl group;
ra and Rb are independently selected from C1-C6Alkyl radical, C3-C6Cycloalkyl, C unsubstituted or substituted by Rc6-C18Aryl, C unsubstituted or substituted by Rc3-C18Heteroaryl, amino unsubstituted or substituted by Rc, and adjacent Ra and Rb can be linked together to form a ring;
R1-R5are identical or different from each other and are independently selected from hydrogen, deuterium, C1-C6Alkyl radical, C3-C6Cycloalkyl, C unsubstituted or substituted by Rc6-C18Aryl, C unsubstituted or substituted by Rc3-C18Heteroaryl, amino unsubstituted or substituted by Rc, and adjacent R1-R5Can be connected into a ring;
R6-R13are identical or different from each other and are independently selected from hydrogen, deuterium, C1-C6Alkyl radical, C3-C6Cycloalkyl radical, C1-C3Heteroalkyl, C unsubstituted or substituted by Rc6-C18Aryl, C unsubstituted or substituted by Rc3-C18Heteroaryl, amino unsubstituted or substituted by Rc, and adjacent R6-R13Can be connected into a ring;
r is selected from hydrogen, deuterium and C1-C6Alkyl radical, C3-C6Cycloalkyl, C unsubstituted or substituted by Rc6-C18Aryl, C unsubstituted or substituted by Rc3-C18Heteroaryl, amino unsubstituted or substituted by Rc, and adjacent R can be linked to form a ring.
3. The compound of claim 1, wherein R1-R5Independently of one another, from hydrogen, deuterium, methyl, ethyl, cyclopentyl, cyclohexyl, the following groups unsubstituted or substituted by Rc: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furyl, benzofuryl, dibenzofuryl, aza-dibenzofuryl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, spirofluorenyl, arylamino, carbazolyl.
4. The compound of claim 1, wherein R6-R13Independently of one another, from hydrogen, deuterium, methyl, ethyl, cyclopentyl, cyclohexyl, the following groups unsubstituted or substituted by Rc: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furyl, benzofuryl, dibenzofuryl, aza-dibenzofuryl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, spirofluorenyl, arylamino, carbazolyl.
5. The compound of claim 1, wherein R is selected from hydrogen, deuterium, methyl, ethyl, cyclopentyl, cyclohexyl, the following groups unsubstituted or substituted with Rc: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furyl, benzofuryl, dibenzofuryl, aza-dibenzofuryl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, spirofluorenyl, arylamino, carbazolyl.
6. A compound according to claim 1, wherein Ra, Rb are independently from each other selected from methyl, ethyl, cyclopentyl, cyclohexyl, the following groups unsubstituted or substituted by Rc: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furyl, benzofuryl, dibenzofuryl, aza-dibenzofuryl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, spirofluorenyl, arylamino, carbazolyl.
7. The compound of claim 1, wherein the compound is selected from the compounds represented by a1 to a 35:
Figure FDA0003050504900000031
Figure FDA0003050504900000041
8. an organic light emitting material comprising at least one of the compounds of any one of claims 1-7.
9. An organic electroluminescent device comprising at least one of the organic light emitting materials of claim 8.
10. The organic electroluminescent device according to claim 9, wherein the organic light emitting material is used as a blue host material.
11. A display device comprising the organic electroluminescent device according to claim 9 or 10.
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Cited By (5)

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CN114807989A (en) * 2022-04-19 2022-07-29 中钢集团南京新材料研究院有限公司 Synthesis method of 9-bromo-10- (2-naphthyl) anthracene
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CN116041296A (en) * 2022-12-29 2023-05-02 深圳市华星光电半导体显示技术有限公司 Compounds, mixtures and organic electronic devices
CN116143738A (en) * 2021-11-16 2023-05-23 烟台显华科技集团股份有限公司 Anthracene asymmetric dibenzoheterocyclic compound and application thereof

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