CN112125813A - Compound, hole transport material and organic electroluminescent device - Google Patents

Compound, hole transport material and organic electroluminescent device Download PDF

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CN112125813A
CN112125813A CN202010996205.5A CN202010996205A CN112125813A CN 112125813 A CN112125813 A CN 112125813A CN 202010996205 A CN202010996205 A CN 202010996205A CN 112125813 A CN112125813 A CN 112125813A
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邢其锋
丰佩川
孙志武
胡灵峰
陈跃
陈雪波
马艳
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Yantai Xianhua Chem Tech Co ltd
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Abstract

The invention provides a compound of general formula (I), which can be used in hole transport materials. The compound has a parent structure of dual fluorene substituted arylamine, high bond energy among atoms, good thermal stability, favorability for solid-state accumulation among molecules, strong transition capability of a cavity, and can effectively reduce voltage of a device and improve voltage of the device when used as a cavity transmission materialThe life of the material. The invention also provides an organic electroluminescent device and a display device comprising the compound of formula (I).
Figure DDA0002692597560000011

Description

Compound, hole transport material and organic electroluminescent device
Technical Field
The invention relates to the technical field of organic light-emitting display, in particular to a compound, a hole transport material and an organic electroluminescent device.
Background
Electroluminescence (EL) refers to a phenomenon in which a light emitting material emits light when excited by a current and an electric field 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, and flexible display and large-area display can be realized; the optical property, the electrical property, 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 (dyes or doped guest materials) and corresponding host materials of each color. The hole transport material, as an important functional material, has a direct influence on the mobility of holes, and ultimately influences the light emitting efficiency of the OLED. However, the hole transport materials currently used in OLEDs have low hole transport rates, poor energy level matching with adjacent layers, and no consideration for efficiency and lifetime, which severely restricts the display function and development of OLED display devices.
Disclosure of Invention
The embodiment of the invention aims to provide a hole transport material, which can improve the working efficiency and prolong the service life of an organic electroluminescent device.
In a first aspect the present invention provides a compound of general formula (i):
Figure BDA0002692597540000021
wherein the content of the first and second substances,
Ar1-Ar4independently of one another, from C6-C30Aryl or C3-C30The hydrogen atoms on the aryl and heteroaryl groups, each independently, may be substituted with Ra;
R1-R4independently of one another, from C1-C6Alkyl radical, C5-C20Cycloalkyl radical, C6-C30Aryl or C3-C30The hydrogen atoms on the aryl and heteroaryl groups are each independentlyMay be substituted by Ra, said R1And R2Can be connected into a ring, R3And R4Can be connected into a ring;
R5-R8independently of one another, from hydrogen, deuterium, C1-C6Alkyl radical, C5-C20Cycloalkyl radical, C6-C30Aryl or C3-C30The hydrogen atoms on the aryl and heteroaryl groups may each independently be substituted by Ra, R5-R8Two adjacent groups in the intermediate can be connected to form a ring;
L1、L2independently of one another, selected from the group consisting of a bond, C6-C30Arylene group of (A) or (C)6-C30The heteroarylene group of (a), wherein the hydrogen atoms on the arylene and heteroarylene groups, independently of each other, may be substituted with Ra;
n is 0 or 1;
each heteroatom on the heteroaryl or heteroarylene is independently selected from O, S or N;
ra, independently of one another, is chosen from deuterium, halogen, nitro, cyano, C1-C4Alkyl of (C)5-C20Cycloalkyl, phenyl, biphenyl, terphenyl, or naphthyl.
In a second aspect, the present invention provides a hole transport material comprising at least one of the compounds provided in the first aspect of the present invention.
In a third aspect, the present invention provides an organic electroluminescent device comprising at least one of the hole transport materials provided in the second aspect of the present invention.
A fourth aspect of the invention provides a display apparatus comprising the organic electroluminescent device of the third aspect of the invention.
The compound disclosed by the invention has a parent structure of a dibenzofluorene substituted arylamine, has high bond energy among atoms, good thermal stability, strong hole transition capability and capability of being used as a hole transport layer material, is favorable for solid-state accumulation among molecules, and can effectively reduce the voltage of a device and prolong the service life of the material.
The compound provided by the invention is applied to a hole transport layer, has a proper energy level with an adjacent layer, is beneficial to injection and migration of holes, can effectively reduce the driving voltage, has a high hole migration rate, and can realize good luminous efficiency in a device. The compound has a larger conjugated plane, is beneficial to molecular accumulation, shows good thermodynamic stability and shows long service life in a device.
Meanwhile, the preparation process of the derivative is simple and feasible, the raw materials are easy to obtain, and the derivative is suitable for industrial production.
Drawings
In order to more clearly illustrate the embodiments or technical solutions in the prior art of the present invention, the drawings used in the description of the embodiments or prior art will be briefly described below, it is obvious that the drawings in the following description are only one embodiment of the present invention, and other embodiments can be obtained by those skilled in the art according to the drawings.
Fig. 1 is a schematic structural view of a typical organic electroluminescent device.
Detailed Description
The technical solutions in the present invention will be described clearly and completely with reference to the accompanying drawings, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments obtained by a person skilled in the art based on the embodiments of the present invention belong to the protection scope of the present invention.
In a first aspect the present invention provides a compound of general formula (i):
Figure BDA0002692597540000041
wherein the content of the first and second substances,
Ar1-Ar4independently of one another, from C6-C30Aryl or C3-C30The hydrogen atoms of said aryl and heteroaryl groupsEach independently may be substituted by Ra;
R1-R4independently of one another, from C1-C6Alkyl radical, C5-C20Cycloalkyl radical, C6-C30Aryl or C3-C30The hydrogen atoms on the aryl and heteroaryl groups may each independently be substituted by Ra, R1And R2Can be connected into a ring, R3And R4Can be connected into a ring;
R5-R8independently of one another, from hydrogen, deuterium, C1-C6Alkyl radical, C5-C20Cycloalkyl radical, C6-C30Aryl or C3-C30The hydrogen atoms on the aryl and heteroaryl groups may each independently be substituted by Ra, R5-R8Two adjacent groups in the intermediate can be connected to form a ring;
L1、L2independently of one another, selected from the group consisting of a bond, C6-C30Arylene of (A) or (C)6-C30The heteroarylene group of (a), wherein the hydrogen atoms on the arylene and heteroarylene groups, independently of each other, may be substituted with Ra;
n is 0 or 1;
the heteroatoms on the heteroaryl or heteroarylene groups are independently selected from O, S or N;
ra, independently of one another, is chosen from deuterium, halogen, nitro, cyano, C1-C4Alkyl of (C)5-C20Cycloalkyl, phenyl, biphenyl, terphenyl, or naphthyl.
Preferably, Ar1-Ar4Independently of one another, from C6-C24Aryl or C3-C18The hydrogen atoms on the aryl and heteroaryl groups, each independently, may be substituted with Ra;
preferably, R1-R4Independently of one another, from C1-C6Alkyl radical, C5-C10Cycloalkyl radical, C6-C18Aryl or C3-C18The hydrogen atoms on the aryl and heteroaryl groups, each independently, may be substituted with Ra;
preferably, R5-R8Independently of one another, from hydrogen, deuterium, C1-C3Alkyl radical, C6-C12Aryl or C3-C12The hydrogen atoms on the aryl and heteroaryl groups, each independently, may be substituted with Ra;
preferably, L1、L2Independently of one another, selected from the group consisting of a bond, C6-C12Arylene group of (A) or (C)6-C12The heteroarylene group of (a), wherein the hydrogen atoms on the arylene and heteroarylene groups, independently of each other, may be substituted with Ra.
More preferably, Ar1-Ar4Independently of one another, from the following groups which are unsubstituted or substituted by Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, spirofluorenyl, arylamine, carbazolyl.
More preferably, R1-R4Independently of one another, from methyl, ethyl, cyclopentyl, cyclohexyl, phenyl, fluorenyl, pyridyl, dibenzofuranyl or dibenzothienyl.
More preferably, R5-R8Independently of one another, from hydrogen, methyl, ethyl, cyclopentyl, cyclohexyl, the following groups which are unsubstituted or substituted by Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, spirofluorenyl, arylamine, carbazolyl.
More preferably, L1、L2Independently of one another, from the group consisting of a bond, the following groups unsubstituted or substituted by Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinylPyridyl, 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-a30 as follows:
Figure BDA0002692597540000061
Figure BDA0002692597540000071
in a second aspect, the present invention provides a hole transport material comprising at least one of the compounds provided in the first aspect of the present invention.
In a third aspect, the present invention provides an organic electroluminescent device comprising at least one of the hole transport materials provided in the second aspect of the present invention.
In the present invention, there is no particular limitation on the kind and structure of the organic electroluminescent device as long as the hole transport material provided by the present invention can be used.
The organic electroluminescent device of the present invention may be a light-emitting device of a top emission structure, for example, comprising an anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, a transparent or semitransparent cathode in this order on a substrate.
The organic electroluminescent device of the present invention may be a light-emitting device having a bottom emission structure, for example, a structure comprising 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 in this order on a substrate.
The organic electroluminescent device of the present invention may also be a light-emitting device having a double-sided light-emitting structure, for example, a structure comprising 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 in this order on a substrate.
In the organic electroluminescent device of the present invention, any material used for the layer in the prior art may be used for the layer except that the hole transport layer comprises the hole transport material provided by the present invention.
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 schematically shows the structure of a typical organic electroluminescent device, and the present invention is not limited to this structure, and the hole transport material of the present invention may be used in any type of organic electroluminescent device. For example, the organic electroluminescent device may further include an electron blocking layer, a hole blocking layer, a light extraction layer, etc., and these layers may be added or omitted as the case may be, in practical use.
For convenience, the organic electroluminescent device of the present invention will be described below with reference to fig. 1, but this is not intended to limit the scope of the present invention in any way. It is understood that all organic electroluminescent devices capable of using the hole transport material of the present invention are within the scope of the present invention.
In the present invention, the substrate 1 is not particularly limited, and conventional substrates used in organic electroluminescent devices in the related art, for example, glass, polymer materials, and glass and polymer materials with TFT components and the like can be used.
In the present invention, the material of the reflective anode electrode 2 is not particularly limited, and may be selected from transparent conductive materials known in the art, such as Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), tin dioxide (SnO2), zinc oxide (ZnO), and Low Temperature Polysilicon (LTPS), metal materials such as silver and its alloy, aluminum and its alloy, organic conductive materials such as PEDOT (poly 3, 4-ethylenedioxythiophene), and a multilayer structure of the above materials.
In the present invention, the material of the hole injection layer 3 is not particularly limited, and a hole injection material known in the art or a hole transport material provided by the present invention may be selected as the hole injection material.
For example, the material of the hole injection layer may be selected from at least one of the following HT-1 to HT-31 compounds:
Figure BDA0002692597540000081
Figure BDA0002692597540000091
Figure BDA0002692597540000101
in the present invention, 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 employed, for example, the p-type dopant may be selected from at least one of the following compounds:
Figure BDA0002692597540000102
in the present invention, 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 invention, the hole transport layer 4 contains at least one of the hole transport materials of the present invention. The hole transport layer 4 may also comprise any combination of at least one of the hole transport materials of the invention with known hole transport materials. The currently known hole transport material may be selected from at least one of the above-mentioned HT-1 to HT-31 compounds, but is not limited to the above-mentioned compounds.
In the present invention, the light emitting material of the light emitting layer 5 is not particularly limited, and any light emitting material known to those skilled in the art may be used, and for example, the light emitting material may include a host material and a guest material. For example, known light emitting layer host materials may be selected from at least one of the following GPH-1 to GPH-80 compounds:
Figure BDA0002692597540000111
Figure BDA0002692597540000121
Figure BDA0002692597540000131
in a preferred embodiment of the invention, the light-emitting layer 5 employs the technique of phosphorescent electroluminescence. The guest material in the light-emitting layer 5 is a phosphorescent dopant, which may be selected from, but not limited to, a combination of one or more of the following compounds. The amount of the phosphorescent dopant is not particularly limited and may be an amount well known in the art.
Figure BDA0002692597540000132
Figure BDA0002692597540000141
In the present invention, the material of the electron transport layer 6 is not particularly limited, and may be made of an electron transport material known in the art. For example, the electron transport layer material may be selected from at least one of the following ET-1 to ET-57 compounds:
Figure BDA0002692597540000142
Figure BDA0002692597540000151
Figure BDA0002692597540000161
Figure BDA0002692597540000171
in the present invention, the electron transport layer 6 may further include an n-type dopant, the kind of which is not particularly limited, and various n-type dopants known in the art may be employed. For example, the n-type dopant may be a compound represented by the following formula:
Figure BDA0002692597540000172
in the present invention, 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 invention, the material of the electron injection layer 7 is not particularly limited, and an electron injection material known in the art may be used, and for example, at least one of the materials of LiQ, LiF, NaCl, CsF, Li2O, Cs2CO3, BaO, Na, Li, Ca, and the like in the related art may be included, but not limited thereto.
In the present invention, 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.
The fourth aspect of the invention provides a display device comprising the organic electroluminescent device provided by the invention. 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 invention is not particularly limited, and any method known in the art may be used, for example, the present invention 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 electron injection material selected from LiQ, LiF, NaCl, CsF, and Li on the electron transport layer 6 as electron injection layer 72O、Cs2CO3One or a combination of more of materials such as BaO, Na, Li, Ca and the like;
(7) a cathode material is vacuum-deposited on the electron injection layer 7 as a cathode electrode 8.
The above description has been made of only a structure of a typical organic electroluminescent device and a method for fabricating the same, and it is to be understood that the present invention is not limited to this structure. The hole transport material of the present invention can be used for an organic electroluminescent device of any structure, and the organic electroluminescent device can be prepared by any preparation method known in the art.
The method for synthesizing the compound of the present invention 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 invention.
Synthesis example 1: synthesis of Compound A1
Figure BDA0002692597540000181
Adding 100mmol of 2-boric acid benzyl into a reaction bottleMethyl ester acid, 100mmol of 2-bromo-4-chlorophenol, 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). The reaction was carried out 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, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M1. Wherein, Pd (PPh)3)4The amount of (A) added was 1 mol% based on 2-bromo-4-chlorophenol.
100mmol of M1 and 200ml of THF are added into a reaction flask, 220mmol of methyl magnesium bromide is added dropwise at 0 ℃, and the temperature is raised to room temperature for reaction for 12 hours after the dropwise addition. After the reaction was completed, water was added, the organic phase was separated and concentrated to obtain intermediate M2.
Into a reaction flask was charged 100mmol of M2, 200ml of trifluoromethanesulfonic anhydride (O (Tf)2) Heating to 120 ℃ and reacting for 12 h. After the reaction, water was added to precipitate a solid, which was then filtered and dried to obtain intermediate M3.
Into a reaction flask were charged 100mmol of 9, 9-dimethylfluorene-2-boronic acid, 100mmol of M3, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out 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, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M4. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M3.
Adding 100mmol of M4, 300ml of dichloromethane and 20ml of triethylamine into a reaction bottle, cooling to 0 ℃, dropwise adding 110mmol of trifluoromethanesulfonic anhydride, stirring at normal temperature, and reacting for 12 h. After the reaction is finished, water is added, an organic phase is separated, concentrated and dried to obtain an intermediate M5, wherein the TfO group in M5 is a triflate group.
100mmol of M5, 100mmol of 2- (9, 9-dimethylfluorene) -4-benzidine, 28.83g of sodium tert-butoxide (300mmol), 800ml of xylene and 1 mol% of palladium bis-dibenzylideneacetone (Pd (dba)) are added to the reaction flask. The reaction was carried out 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 1. Wherein Pd (dba) is added in an amount of 1 mol% based on M5.
1H NMR(400MHz,Chloroform)8.09(s,1H),7.93(d,J＝12.0Hz,4H),7.88–7.74(m,4H),7.74(s,1H),7.73–7.47(m,8H),7.42(d,J＝8.2Hz,3H),7.36(d,J＝13.6Hz,6H),7.24(s,2H),1.69(s,18H).
M/Z: experimental value, 745.1; theoretical value, 745.3.
Synthesis example 2: synthesis of Compound A5
Figure BDA0002692597540000191
Into a reaction flask were charged 100mmol of methyl 2-borate benzoate, 100mmol of 2-bromo-4-chlorophenol, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out 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, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M1. Wherein, Pd (PPh)3)4The amount of (A) added was 1 mol% based on 2-bromo-4-chlorophenol.
100mmol of M1 and 200ml of THF are added into a reaction flask, 220mmol of methyl magnesium bromide is added dropwise at 0 ℃, and the temperature is raised to room temperature for reaction for 12 hours after the dropwise addition. After the reaction was completed, water was added, the organic phase was separated and concentrated to obtain intermediate M2.
100mmol of M2 and 200ml of trifluoromethanesulfonic anhydride were added to a reaction flask, heated to 120 ℃ and reacted for 12 hours. After the reaction, water was added to precipitate a solid, which was then filtered and dried to obtain intermediate M3.
Into a reaction flask were charged 100mmol of 9, 9-bis (cyclopentyl) fluorene-2-boronic acid, 100mmol of M3, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. Stopping reaction after the reaction is finished, cooling the reactant to room temperature, adding water and organic matterThe phases were concentrated to give a white solid, filtered and washed with water, and the solid obtained was purified by recrystallization from toluene to give white powder M4. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M3.
Adding 100mmol of M4, 300ml of dichloromethane and 20ml of triethylamine into a reaction bottle, cooling to 0 ℃, dropwise adding 110mmol of trifluoromethanesulfonic anhydride, stirring at normal temperature, and reacting for 12 h. After the reaction is finished, water is added, an organic phase is separated, concentrated and dried to obtain an intermediate M5, wherein the TfO group in M5 is a triflate group.
A reaction flask was charged with 100mmol of M5, 100mmol of 2- (9, 9-dimethylfluorene) -2-naphthylamine, 28.83g sodium tert-butoxide (300mmol), 800ml xylene, and 1 mol% Pd (dba) was added. The reaction was carried out 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 5. Wherein Pd (dba) is added in an amount of 1 mol% based on M5.
1H NMR(400MHz,Chloroform)8.09(s,2H),7.91(d,J＝13.6Hz,4H),7.86(s,2H),7.78(s,2H),7.71(s,1H),7.66–7.40(m,8H),7.36(d,J＝9.6Hz,5H),7.24(s,2H),7.11(s,1H),2.24(s,2H),1.90(s,6H),1.76(s,6H),1.71–1.63(m,16H).
M/Z: experimental value, 827.2; theoretical value, 827.4.
Synthesis example 3: synthesis of Compound A7
Figure BDA0002692597540000211
Into a reaction flask were charged 100mmol of methyl 2-borate benzoate, 100mmol of 2-bromo-4-chlorophenol, 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). The reaction was carried out 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, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M1. Wherein, Pd (PPh)3)4The amount of (A) added was 1 mol% based on 2-bromo-4-chlorophenol.
100mmol of M1 and 200ml of THF are added into a reaction flask, 220mmol of methyl magnesium bromide is added dropwise at 0 ℃, and the temperature is raised to room temperature for reaction for 12 hours after the dropwise addition. After the reaction was completed, water was added, the organic phase was separated and concentrated to obtain intermediate M2.
Into a reaction flask was charged 100mmol of M2, 200ml of trifluoromethanesulfonic anhydride (O (Tf)2) Heating to 120 ℃ and reacting for 12 h. After the reaction, water was added to precipitate a solid, which was then filtered and dried to obtain intermediate M3.
Into a reaction flask were charged 100mmol of 9, 9-dimethylfluorene-4-boronic acid, 100mmol of M3, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out 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, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M4. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M3.
Adding 100mmol of M4, 300ml of dichloromethane and 20ml of triethylamine into a reaction bottle, cooling to 0 ℃, dropwise adding 110mmol of trifluoromethanesulfonic anhydride, stirring at normal temperature, and reacting for 12 h. After the reaction is finished, water is added, an organic phase is separated, concentrated and dried to obtain an intermediate M5, wherein the TfO group in M5 is a triflate group.
100mmol of M5, 100mmol of 3- (dibenzofuranyl) -4-benzidine, 28.83g of sodium tert-butoxide (300mmol), 800ml of xylene and 1 mol% of palladium bis-dibenzylideneacetone (Pd (dba)) are added to a reaction flask. The reaction was carried out 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 (dba) is added in an amount of 1 mol% based on M5.
1H NMR(400MHz,Chloroform)8.03(s,1H),7.98(s,1H),7.79(dd,J＝12.0,8.0Hz,4H),7.64(d,J＝8.8Hz,3H),7.61–7.50(m,8H),7.46–7.29(m,7H),7.16(d,J＝12.4,4H),7.24(s,1H),1.69(s,12H).
M/Z: experimental value, 719.1; theoretical value, 719.3.
Synthesis example 4: synthesis of Compound A8
Figure BDA0002692597540000221
Into a reaction flask were charged 100mmol of methyl 2-borate benzoate, 100mmol of 2-bromo-4-chlorophenol, 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). The reaction was carried out 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, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M1. Wherein, Pd (PPh)3)4The amount of (A) added was 1 mol% based on 2-bromo-4-chlorophenol.
100mmol of M1 and 200ml of THF are added into a reaction flask, 220mmol of methyl magnesium bromide is added dropwise at 0 ℃, and the temperature is raised to room temperature for reaction for 12 hours after the dropwise addition. After the reaction was completed, water was added, the organic phase was separated and concentrated to obtain intermediate M2.
Into a reaction flask was charged 100mmol of M2, 200ml of trifluoromethanesulfonic anhydride (O (Tf)2) Heating to 120 ℃ and reacting for 12 h. After the reaction, water was added to precipitate a solid, which was then filtered and dried to obtain intermediate M3.
Into a reaction flask were charged 100mmol of 9, 9-spirobifluorene-2-boronic acid, 100mmol of M3, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out 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, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M4. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M3.
Adding 100mmol of M4, 300ml of dichloromethane and 20ml of triethylamine into a reaction bottle, cooling to 0 ℃, dropwise adding 110mmol of trifluoromethanesulfonic anhydride, stirring at normal temperature, and reacting for 12 h. After the reaction is finished, water is added, an organic phase is separated, concentrated and dried to obtain an intermediate M5, wherein the TfO group in M5 is a triflate group.
100mmol of M5, 100mmol of 2- (9, 9-dimethylfluorene) -2-benzidine, 28.83g of sodium tert-butoxide (300mmol), 800ml of xylene and 1 mol% of palladium bis-dibenzylideneacetone (Pd (dba)) are added to the reaction flask. The reaction was carried out 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 A8. Wherein Pd (dba) is added in an amount of 1 mol% based on M5.
1H NMR(400MHz,Chloroform)8.09(s,1H),7.93(d,J＝12.0Hz,4H),7.88–7.74(m,4H),7.74(s,1H),7.73–7.47(m,8H),7.42(d,J＝8.2Hz,3H),7.36(d,J＝13.6Hz,6H),7.24(s,2H),1.69(s,18H).
M/Z: experimental value, 867.2; theoretical value, 867.4.
Synthesis example 5: synthesis of Compound A12
Figure BDA0002692597540000231
Into a reaction flask were charged 100mmol of methyl 2-borate benzoate, 100mmol of 2-bromo-4-chlorophenol, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out 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, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M1. Wherein, Pd (PPh)3)4The amount of (A) added was 1 mol% based on 2-bromo-4-chlorophenol.
100mmol of M1 and 200ml of THF are added into a reaction flask, 220mmol of methyl magnesium bromide is added dropwise at 0 ℃, and the temperature is raised to room temperature for reaction for 12 hours after the dropwise addition. After the reaction was completed, water was added, the organic phase was separated and concentrated to obtain intermediate M2.
100mmol of M2 and 200ml of trifluoromethanesulfonic anhydride were added to a reaction flask, heated to 120 ℃ and reacted for 12 hours. After the reaction, water was added to precipitate a solid, which was then filtered and dried to obtain intermediate M3.
Into a reaction flask were charged 100mmol of 9, 9-dimethylfluorene-2-boronic acid, 100mmol of M3, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out 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, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M4. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M3.
Adding 100mmol of M4, 300ml of dichloromethane and 20ml of triethylamine into a reaction bottle, cooling to 0 ℃, dropwise adding 110mmol of trifluoromethanesulfonic anhydride, stirring at normal temperature, and reacting for 12 h. After the reaction is finished, water is added, an organic phase is separated, concentrated and dried to obtain an intermediate M5, wherein the TfO group in M5 is a triflate group.
100mmol of M5, 100mmol of 4- (3, 5-dimethyl-1, 1' -biphenyl) -4-benzidine, 28.83g of sodium tert-butoxide (300mmol), 800ml of xylene and 1 mol% of Pd (dba) are added to the reaction flask. The reaction was carried out 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 12. Wherein Pd (dba) is added in an amount of 1 mol% based on M5.
1H NMR(400MHz,Chloroform)8.09(s,1H),8.08(s,1H),7.94(s,2H),7.91–7.64(m,9H),7.63(s,1H),7.59–7.46(m,7H),7.41(s,2H),7.39–7.31(m,5H),7.24(s,1H),2.13(s,6H),1.69(s,12H).
M/Z: experimental value, 732.8; theoretical value, 733.3.
Synthesis example 6: synthesis of Compound A15
Figure BDA0002692597540000241
100mmol of methyl 2-borate benzoate, 100mmol of 2-bromo-4-chlorophenol, 41.4g of potassium carbonate (300mmol) and 8 mmol of potassium carbonate were charged in a reaction flask00ml of THF and 200ml of water, and 1 mol% of Pd (PPh)3)4. The reaction was carried out 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, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M1. Wherein, Pd (PPh)3)4The amount of (A) added was 1 mol% based on 2-bromo-4-chlorophenol.
100mmol of M1 and 200ml of THF are added into a reaction flask, 220mmol of methyl magnesium bromide is added dropwise at 0 ℃, and the temperature is raised to room temperature for reaction for 12 hours after the dropwise addition. After the reaction was completed, water was added, the organic phase was separated and concentrated to obtain intermediate M2.
100mmol of M2 and 200ml of trifluoromethanesulfonic anhydride were added to a reaction flask, heated to 120 ℃ and reacted for 12 hours. After the reaction, water was added to precipitate a solid, which was then filtered and dried to obtain intermediate M3.
Into a reaction flask were charged 100mmol of 9-methyl-9-cyclopentylfluorene-2-boronic acid, 100mmol of M3, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out 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, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M4. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M3.
Adding 100mmol of M4, 300ml of dichloromethane and 20ml of triethylamine into a reaction bottle, cooling to 0 ℃, dropwise adding 110mmol of trifluoromethanesulfonic anhydride, stirring at normal temperature, and reacting for 12 h. After the reaction is finished, water is added, an organic phase is separated, concentrated and dried to obtain an intermediate M5, wherein the TfO group in M5 is a triflate group.
100mmol of M5, 100mmol of 3-N-phenylcarbazolyl-2-naphthylamine, 28.83g of sodium tert-butoxide (300mmol), 800ml of xylene and 1 mol% of Pd (dba) are added to a reaction flask. The reaction was carried out 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 15. Wherein Pd (dba) is added in an amount of 1 mol% based on M5.
1H NMR(400MHz,Chloroform)8.55(s,1H),8.19-8.09(m,3H),7.88(t,J＝8.0Hz,3H),7.78(s,1H),7.59–7.48(m,5H),7.45–7.31(m,6H),7.28–7.14(m,9H),7.11(s,1H),7.04(s,1H),2.11(s,1H),1.90(s,6H),1.78–1.35(m,8H),1.59(s,3H).
M/Z: experimental value, 822.1; theoretical value, 822.4.
Synthesis example 7: synthesis of Compound A19
Figure BDA0002692597540000251
Into a reaction flask were charged 100mmol of methyl 2-borate 3-naphthoate, 100mmol of 2-bromo-4-chlorophenol, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out 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, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M1. Wherein, Pd (PPh)3)4The amount of (A) added was 1 mol% based on 2-bromo-4-chlorophenol.
100mmol of M1 and 200ml of THF are added into a reaction flask, 220mmol of methyl magnesium bromide is added dropwise at 0 ℃, and the temperature is raised to room temperature for reaction for 12 hours after the dropwise addition. After the reaction was completed, water was added, the organic phase was separated and concentrated to obtain intermediate M2.
100mmol of M2 and 200ml of trifluoromethanesulfonic anhydride were added to a reaction flask, heated to 120 ℃ and reacted for 12 hours. After the reaction, water was added to precipitate a solid, which was then filtered and dried to obtain intermediate M3.
Into a reaction flask were charged 100mmol of 9, 9-dimethylfluorene-2-boronic acid, 100mmol of M3, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. Stopping reaction after the reaction is finished, cooling the reactant to room temperature, adding water, concentrating an organic phase to obtain a white solid, filtering, washing with water, and recrystallizing and purifying the obtained solid with toluene to obtain whiteColor powder M4. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M3.
Adding 100mmol of M4, 300ml of dichloromethane and 20ml of triethylamine into a reaction bottle, cooling to 0 ℃, dropwise adding 110mmol of trifluoromethanesulfonic anhydride, stirring at normal temperature, and reacting for 12 h. After the reaction is finished, water is added, an organic phase is separated, concentrated and dried to obtain an intermediate M5, wherein the TfO group in M5 is a triflate group.
A reaction flask was charged with 100mmol of M5, 100mmol of 2- (9, 9-dimethylfluorenyl) -4- (9, 9-dimethylfluorene) amine, 28.83g of sodium tert-butoxide (300mmol), 800ml of xylene, and 1 mol% of Pd (dba) was added. The reaction was carried out 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 19. Wherein Pd (dba) is added in an amount of 1 mol% based on M5.
1H NMR(400MHz,Chloroform)8.18(d,J＝7.6Hz,2H),8.01(s,1H),7.98(t,J＝8.8Hz,1H),7.93(d,J＝12.0Hz,4H),7.82(d,J＝10.0Hz,2H),7.75–7.65(m,6H),7.56(dt,J＝12.0,8.4Hz,6H),7.40(s,1H),7.34(s,1H),7.29(s,2H),7.26–7.18(m,5H),1.75(s,6H),1.69(s,18H).
M/Z: experimental value, 835.2; theoretical value, 835.4.
Synthesis example 8: synthesis of Compound A20
Figure BDA0002692597540000261
Into a reaction flask were charged 100mmol of methyl 2-borate-6-chloro-benzoate, 100mmol of 2-bromo-4-chlorophenol, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out 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, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M1. Wherein, Pd (PPh)3)4The amount of (A) added was 1 mol% based on 2-bromo-4-chlorophenol.
100mmol of M1 and 200ml of THF are added into a reaction flask, 220mmol of methyl magnesium bromide is added dropwise at 0 ℃, and the temperature is raised to room temperature for reaction for 12 hours after the dropwise addition. After the reaction was completed, water was added, the organic phase was separated and concentrated to obtain intermediate M2.
100mmol of M2 and 200ml of trifluoromethanesulfonic anhydride were added to a reaction flask, heated to 120 ℃ and reacted for 12 hours. After the reaction, water was added to precipitate a solid, which was then filtered and dried to obtain intermediate M3.
Into a reaction flask were charged 100mmol of 9, 9-dimethylfluorene-1-boronic acid, 100mmol of M3, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out 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, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M4. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M3.
Into a reaction flask were charged 100mmol of phenylboronic acid, 100mmol of M4, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% Pd (PPh) was added3)4. The reaction was carried out 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, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M5. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M4.
Adding 100mmol of M5, 300ml of dichloromethane and 20ml of triethylamine into a reaction bottle, cooling to 0 ℃, dropwise adding 110mmol of trifluoromethanesulfonic anhydride, stirring at normal temperature, and reacting for 12 h. After the reaction is finished, water is added, an organic phase is separated, concentrated and dried to obtain an intermediate M6, wherein the TfO group in M6 is a triflate group.
100mmol of M6, 100mmol of 2- (dibenzothiophene) -2-benzidine, 28.83g of sodium tert-butoxide (300mmol), 800ml of xylene and 1 mol% of palladium dibenzylacetonate (Pd (dba)) are added to a reaction flask. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction was cooled to room temperature, water was added, the organic phase was separated, concentrated, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder a 20. Wherein Pd (dba) is added in an amount of 1 mol% based on M6.
1H NMR(400MHz,Chloroform)8.44(s,1H),8.09(s,1H),8.08–7.89(m,4H),7.84(d,J＝8.4Hz,1H),7.75–7.50(m,8H),7.48–7.28(m,9H),7.24(s,1H),7.14(s,1H),7.08(s,1H),7.01(s,2H),1.69(s,12H).
M/Z: experimental value, 810.8; theoretical value, 811.3.
Synthesis example 9: synthesis of Compound A21
Figure BDA0002692597540000281
Into a reaction flask were charged 100mmol of methyl 2-borate benzoate, 100mmol of 2-bromo-4-chlorophenol, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out 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, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M1. Wherein, Pd (PPh)3)4The amount of (A) added was 1 mol% based on 2-bromo-4-chlorophenol.
100mmol of M1 and 200ml of THF are added into a reaction flask, 220mmol of methyl magnesium bromide is added dropwise at 0 ℃, and the temperature is raised to room temperature for reaction for 12 hours after the dropwise addition. After the reaction was completed, water was added, the organic phase was separated and concentrated to obtain intermediate M2.
100mmol of M2 and 200ml of trifluoromethanesulfonic anhydride were added to a reaction flask, heated to 120 ℃ and reacted for 12 hours. After the reaction, water was added to precipitate a solid, which was then filtered and dried to obtain intermediate M3.
Into a reaction flask were charged 100mmol of 9, 9-dimethylfluorene-2-boronic acid, 100mmol of M3, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. Stopping reaction after the reaction is finished, cooling the reactant to room temperature, adding water, and concentrating an organic phase to obtain whiteThe solid was filtered, washed with water and the resulting solid was purified by recrystallization from toluene to give M4 as a white powder. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M3.
Adding 100mmol of M4, 300ml of dichloromethane and 20ml of triethylamine into a reaction bottle, cooling to 0 ℃, dropwise adding 110mmol of trifluoromethanesulfonic anhydride, stirring at normal temperature, and reacting for 12 h. After the reaction is finished, water is added, an organic phase is separated, concentrated and dried to obtain an intermediate M5, wherein the TfO group in M5 is a triflate group.
100mmol of p-bromoiodobenzene, 100mmol of 2- (9, 9-dimethylfluorene) -4-benzidine, 28.83g of sodium tert-butoxide (300mmol), 800ml of xylene and 1 mol% of palladium dibenzylacetonate (Pd (dba)) were charged into a reaction flask. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction was cooled to room temperature, water was added, the organic phase was separated, concentrated, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M6. Wherein the addition amount of Pd (dba) is 1mol percent of the p-bromoiodobenzene.
100mmol of M6, 110mmol of pinacol diboron, 41.4g of potassium acetate (300mmol), 800ml of dioxane and 1 mol% of dichloro [1,1' -bis (diphenylphosphino) ferrocene are added to a reaction flask]Palladium (Pd (dppf) Cl2). The reaction was carried out at 100 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction was cooled to room temperature, water was added, the organic phase was separated, concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M7. Wherein Pd (dppf) Cl2Was added in an amount of 1 mol% based on M6.
Into a reaction flask were charged 100mmol of M5, 100mmol of M7, 41.4g potassium carbonate (300mmol), 800ml THF and 200ml water, and 1 mol% Pd (PPh) was added3)4. The reaction was carried out 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, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder a 21. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M5.
1H NMR(400MHz,Chloroform)8.11–7.93(m,3H),7.88(t,J＝10.0Hz,5H),7.77(d,J＝12.0Hz,3H),7.60–7.52(m,8H),7.49(s,2H),7.41(s,1H),7.35(t,J＝11.6Hz,8H),7.24(s,2H),1.69(s,18H).
M/Z: experimental value, 821.3; theoretical value, 821.4.
Synthesis example 10: synthesis of Compound A25
Figure BDA0002692597540000291
Into a reaction flask were charged 100mmol of methyl 2-borate benzoate, 100mmol of 2-bromo-4-chlorophenol, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out 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, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M1. Wherein, Pd (PPh)3)4The amount of (A) added was 1 mol% based on 2-bromo-4-chlorophenol.
100mmol of M1 and 200ml of THF are added into a reaction flask, 220mmol of methyl magnesium bromide is added dropwise at 0 ℃, and the temperature is raised to room temperature for reaction for 12 hours after the dropwise addition. After the reaction was completed, water was added, the organic phase was separated and concentrated to obtain intermediate M2.
100mmol of M2 and 200ml of trifluoromethanesulfonic anhydride were added to a reaction flask, heated to 120 ℃ and reacted for 12 hours. After the reaction, water was added to precipitate a solid, which was then filtered and dried to obtain intermediate M3.
100mmol of M3, 100mmol of diphenylamine, 28.83g of sodium tert-butoxide (300mmol), 800ml of xylene and 1 mol% of Pd (dba) are added to the reaction flask. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction was cooled to room temperature, water was added, the organic phase was separated, concentrated, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M4. Wherein Pd (dba) is added in an amount of 1 mol% based on M3.
100mmol of M3, 110mmol of pinacol diborate, 41.4g of acetic acid were placed in a reaction flaskPotassium (300mmol), 800ml dioxane, and 1 mol% Pd (dppf) Cl2. The reaction was carried out at 100 ℃ for 12 h. And stopping the reaction after the reaction is finished, cooling the reactant to room temperature, adding water, separating an organic phase, concentrating to obtain a white solid, filtering, washing with water, and recrystallizing and purifying the obtained solid with toluene to obtain white powder M5, wherein the TfO group in M5 is a triflate group. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M3.
Adding 100mmol of M4, 300ml of dichloromethane and 20ml of triethylamine into a reaction bottle, cooling to 0 ℃, dropwise adding 110mmol of trifluoromethanesulfonic anhydride, stirring at normal temperature, and reacting for 12 h. After the reaction, water was added, the organic phase was separated, concentrated and dried to obtain intermediate M6.
Into a reaction flask were charged 100mmol of M5, 100mmol of M6, 41.4g potassium carbonate (300mmol), 800ml THF and 200ml water, and 1 mol% Pd (PPh) was added3)4. The reaction was carried out 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, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M7. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M6.
Adding 100mmol of M7, 300ml of dichloromethane and 20ml of triethylamine into a reaction bottle, cooling to 0 ℃, dropwise adding 110mmol of trifluoromethanesulfonic anhydride, stirring at normal temperature, and reacting for 12 h. After the reaction is finished, water is added, an organic phase is separated, concentrated and dried to obtain an intermediate M8, wherein the TfO group in M8 is a triflate group.
A reaction flask was charged with 100mmol of M8, 100mmol of 2- (9, 9-dimethylfluorene) -2-naphthylamine, 28.83g sodium tert-butoxide (300mmol), 800ml xylene, and 1 mol% Pd (dba) was added. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction was cooled to room temperature, water was added, the organic phase was separated, concentrated, filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder a 25. Wherein the addition amount of Pd (dba) is 1mol percent of the p-bromoiodobenzene.
1H NMR(400MHz,Chloroform)7.90(s,2H),7.90(s,2H),7.80(dd,J＝12.8,9.6Hz,5H),7.63(t,J＝8.0Hz,3H),7.60–7.49(m,6H),7.43(d,J＝12.0Hz,2H),7.36(d,J＝9.6Hz,4H),7.24(d,J＝8.4Hz,6H),7.10(d,J＝12.0Hz,4H),7.00(s,1H),1.69(s,18H).
M/Z: experimental value, 886.2; theoretical value, 886.4.
Other compounds of the present invention can be synthesized by selecting suitable starting materials according to the above-mentioned concepts of examples 1 to 10, 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;
placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to less than 10 DEG-5In the torr, HT-11 is evaporated in vacuum on the anode layer film to be used as a hole injection layer, the evaporation rate is 0.1nm/s, and the evaporation film thickness is 10 nm;
vacuum evaporating an A1 material on the hole injection layer to form a hole transport layer, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 80 nm;
a luminescent layer is evaporated on the hole transport layer in vacuum, the luminescent layer comprises a main material GHP-16 and a dye material RPD-1, evaporation is carried out by a multi-source co-evaporation method, the evaporation rate of the main material GHP-16 is adjusted to be 0.1nm/s, the evaporation rate of the dye RPD-1 is 3% of the evaporation rate of the main material, and the total thickness of the evaporation film is 30 nm;
vacuum evaporating an electron transport layer on the light emitting layer, wherein an ET-42 material is selected as an electron transport material, the evaporation rate is 0.1nm/s, and the evaporation film thickness is 30 nm;
vacuum evaporating LiF with the thickness of 0.5nm on the Electron Transport Layer (ETL) to be used as an electron injection layer, wherein the evaporation rate is 0.1 nm/s;
and finally, evaporating an aluminum layer with the thickness of 150nm on the electron injection layer to be used as a cathode of the organic electroluminescent device, wherein the evaporation rate is 0.1 nm/s.
Examples 2 to 10
The procedure was as in example 1 except that A5, A7, A8, A12, A15, A19, A20, A21 and A25 were used in place of A1. The test results are shown in Table 1.
Comparative example 1
The test results were as in example 1 except that HT-27 was used in place of A1, and are shown in Table 1.
The organic electroluminescent device prepared by the above process was subjected to the following performance measurement:
the organic electroluminescent devices obtained in examples and comparative examples were measured for driving voltage and 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 devices reached 5000cd/m when the voltage was increased at a rate of 0.1V/sec2The 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 5000cd/m2The luminance drop of the organic electroluminescent device was measured to be 4750cd/m by maintaining a constant current at luminance2Time in hours.
Table 1 organic electroluminescent device performance results
Figure BDA0002692597540000321
The data in the table show that the compound prepared by the invention is used for the hole transport material of the organic electroluminescent device, can effectively reduce the driving voltage, improve the current efficiency and prolong the service life of the device, and is a hole transport material with good performance.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.

Claims (10)

1. A compound of general formula (I):
Figure FDA0002692597530000011
wherein the content of the first and second substances,
Ar1-Ar4independently of one another, from C6-C30Aryl or C3-C30The hydrogen atoms on the aryl and heteroaryl groups, each independently, may be substituted with Ra;
R1-R4independently of one another, from C1-C6Alkyl radical, C5-C20Cycloalkyl radical, C6-C30Aryl or C3-C30The hydrogen atoms on the aryl and heteroaryl groups may each independently be substituted by Ra, R1And R2Can be connected into a ring, R3And R4Can be connected into a ring;
R5-R8independently of one another, from hydrogen, deuterium, C1-C6Alkyl radical, C5-C20Cycloalkyl radical, C6-C30Aryl or C3-C30The hydrogen atoms on the aryl and heteroaryl groups may each independently be substituted by Ra, R5-R8Two adjacent groups in the intermediate can be connected to form a ring;
L1、L2independently of one another, selected from the group consisting of a bond, C6-C30Arylene group of (A) or (C)6-C30The heteroarylene group of (a), wherein the hydrogen atoms on the arylene and heteroarylene groups, independently of each other, may be substituted with Ra;
n is 0 or 1;
each heteroatom on the heteroaryl or heteroarylene is independently selected from O, S or N;
ra, independently of one another, is chosen from deuterium, halogen, nitro, cyano, C1-C4Alkyl of (C)5-C20Cycloalkyl, phenyl, biphenyl, terphenyl, or naphthyl.
2. The compound of claim 1, wherein,
Ar1-Ar4independently of one another, from C6-C24Aryl or C3-C18The hydrogen atoms on the aryl and heteroaryl groups, each independently, may be substituted with Ra;
R1-R4independently of one another, from C1-C6Alkyl radical, C5-C10Cycloalkyl radical, C6-C18Aryl or C3-C18The hydrogen atoms on the aryl and heteroaryl groups, each independently, may be substituted with Ra;
R5-R8independently of one another, from hydrogen, deuterium, C1-C3Alkyl radical, C6-C12Aryl or C3-C12The hydrogen atoms on the aryl and heteroaryl groups, each independently, may be substituted with Ra;
L1、L2independently of one another, selected from the group consisting of a bond, C6-C12Arylene group of (A) or (C)6-C12The heteroarylene group of (a), wherein the hydrogen atoms on the arylene and heteroarylene groups, independently of each other, may be substituted with Ra.
3. The compound of claim 1, wherein Ar1-Ar4Independently of one another, from the following groups which are unsubstituted or substituted by Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, spirofluorenyl, arylamine, carbazolyl.
4. The compound of claim 1, wherein R1-R4Independently of one another, from methyl, ethyl, cyclopentyl, cyclohexyl, phenyl, fluorenyl, pyridyl, dibenzofuranyl or dibenzothienyl.
5. The compound of claim 1, wherein R5-R8Independently of one another, from hydrogen, methyl, ethyl, cyclopentyl, cyclohexyl, the following groups which are unsubstituted or substituted by Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, spirofluorenyl, arylamine, carbazolyl.
6. The compound of claim 1, wherein L1、L2Independently of one another, from the group consisting of a bond, the following groups unsubstituted or substituted by Ra: 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, selected from the compounds represented by a1-a 30:
Figure FDA0002692597530000031
Figure FDA0002692597530000041
8. a hole transport material comprising at least one of the compounds of any one of claims 1-7.
9. An organic electroluminescent device comprising at least one hole transport material of claim 8.
10. A display device comprising the organic electroluminescent device according to claim 9.
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