CN112125813B - Compound, hole transport material and organic electroluminescent device - Google Patents

Compound, hole transport material and organic electroluminescent device Download PDF

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CN112125813B
CN112125813B CN202010996205.5A CN202010996205A CN112125813B CN 112125813 B CN112125813 B CN 112125813B CN 202010996205 A CN202010996205 A CN 202010996205A CN 112125813 B CN112125813 B CN 112125813B
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CN112125813A (en
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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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    • C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
    • C07C211/61—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton with at least one of the condensed ring systems formed by three or more rings
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    • C07D209/82—Carbazoles; Hydrogenated carbazoles
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    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
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    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/76—Dibenzothiophenes
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
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    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
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    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
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Abstract

The invention provides a compound of formula (I) which can be used in hole transport materials. The compound has a parent structure of double fluorene substituted aromatic amine, has high bond energy among atoms, good thermal stability, is favorable for solid accumulation among molecules, has strong hole transition capability, can effectively reduce device voltage when being used as a hole transport material, and improves the service life of the material. The invention also provides an organic electroluminescent device and a display device comprising the compound of the general formula (I).

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 under the excitation of electric current and electric field, and is a light emitting process in which electric energy is directly converted into light energy. The organic electroluminescent display (OLED) has the advantages of self-luminescence, low voltage DC drive, full solidification, wide viewing angle, light weight, simple composition and process, etc., compared with the liquid crystal display, the organic electroluminescent display does not need a backlight source, has large viewing angle and low power, the response speed can reach 1000 times of the liquid crystal display, and the manufacturing cost is 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 advancement of OLED technology in the two fields of illumination 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 usually the result of the optimized collocation 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, film can be formed on any substrate by a vapor deposition 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 the molecule, and the material has a large space to select. In the most common OLED device structures, the following classes of organic materials are typically included: a hole injection material, a hole transport material, an electron transport material, a light emitting material (dye or doped guest material) of each color, a corresponding host material, and the like. Among them, the hole transport material, which is an important functional material, has a direct effect on the mobility of holes and ultimately affects the luminous efficiency of the OLED. However, the hole transport material applied to the OLED at present has low hole migration rate, poor energy level matching with the adjacent layer, and cannot give consideration to efficiency and service life, thus severely restricting the display function and development of the OLED display device.
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 formula (I):
wherein, the liquid crystal display device comprises a liquid crystal display device,
Ar 1 -Ar 4 independently of one another selected from C 6 -C 30 Or C 3 -C 30 The hydrogen atoms on the aryl and heteroaryl groups each independently may be substituted with Ra;
R 1 -R 4 independently of one another selected from C 1 -C 6 Alkyl, C 5 -C 20 Cycloalkyl, C 6 -C 30 Aromatic groups or C of (2) 3 -C 30 The hydrogen atoms on the aryl and heteroaryl groups may each independently be substituted with Ra, the R 1 And R is 2 Can be linked into a ring, said R 3 And R is 4 Can be connected into a ring;
R 5 -R 8 independently of one another selected from hydrogen, deuterium, C 1 -C 6 Alkyl, C 5 -C 20 Cycloalkyl, C 6 -C 30 Aromatic groups or C of (2) 3 -C 30 The hydrogen atoms on the aryl and heteroaryl groups may each independently be substituted with Ra, the R 5 -R 8 Can be connected between two adjacent groups to form a ring;
L 1 、L 2 independently of one another, from chemical bonds, C 6 -C 30 Or C 6 -C 30 The hydrogen atoms on the arylene and heteroarylene groups each independently may be substituted with Ra;
n is 0 or 1;
the heteroatoms on the heteroaryl or heteroarylene are each independently selected from O, S or N;
The Ra groups are independently selected from deuterium, halogen, nitro, cyano, C 1 -C 4 Alkyl, C of (2) 5 -C 20 Cycloalkyl, 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.
The third aspect of 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 device comprising the organic electroluminescent device of the third aspect of the invention.
The compound disclosed by the invention has a parent structure of the double fluorene substituted aromatic amine, has high bond energy among atoms, good thermal stability, is favorable for solid accumulation among molecules, has strong hole transition capability, can effectively reduce the voltage of a device when being used as a hole transport layer material, and improves the service life of the material.
The compound disclosed by the invention is applied to a hole transport layer, has a proper energy level with adjacent layers, is favorable for hole injection and migration, can effectively reduce driving voltage, has a higher hole migration rate, and can realize good luminous efficiency in a device. The compound provided by the invention has a larger conjugate plane, is favorable for 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, raw materials are easy to obtain, and the derivative is suitable for industrial production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described, and it is apparent that the drawings in the description below are only one embodiment of the present invention, and other embodiments may be obtained according to these drawings by those skilled in the art.
Fig. 1 is a schematic structural view of a typical organic electroluminescent device.
Detailed Description
The following description of the embodiments of the present invention will be made more apparent and fully hereinafter with reference to the accompanying drawings, in which some, but not all embodiments of the invention are shown. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention are within the scope of the present invention.
In a first aspect the present invention provides a compound of formula (I):
wherein, the liquid crystal display device comprises a liquid crystal display device,
Ar 1 -Ar 4 independently of one another selected from C 6 -C 30 Or C 3 -C 30 The hydrogen atoms on the aryl and heteroaryl groups each independently may be substituted with Ra;
R 1 -R 4 Independently of one another selected from C 1 -C 6 Alkyl, C 5 -C 20 Cycloalkyl, C 6 -C 30 Aromatic groups or C of (2) 3 -C 30 The hydrogen atoms on the aryl and heteroaryl groups may each independently be substituted with Ra, the R 1 And R is 2 Can be linked into a ring, said R 3 And R is 4 Can be connected into a ring;
R 5 -R 8 independently of one another selected from hydrogen, deuterium, C 1 -C 6 Alkyl, C 5 -C 20 Cycloalkyl, C 6 -C 30 Aromatic groups or C of (2) 3 -C 30 The hydrogen atoms on the aryl and heteroaryl groups may each independently be substituted with Ra, the R 5 -R 8 Can be connected between two adjacent groups to form a ring;
L 1 、L 2 independent of each otherSelected from chemical bonds, C 6 -C 30 Arylene or C of (2) 6 -C 30 The hydrogen atoms on the arylene and heteroarylene groups each independently may be substituted with Ra;
n is 0 or 1;
the heteroatoms on the heteroaryl or heteroarylene are independently selected from O, S or N;
the Ra groups are independently selected from deuterium, halogen, nitro, cyano, C 1 -C 4 Alkyl, C of (2) 5 -C 20 Cycloalkyl, phenyl, biphenyl, terphenyl or naphthyl.
Preferably Ar 1 -Ar 4 Independently of one another selected from C 6 -C 24 Aromatic groups or C 3 -C 18 The hydrogen atoms on the aryl and heteroaryl groups each independently may be substituted with Ra;
preferably, R 1 -R 4 Independently of one another selected from C 1 -C 6 Alkyl, C 5 -C 10 Cycloalkyl, C 6 -C 18 Aromatic groups or C of (2) 3 -C 18 The hydrogen atoms on the aryl and heteroaryl groups each independently may be substituted with Ra;
preferably, R 5 -R 8 Independently of one another selected from hydrogen, deuterium, C 1 -C 3 Alkyl, C 6 -C 12 Aromatic groups or C of (2) 3 -C 12 The hydrogen atoms on the aryl and heteroaryl groups each independently may be substituted with Ra;
preferably L 1 、L 2 Independently of one another, from chemical bonds, C 6 -C 12 Arylene or C of (2) 6 -C 12 The hydrogen atoms on the arylene and heteroarylene groups may each independently be substituted with Ra.
More preferably Ar 1 -Ar 4 Independently of each other selected from the following groups unsubstituted or substituted by Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranA pyranyl group, a benzothienyl group, a dibenzothienyl group, an aza-dibenzothienyl group, a 9, 9-dimethylfluorenyl group, a spirofluorenyl group, an arylamino group, a carbazolyl group.
More preferably, R 1 -R 4 Independently of each other, selected from methyl, ethyl, cyclopentyl, cyclohexyl, phenyl, fluorenyl, pyridinyl, dibenzofuranyl or dibenzothiophenyl.
More preferably, R 5 -R 8 Independently of one another, selected from the following radicals, which are unsubstituted or substituted by Ra, hydrogen, methyl, ethyl, cyclopentyl, cyclohexyl: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, spirofluorenyl, arylamino, carbazolyl.
More preferably L 1 、L 2 Independently of each other selected from the following groups, which are bonded, unsubstituted or substituted by Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, spirofluorenyl, arylamino, carbazolyl.
For example, the compound of formula (I) may be selected from the compounds shown in the following A1-A30:
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.
The third aspect of 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, the kind and structure of the organic electroluminescent device are not particularly limited 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 light emitting structure, for example, a transparent or semitransparent anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode structure are sequentially formed on a substrate.
The organic electroluminescent device of the present invention may be a light emitting device of a double-sided light emitting structure, for example, a transparent or semitransparent 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 semitransparent cathode structure are sequentially included 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 other layers, except that the hole transport layer contains the hole transport material provided by the present invention.
Fig. 1 shows a schematic view 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 disposed in this order from bottom to top.
It will be appreciated that fig. 1 schematically illustrates only one typical organic electroluminescent device structure, 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 depending on the specific circumstances in practical applications.
For convenience, the organic electroluminescent device of the present invention will be described below with reference to fig. 1, but this is not meant 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 a conventional substrate used in the organic electroluminescent device in the related art, for example, glass, polymer material, glass with TFT devices, polymer material, 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 such as Indium Tin Oxide (ITO), indium Zinc Oxide (IZO), tin dioxide (SnO 2), zinc oxide (ZnO), 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 multilayer structures of the above materials, and the like, which are known in the prior art.
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 through HT-31 compounds:
in the present invention, the hole injection layer 3 may further include a p-type dopant, the kind 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:
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 present invention with a known hole transport material. The currently known hole transport material may be selected from at least one of the above-mentioned HT-1 through 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, for example, the light emitting material may include a host material and a guest material. For example, the known host material of the light emitting layer may be selected from at least one of the following GPH-1 to GPH-80 compounds:
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In a preferred embodiment of the present invention, the light-emitting layer 5 employs a phosphorescent electroluminescence technique. The guest material in its light emitting layer 5 is a phosphorescent dopant which may be selected from, but is 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.
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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:
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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 formula:
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 electron injection materials known in the art may be used, for example, at least one of materials LiQ, liF, naCl, csF, li2O, cs CO3, baO, na, li, ca, etc. 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, for example, metals such as magnesium-silver mixture, liF/Al, ITO, al, metal mixtures, oxides, and the like.
The fourth aspect of the invention provides a display device comprising the organic electroluminescent device provided by the invention. Including but not limited to displays, televisions, tablet computers, mobile communication terminals, etc.
The method of preparing the organic electroluminescent device of the present invention is not particularly limited, and any method known in the art may be employed, 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 light emission, respectively performing steps of medicine washing, water washing, hairbrushes, high-pressure water washing, air knives and the like in a cleaning machine, and then performing heating treatment;
(2) Vacuum evaporating a hole injection material on the reflective anode electrode 2 as a hole injection layer 3;
(3) Vacuum evaporating a hole transport material on the hole injection layer 3 as a hole transport layer 4;
(4) Vacuum evaporating a light-emitting layer 5 on the hole transport layer 4, wherein the light-emitting layer 5 comprises a host material and a guest material;
(5) Vacuum evaporating an electron transport material on the light-emitting layer 5 as an electron transport layer 6;
(6) Vacuum evaporating electron injection material selected from LiQ, liF, naCl, csF, li as electron injection layer 7 on electron transport layer 6 2 O、Cs 2 CO 3 One or a combination of a plurality of materials such as BaO, na, li, ca;
(7) A cathode material is vacuum-evaporated on the electron injection layer 7 as a cathode electrode 8.
Only the structure of a typical organic electroluminescent device and a method for manufacturing the same are described above, and it should be understood that the present invention is not limited to such a structure. The hole transport material of the present invention may be used in any structure of organic electroluminescent device, and the organic electroluminescent device may be prepared using any preparation method known in the art.
The method for synthesizing the compound of the present invention is not particularly limited, and may be synthesized by any method known to those skilled in the art. The synthesis of the compounds of the present invention is illustrated below.
Synthesis example 1: synthesis of Compound A1
Into a reaction flask were charged 100mmol of methyl 2-borate, 100mmol of 2-bromo-4-chlorophenol, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh 3 ) 4 ). The reaction was carried out at 120℃for 12h. After the reaction, the reaction is stopped, the reactant is cooled to room temperature, water is added, the organic phase is concentrated to obtain white solid, the white solid is filtered and washed, and the obtained solid is recrystallized and purified by toluene to obtain white powder M1. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of 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 reaction flask is warmed to room temperature for reaction for 12h after the dropwise addition. After the reaction, water is added, the organic phase is separated and concentrated to obtain an intermediate M2.
Into a reaction flask was charged 100mmol of M2, 200ml of trifluoromethanesulfonic anhydride (O (Tf) 2 ) Heated to 120 ℃ and reacted for 12 hours. After the reaction, water is added, solid is separated out, filtered and dried to obtain an intermediate M3.
Into a reaction flask were charged 100mmol of 9, 9-dimethylfluorene-2-boronic acid, 100mmol of M3, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh 3 ) 4 . The reaction was carried out at 120℃for 12h. After the reaction, the reaction is stopped, the reactant is cooled to room temperature, water is added, the organic phase is concentrated to obtain white solid, the white solid is filtered and washed, and the obtained solid is recrystallized and purified by toluene to obtain white powder M4. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M3.
100mmol of M4, 300ml of dichloromethane and 20ml of triethylamine are added into a reaction bottle, the temperature is reduced to 0 ℃, 110mmol of trifluoromethanesulfonic anhydride is added dropwise, and the mixture is stirred at normal temperature and reacts for 12 hours. After the reaction, adding water, separating an organic phase, concentrating and drying to obtain an intermediate M5, wherein a group TfO in the M5 is a trifluoro sulfonic group.
Into the reaction flask were charged 100mmol of M5, 100mmol of 2- (9, 9-dimethylfluorene) -4-benzidine, 28.83g of sodium tert-butoxide (300 mmol), 800ml of xylene, and 1mol% of palladium bis dibenzylidene acetonate (Pd (dba)). The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder A1. Wherein, the addition amount of Pd (dba) is 1mol% of M5.
1 H NMR(400MHz,Chloroform)δ8.09(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 values, 745.1; theoretical value, 745.3.
Synthesis example 2: synthesis of Compound A5
Into a reaction flask were charged 100mmol of methyl 2-borate, 100mmol of 2-bromo-4-chlorophenol, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh 3 ) 4 . The reaction was carried out at 120℃for 12h. After the reaction, the reaction is stopped, the reactant is cooled to room temperature, water is added, the organic phase is concentrated to obtain white solid, the white solid is filtered and washed, and the obtained solid is recrystallized and purified by toluene to obtain white powder M1. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of 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 reaction flask is warmed to room temperature for reaction for 12h after the dropwise addition. After the reaction, water is added, the organic phase is separated and concentrated to obtain an intermediate M2.
100mmol of M2 and 200ml of trifluoromethanesulfonic anhydride were added to the reaction flask, and the mixture was heated to 120℃and reacted for 12 hours. After the reaction, water is added, solid is separated out, filtered and dried to obtain an 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 (300 mmol), 800ml of THF and 200ml of water, and 1mol% Pd (PPh 3 ) 4 . The reaction was carried out at 120℃for 12h. After the reaction, the reaction is stopped, the reactant is cooled to room temperature, water is added, the organic phase is concentrated to obtain white solid, the white solid is filtered and washed, and the obtained solid is recrystallized and purified by toluene to obtain white powder M4. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M3.
100mmol of M4, 300ml of dichloromethane and 20ml of triethylamine are added into a reaction bottle, the temperature is reduced to 0 ℃, 110mmol of trifluoromethanesulfonic anhydride is added dropwise, and the mixture is stirred at normal temperature and reacts for 12 hours. After the reaction, adding water, separating an organic phase, concentrating and drying to obtain an intermediate M5, wherein a group TfO in the M5 is a trifluoro sulfonic group.
To the reaction flask were added 100mmol of M5, 100mmol of 2- (9, 9-dimethylfluorene) -2-naphthylamine, 28.83g of sodium tert-butoxide (300 mmol), 800ml of xylene, and 1mol% of Pd (dba). The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder A5. Wherein, the addition amount of Pd (dba) is 1mol% of M5.
1 H NMR(400MHz,Chloroform)δ8.09(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 values, 827.2; theoretical value, 827.4.
Synthesis example 3: synthesis of Compound A7
Into a reaction flask were charged 100mmol of methyl 2-borate, 100mmol of 2-bromo-4-chlorophenol, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh 3 ) 4 ). The reaction was carried out at 120℃for 12h. After the reaction, the reaction is stopped, the reactant is cooled to room temperature, water is added, the organic phase is concentrated to obtain white solid, the white solid is filtered and washed, and the obtained solid is recrystallized and purified by toluene to obtain white powder M1. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of 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 reaction flask is warmed to room temperature for reaction for 12h after the dropwise addition. After the reaction, water is added, the organic phase is separated and concentrated to obtain an intermediate M2.
Into a reaction flask was charged 100mmol of M2, 200ml of trifluoromethanesulfonic anhydride (O (Tf) 2 ) Heated to 120 ℃ and reacted for 12 hours. After the reaction, water is added, solid is separated out, filtered and dried to obtain an intermediate M3.
Into a reaction flask were charged 100mmol of 9, 9-dimethylfluorene-4-boronic acid, 100mmol of M3, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh 3 ) 4 . The reaction was carried out at 120℃for 12h. After the reaction, the reaction is stopped, the reactant is cooled to room temperature, water is added, the organic phase is concentrated to obtain white solid, the white solid is filtered and washed, and the obtained solid is recrystallized and purified by toluene to obtain white powder M4.Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M3.
100mmol of M4, 300ml of dichloromethane and 20ml of triethylamine are added into a reaction bottle, the temperature is reduced to 0 ℃, 110mmol of trifluoromethanesulfonic anhydride is added dropwise, and the mixture is stirred at normal temperature and reacts for 12 hours. After the reaction, adding water, separating an organic phase, concentrating and drying to obtain an intermediate M5, wherein a group TfO in the M5 is a trifluoro sulfonic group.
To the reaction flask were added 100mmol of M5, 100mmol of 3- (dibenzofuranyl) -4-benzidine, 28.83g of sodium tert-butoxide (300 mmol), 800ml of xylene, and 1mol% of palladium bis dibenzylidene acetonate (Pd (dba)). The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder A7. Wherein, the addition amount of Pd (dba) is 1mol% of M5.
1 H NMR(400MHz,Chloroform)δ8.03(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 values, 719.1; theoretical value, 719.3.
Synthesis example 4: synthesis of Compound A8
Into a reaction flask were charged 100mmol of methyl 2-borate, 100mmol of 2-bromo-4-chlorophenol, 41.4g of potassium carbonate (300 mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 1mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh 3 ) 4 ). The reaction was carried out at 120℃for 12h. After the reaction, the reaction is stopped, the reactant is cooled to room temperature, water is added, the organic phase is concentrated to obtain white solid, the white solid is filtered and washed, and the obtained solid is recrystallized and purified by toluene to obtain white powder M1. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of 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 reaction flask is warmed to room temperature for reaction for 12h after the dropwise addition. After the reaction, water is added, the organic phase is separated and concentrated to obtain an intermediate M2.
Into a reaction flask was charged 100mmol of M2, 200ml of trifluoromethanesulfonic anhydride (O (Tf) 2 ) Heated to 120 ℃ and reacted for 12 hours. After the reaction, water is added, solid is separated out, filtered and dried to obtain an intermediate M3.
Into a reaction flask were charged 100mmol of 9, 9-spirobifluorene-2-boronic acid, 100mmol of M3, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh 3 ) 4 . The reaction was carried out at 120℃for 12h. After the reaction, the reaction is stopped, the reactant is cooled to room temperature, water is added, the organic phase is concentrated to obtain white solid, the white solid is filtered and washed, and the obtained solid is recrystallized and purified by toluene to obtain white powder M4. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M3.
100mmol of M4, 300ml of dichloromethane and 20ml of triethylamine are added into a reaction bottle, the temperature is reduced to 0 ℃, 110mmol of trifluoromethanesulfonic anhydride is added dropwise, and the mixture is stirred at normal temperature and reacts for 12 hours. After the reaction, adding water, separating an organic phase, concentrating and drying to obtain an intermediate M5, wherein a group TfO in the M5 is a trifluoro sulfonic group.
Into the reaction flask were charged 100mmol of M5, 100mmol of 2- (9, 9-dimethylfluorene) -2-benzidine, 28.83g of sodium tert-butoxide (300 mmol), 800ml of xylene, and 1mol% of palladium bis dibenzylidene acetonate (Pd (dba)). The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder A8. Wherein, the addition amount of Pd (dba) is 1mol% of M5.
1 H NMR(400MHz,Chloroform)δ8.09(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 values, 867.2; theoretical value, 867.4.
Synthesis example 5: synthesis of Compound A12
Into a reaction flask were charged 100mmol of methyl 2-borate, 100mmol of 2-bromo-4-chlorophenol, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh 3 ) 4 . The reaction was carried out at 120℃for 12h. After the reaction, the reaction is stopped, the reactant is cooled to room temperature, water is added, the organic phase is concentrated to obtain white solid, the white solid is filtered and washed, and the obtained solid is recrystallized and purified by toluene to obtain white powder M1. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of 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 reaction flask is warmed to room temperature for reaction for 12h after the dropwise addition. After the reaction, water is added, the organic phase is separated and concentrated to obtain an intermediate M2.
100mmol of M2 and 200ml of trifluoromethanesulfonic anhydride were added to the reaction flask, and the mixture was heated to 120℃and reacted for 12 hours. After the reaction, water is added, solid is separated out, filtered and dried to obtain an intermediate M3.
Into a reaction flask were charged 100mmol of 9, 9-dimethylfluorene-2-boronic acid, 100mmol of M3, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh 3 ) 4 . The reaction was carried out at 120℃for 12h. After the reaction, the reaction is stopped, the reactant is cooled to room temperature, water is added, the organic phase is concentrated to obtain white solid, the white solid is filtered and washed, and the obtained solid is recrystallized and purified by toluene to obtain white powder M4. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M3.
100mmol of M4, 300ml of dichloromethane and 20ml of triethylamine are added into a reaction bottle, the temperature is reduced to 0 ℃, 110mmol of trifluoromethanesulfonic anhydride is added dropwise, and the mixture is stirred at normal temperature and reacts for 12 hours. After the reaction, adding water, separating an organic phase, concentrating and drying to obtain an intermediate M5, wherein a group TfO in the M5 is a trifluoro sulfonic group.
Into the reaction flask were charged 100mmol of M5, 100mmol of 4- (3, 5-dimethyl-1, 1' -biphenyl) -4-benzidine, 28.83g of sodium tert-butoxide (300 mmol), 800ml of xylene, and 1mol% Pd (dba). The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder a12. Wherein, the addition amount of Pd (dba) is 1mol% of M5.
1 H NMR(400MHz,Chloroform)δ8.09(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 values, 732.8; theoretical value, 733.3.
Synthesis example 6: synthesis of Compound A15
Into a reaction flask were charged 100mmol of methyl 2-borate, 100mmol of 2-bromo-4-chlorophenol, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh 3 ) 4 . The reaction was carried out at 120℃for 12h. After the reaction, the reaction is stopped, the reactant is cooled to room temperature, water is added, the organic phase is concentrated to obtain white solid, the white solid is filtered and washed, and the obtained solid is recrystallized and purified by toluene to obtain white powder M1. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of 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 reaction flask is warmed to room temperature for reaction for 12h after the dropwise addition. After the reaction, water is added, the organic phase is separated and concentrated to obtain an intermediate M2.
100mmol of M2 and 200ml of trifluoromethanesulfonic anhydride were added to the reaction flask, and the mixture was heated to 120℃and reacted for 12 hours. After the reaction, water is added, solid is separated out, filtered and dried to obtain an 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 (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh) 3 ) 4 . The reaction was carried out at 120℃for 12h. After the reaction, the reaction is stopped, the reactant is cooled to room temperature, water is added, the organic phase is concentrated to obtain white solid, the white solid is filtered and washed, and the obtained solid is recrystallized and purified by toluene to obtain white powder M4. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M3.
100mmol of M4, 300ml of dichloromethane and 20ml of triethylamine are added into a reaction bottle, the temperature is reduced to 0 ℃, 110mmol of trifluoromethanesulfonic anhydride is added dropwise, and the mixture is stirred at normal temperature and reacts for 12 hours. After the reaction, adding water, separating an organic phase, concentrating and drying to obtain an intermediate M5, wherein a group TfO in the M5 is a trifluoro sulfonic group.
To the reaction flask were added 100mmol of M5, 100mmol of 3-N-phenylcarbazolyl-2-naphthylamine, 28.83g of sodium tert-butoxide (300 mmol), 800ml of xylene, and 1mol% of Pd (dba). The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder a15. Wherein, the addition amount of Pd (dba) is 1mol% of M5.
1 H NMR(400MHz,Chloroform)δ8.55(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 values, 822.1; theoretical value, 822.4.
Synthesis example 7: synthesis of Compound A19
Into a reaction flask were charged 100mmol of methyl 2-borate 3-naphthoate, 100mmol of 2-bromo-4-chlorophenol, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh 3 ) 4 . The reaction was carried out at 120℃for 12h. Stopping the reaction after the reaction is completed, and cooling the reactantTo room temperature, water was added, and the organic phase was concentrated to give a white solid, which was filtered and washed with water, and the obtained solid was purified by recrystallization from toluene to give white powder M1. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of 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 reaction flask is warmed to room temperature for reaction for 12h after the dropwise addition. After the reaction, water is added, the organic phase is separated and concentrated to obtain an intermediate M2.
100mmol of M2 and 200ml of trifluoromethanesulfonic anhydride were added to the reaction flask, and the mixture was heated to 120℃and reacted for 12 hours. After the reaction, water is added, solid is separated out, filtered and dried to obtain an intermediate M3.
Into a reaction flask were charged 100mmol of 9, 9-dimethylfluorene-2-boronic acid, 100mmol of M3, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh 3 ) 4 . The reaction was carried out at 120℃for 12h. After the reaction, the reaction is stopped, the reactant is cooled to room temperature, water is added, the organic phase is concentrated to obtain white solid, the white solid is filtered and washed, and the obtained solid is recrystallized and purified by toluene to obtain white powder M4. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M3.
100mmol of M4, 300ml of dichloromethane and 20ml of triethylamine are added into a reaction bottle, the temperature is reduced to 0 ℃, 110mmol of trifluoromethanesulfonic anhydride is added dropwise, and the mixture is stirred at normal temperature and reacts for 12 hours. After the reaction, adding water, separating an organic phase, concentrating and drying to obtain an intermediate M5, wherein a group TfO in the M5 is a trifluoro sulfonic group.
To the reaction flask were added 100mmol of M5, 100mmol of 2- (9, 9-dimethylfluorenyl) -4- (9, 9-dimethylfluorenyl) amine, 28.83g of sodium t-butoxide (300 mmol), 800ml of xylene, and 1mol% of Pd (dba). The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder a19. Wherein, the addition amount of Pd (dba) is 1mol% of M5.
1 H NMR(400MHz,Chloroform)δ8.18(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 values, 835.2; theoretical value, 835.4.
Synthesis example 8: synthesis of Compound A20
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 (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh 3 ) 4 . The reaction was carried out at 120℃for 12h. After the reaction, the reaction is stopped, the reactant is cooled to room temperature, water is added, the organic phase is concentrated to obtain white solid, the white solid is filtered and washed, and the obtained solid is recrystallized and purified by toluene to obtain white powder M1. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of 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 reaction flask is warmed to room temperature for reaction for 12h after the dropwise addition. After the reaction, water is added, the organic phase is separated and concentrated to obtain an intermediate M2.
100mmol of M2 and 200ml of trifluoromethanesulfonic anhydride were added to the reaction flask, and the mixture was heated to 120℃and reacted for 12 hours. After the reaction, water is added, solid is separated out, filtered and dried to obtain an intermediate M3.
Into a reaction flask were charged 100mmol of 9, 9-dimethylfluorene-1-boronic acid, 100mmol of M3, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh 3 ) 4 . The reaction was carried out at 120℃for 12h. After the reaction, the reaction is stopped, the reactant is cooled to room temperature, water is added, the organic phase is concentrated to obtain white solid, the white solid is filtered and washed, and the obtained solid is recrystallized and purified by toluene to obtain white powder M4. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M3.
Into a reaction flask were charged 100mmol of phenylboronic acid, 100mmol of M4, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh) 3 ) 4 . The reaction was carried out at 120℃for 12h. After the reaction, the reaction is stopped, the reactant is cooled to room temperature, water is added, the organic phase is concentrated to obtain white solid, the white solid is filtered and washed, and the obtained solid is recrystallized and purified by toluene to obtain white powder M5. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M4.
100mmol of M5, 300ml of dichloromethane and 20ml of triethylamine are added into a reaction bottle, the temperature is reduced to 0 ℃, 110mmol of trifluoromethanesulfonic anhydride is added dropwise, and the mixture is stirred at normal temperature and reacts for 12 hours. After the reaction, adding water, separating an organic phase, concentrating and drying to obtain an intermediate M6, wherein a group TfO in the M6 is a trifluoro sulfonic group.
To the reaction flask were added 100mmol of M6, 100mmol of 2- (dibenzothiophene) -2-benzidine, 28.83g of sodium tert-butoxide (300 mmol), 800ml of xylene, and 1mol% of palladium dibenzyl acetonate (Pd (dba)). The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, the organic phase was separated, concentrated, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder a20. Wherein, the addition amount of Pd (dba) is 1mol% of M6.
1 H NMR(400MHz,Chloroform)δ8.44(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 values, 810.8; theoretical value, 811.3.
Synthesis example 9: synthesis of Compound A21
Into a reaction flask were charged 100mmol of methyl 2-borate, 100mmol of 2-bromo-4-chlorophenol, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh 3 ) 4 . The reaction was carried out at 120℃for 12h. After the reaction, the reaction is stopped, the reactant is cooled to room temperature, water is added, the organic phase is concentrated to obtain white solid, the white solid is filtered and washed, and the obtained solid is recrystallized and purified by toluene to obtain white powder M1. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of 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 reaction flask is warmed to room temperature for reaction for 12h after the dropwise addition. After the reaction, water is added, the organic phase is separated and concentrated to obtain an intermediate M2.
100mmol of M2 and 200ml of trifluoromethanesulfonic anhydride were added to the reaction flask, and the mixture was heated to 120℃and reacted for 12 hours. After the reaction, water is added, solid is separated out, filtered and dried to obtain an intermediate M3.
Into a reaction flask were charged 100mmol of 9, 9-dimethylfluorene-2-boronic acid, 100mmol of M3, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh 3 ) 4 . The reaction was carried out at 120℃for 12h. After the reaction, the reaction is stopped, the reactant is cooled to room temperature, water is added, the organic phase is concentrated to obtain white solid, the white solid is filtered and washed, and the obtained solid is recrystallized and purified by toluene to obtain white powder M4. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M3.
100mmol of M4, 300ml of dichloromethane and 20ml of triethylamine are added into a reaction bottle, the temperature is reduced to 0 ℃, 110mmol of trifluoromethanesulfonic anhydride is added dropwise, and the mixture is stirred at normal temperature and reacts for 12 hours. After the reaction, adding water, separating an organic phase, concentrating and drying to obtain an intermediate M5, wherein a group TfO in the M5 is a trifluoro sulfonic group.
To the reaction flask were added 100mmol of p-bromoiodobenzene, 100mmol of 2- (9, 9-dimethylfluorene) -4-benzidine, 28.83g of sodium t-butoxide (300 mmol), 800ml of xylene, and 1mol% of palladium dibenzyl acetonate (Pd (dba)). The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was separated, concentrated, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M6. Wherein, the addition amount of Pd (dba) is 1mol% of the p-bromoiodobenzene.
Into a reaction flask were charged 100mmol of M6, 110mmol of pinacol biborate, 41.4g of potassium acetate (300 mmol), 800ml of dioxane, and 1mol% of dichloro [1,1' -bis (diphenylphosphine) ferrocene ]Palladium (Pd (dppf) Cl) 2 ). The reaction was carried out at 100℃for 12h. After the reaction, the reaction was stopped, and the reaction product was cooled to room temperature, water was added, the organic phase was separated, and a white solid was obtained by concentration, filtration and washing with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M7. Wherein Pd (dppf) Cl 2 The amount of (2) added was 1mol% of M6.
Into a reaction flask were charged 100mmol of M5, 100mmol of M7, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh) 3 ) 4 . The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to give a white solid, which was filtered and washed with water, and the obtained solid was purified by recrystallization with toluene to give white powder a21. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M5.
1 H NMR(400MHz,Chloroform)δδ8.11–7.93(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 values, 821.3; theoretical value, 821.4.
Synthesis example 10: synthesis of Compound A25
Into a reaction flask were charged 100mmol of methyl 2-borate, 100mmol of 2-bromo-4-chlorophenol, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh 3 ) 4 . The reaction was carried out at 120℃for 12h. Stopping the reaction after the reaction is completed, cooling the reactant to room temperature, adding water, concentrating the organic phase to obtain white solid, filtering, washing the obtained solid with water, and using toluene to make weight treatment Crystallization and purification gave white powder M1. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of 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 reaction flask is warmed to room temperature for reaction for 12h after the dropwise addition. After the reaction, water is added, the organic phase is separated and concentrated to obtain an intermediate M2.
100mmol of M2 and 200ml of trifluoromethanesulfonic anhydride were added to the reaction flask, and the mixture was heated to 120℃and reacted for 12 hours. After the reaction, water is added, solid is separated out, filtered and dried to obtain an intermediate M3.
To the reaction flask were added 100mmol of M3, 100mmol of diphenylamine, 28.83g of sodium t-butoxide (300 mmol), 800ml of xylene, and 1mol% Pd (dba). The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was separated, concentrated, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder M4. Wherein, the addition amount of Pd (dba) is 1mol% of M3.
Into a reaction flask were charged 100mmol of M3, 110mmol of pinacol biborate, 41.4g of potassium acetate (300 mmol), 800ml of dioxane, and 1mol% of Pd (dppf) Cl 2 . The reaction was carried out at 100℃for 12h. Stopping the reaction after the reaction, cooling the reactant to room temperature, adding water, separating an organic phase, concentrating to obtain a white solid, filtering, washing the white solid, and recrystallizing and purifying the obtained solid by using toluene to obtain white powder M5, wherein a group TfO in the M5 is a trifluoro sulfonic acid group. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M3.
100mmol of M4 and 300ml of dichloromethane, 20ml of triethylamine are added into a reaction bottle, the temperature is reduced to 0 ℃, 110mmol of trifluoromethanesulfonic anhydride is added dropwise, and the mixture is stirred at normal temperature and reacts for 12 hours. After the reaction, water is added, the organic phase is separated, concentrated and dried to obtain an intermediate M6.
Into a reaction flask were charged 100mmol of M5, 100mmol of M6, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water, and 1mol% of Pd (PPh) 3 ) 4 . The reaction was carried out at 120℃for 12h. Stopping the reaction after the reaction is finishedThe reaction was cooled to room temperature, water was added, the organic phase was concentrated to give a white solid, which was filtered and washed with water, and the obtained solid was purified by recrystallization from toluene to give white powder M7. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M6.
100mmol of M7, 300ml of dichloromethane and 20ml of triethylamine are added into a reaction bottle, the temperature is reduced to 0 ℃, 110mmol of trifluoromethanesulfonic anhydride is added dropwise, and the mixture is stirred at normal temperature and reacts for 12 hours. After the reaction, adding water, separating an organic phase, concentrating and drying to obtain an intermediate M8, wherein a group TfO in the M8 is a trifluoro sulfonic group.
To the reaction flask were added 100mmol of M8, 100mmol of 2- (9, 9-dimethylfluorene) -2-naphthylamine, 28.83g of sodium tert-butoxide (300 mmol), 800ml of xylene, and 1mol% of Pd (dba). The reaction was carried out at 120℃for 12h. After the reaction, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was separated, concentrated, filtered, and washed with water, and the obtained solid was purified by recrystallization with toluene to obtain white powder a25. Wherein, the addition amount of Pd (dba) is 1mol% of the p-bromoiodobenzene.
1 H NMR(400MHz,Chloroform)δ7.90(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 values, 886.2; theoretical value, 886.4.
Other compounds of the present invention can be synthesized by selecting appropriate starting materials according to the concepts of examples 1 to 10, or by selecting any other appropriate methods and starting materials.
Example 1
Ultrasonic treating the glass plate coated with the ITO transparent conductive layer in a commercial cleaning agent, flushing in deionized water, ultrasonic degreasing in an acetone-ethanol mixed solvent, baking in a clean environment until water is completely removed, cleaning with ultraviolet light and ozone, and bombarding the surface with a low-energy cation beam;
placing the above glass substrate with anode in vacuum cavity, and vacuumizing to less than 10 -5 Vacuum evaporating HT-11 on the anode layer film as a hole injection layer at an evaporation rate of 0.1nm/s and an evaporation film thickness of 10nm;
vacuum evaporating A1 material on the hole injection layer to serve as a hole transport layer, wherein the evaporation rate is 0.1nm/s, and the thickness of the evaporation film is 80nm;
vacuum evaporating a light-emitting layer on the hole transmission layer, wherein the light-emitting layer comprises a main material GHP-16 and a dye material RPD-1, evaporating by utilizing a multi-source co-evaporation method, adjusting the evaporation rate of the main material GHP-16 to be 0.1nm/s, wherein the evaporation rate of the dye RPD-1 is 3% of the evaporation rate of the main material, and the total evaporation film thickness is 30nm;
Vacuum evaporating an electron transport layer on the luminescent layer, wherein a material ET-42 is selected as the electron transport material, the evaporation rate is 0.1nm/s, and the thickness of the evaporation film is 30nm;
vacuum evaporating LiF with the thickness of 0.5nm on an Electron Transport Layer (ETL) as an electron injection layer, wherein the evaporation rate is 0.1nm/s;
finally, an aluminum layer with the thickness of 150nm is evaporated on the electron injection layer to be used as a cathode of the organic electroluminescent device, and the evaporation rate is 0.1nm/s.
Examples 2 to 10
The procedure of example 1 was repeated 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 are shown in Table 1, except that HT-27 was used in place of A1, which was the same as in example 1.
The organic electroluminescent device prepared by the above procedure was subjected to the following performance measurement:
the driving voltage and current efficiency and the lifetime of the organic electroluminescent devices prepared in examples and comparative examples were measured using a digital source meter and a luminance meter at the same luminance, specifically, the luminance of the organic electroluminescent devices was measured to be 5000cd/m by increasing the voltage at a rate of 0.1V per second 2 The voltage at the time is the driving voltage, and the current density at the time is measured; the ratio of brightness to current density is the current efficiency; the lifetime test of LT95 is as follows : at 5000cd/m using a luminance meter 2 Under the condition of brightness, constant current is kept, and the brightness of the organic electroluminescent device is measured to be reduced to 4750cd/m 2 Time in hours.
TABLE 1 organic electroluminescent device Performance results
As can be seen from the data in the table, 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, prolong the service life of the device, and is a hole transport material with good performance.
The foregoing description is only of the preferred embodiments of the present invention and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention are included in the protection scope of the present invention.

Claims (4)

1. A compound, wherein the compound is selected from the group consisting of:
2. a hole transport material comprising at least one of the compounds of claim 1.
3. An organic electroluminescent device comprising at least one of the hole transport materials of claim 2.
4. A display device comprising the organic electroluminescent device of claim 3.
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