CN112125892B - Compound, electron transport material and organic electroluminescent device - Google Patents

Compound, electron transport material and organic electroluminescent device Download PDF

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CN112125892B
CN112125892B CN202010905494.3A CN202010905494A CN112125892B CN 112125892 B CN112125892 B CN 112125892B CN 202010905494 A CN202010905494 A CN 202010905494A CN 112125892 B CN112125892 B CN 112125892B
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CN112125892A (en
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邢其锋
丰佩川
单鸿斌
胡灵峰
陈跃
陈雪波
马艳
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Yantai Xianhua Chem Tech Co ltd
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    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/24—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to three ring carbon atoms
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    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
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    • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
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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
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    • H10K85/649—Aromatic compounds comprising a hetero atom
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    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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    • H10K85/649—Aromatic compounds comprising a hetero atom
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    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene

Abstract

The application provides a compound of formula (I) which can be used in electron transport materials. The compound has a parent structure of asymmetrically substituted dibenzoheterocycle, has high bond energy among atoms, good thermal stability, is favorable for solid accumulation among molecules, has strong electron transition capability, and can effectively reduce the driving voltage of an organic electroluminescent device, improve the current efficiency and prolong the service life when being used as an electron transport material. The application also provides an organic electroluminescent device and a display device comprising the compound of the general formula (I).

Description

Compound, electron transport material and organic electroluminescent device
Technical Field
The application relates to the technical field of organic light-emitting display, in particular to an electron transport material and an organic electroluminescent device containing the electron transport material.
Background
Electroluminescence (EL) refers to a phenomenon in which a light emitting material emits light when excited by current and voltage under the action of an electric field, and is a light emitting process in which electric energy is directly converted into light energy. The organic electroluminescent display (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. Currently, an electron transport material is an important functional material, which has a direct effect on the mobility of electrons and ultimately affects the luminous efficiency of an OLED. However, the electron transfer rate achieved by the electron transport materials currently applied to the OLED is low, and the energy level matching with the adjacent layers is poor, which severely restricts the light emitting efficiency of the OLED and the display function of the OLED display device.
KR20180061075A reports an ET (electron transport) structure of a disubstituted dibenzoheterocycle, and the material has good performance as an ET material, but the mobility of the material is still provided with a room for improvement through research, and meanwhile, the film forming property is poor. Aiming at the improvement of the mobility and the film forming property of the material, the structure of the application is designed and invented.
Disclosure of Invention
The embodiment of the application aims to provide an electron transport material so as to improve the working efficiency and prolong the service life of an organic electroluminescent device.
In a first aspect the present application provides a compound of formula (I):
wherein, the liquid crystal display device comprises a liquid crystal display device,
R 1 -R 6 each independently selected from hydrogen, deuterium, C 1 -C 6 Alkyl, C of (2) 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 -R 3 Wherein two adjacent groups can be linked to form a ring, said R 5 And R is 6 Can be connected into a ring;
a is selected from C 6 -C 30 Aromatic groups or C of (2) 3 -C 30 The hydrogen atoms on the aryl and heteroaryl groups each independently may be substituted with Ra;
y is selected from O, S, CR 7 R 8 ，R 7 And R is 8 Each independently selected from C 1 -C 6 Alkyl, C of (2) 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 7 And R is 8 Can be connected into a ring；
X 1 -X 4 Each independently selected from CR 9 Or N, R 9 Selected from hydrogen, deuterium, C 1 -C 6 Alkyl, C of (2) 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, and adjacent R 9 Can be connected into a ring;
L 1 and L 2 Each independently selected from chemical bonds, C 6 -C 30 Arylene group or C of (C) 3 -C 30 The hydrogen atoms on the arylene and heteroarylene groups each independently may be substituted with Ra;
the heteroatoms on the heteroaryl or the heteroarylene are each independently selected from O, S, N;
each Ra is independently selected from deuterium, halogen, nitro, cyano, C 1 -C 4 Alkyl, phenyl, biphenyl, terphenyl or naphthyl.
The second aspect of the present application provides an electron transport material comprising at least one of the compounds provided by the present application.
The third aspect of the present application provides an organic electroluminescent device comprising at least one of the electron transport materials provided by the present application.
The fourth aspect of the application provides a display device comprising the organic electroluminescent device provided by the application.
The compound provided by the application has a parent structure of asymmetrically substituted dibenzoheterocycle, has high bond energy among atoms, good thermal stability, is favorable for solid accumulation among molecules, and has strong electron transition capability. When the organic electroluminescent material is used as an electron transport material, the organic electroluminescent material has proper energy level with adjacent layers, is favorable for electron injection and migration, can effectively reduce driving voltage, has higher electron migration rate, and can realize good luminous efficiency in the organic electroluminescent device. The organic electroluminescent device provided by the application comprises the compound as an electron transport material, so that the driving voltage can be effectively reduced, the luminous efficiency can be improved, and the service life of the organic electroluminescent device can be prolonged. The display device provided by the application has excellent display effect.
Of course, it is not necessary for any one product or method of practicing the application to achieve all of the advantages set forth above at the same time.
Drawings
In order to more clearly illustrate the embodiments of the present application 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 application, 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 application will be made more apparent and fully hereinafter with reference to the accompanying drawings, in which some, but not all embodiments of the application are shown. All other embodiments obtained by those skilled in the art based on the embodiments of the present application are within the scope of the present application.
In a first aspect the present application provides a compound of formula (I):
wherein, the liquid crystal display device comprises a liquid crystal display device,
R 1 -R 6 each independently selected from hydrogen, deuterium, C 1 -C 6 Alkyl, C of (2) 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 -R 3 Wherein two adjacent groups can be linked to form a ring, said R 5 And R is 6 Can be connected into a ring;
a is selected from C 6 -C 30 Aromatic groups or C of (2) 3 -C 30 The hydrogen atoms on the aryl and heteroaryl groups each independently may be substituted with Ra;
y is selected from O, S, CR 7 R 8 ，R 7 And R is 8 Each independently selected from C 1 -C 6 Alkyl, C of (2) 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 7 And R is 8 Can be connected into a ring;
X 1 -X 4 each independently selected from CR 9 Or N, R 9 Selected from hydrogen, deuterium, C 1 -C 6 Alkyl, C of (2) 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, and adjacent R 9 Can be connected into a ring;
L 1 and L 2 Each independently selected from chemical bonds, C 6 -C 30 Arylene group or C of (C) 3 -C 30 The hydrogen atoms on the arylene and heteroarylene groups each independently may be substituted with Ra;
the heteroatoms on the heteroaryl or the heteroarylene are each independently selected from O, S, N;
each Ra is independently selected from deuterium, halogen, nitro, cyano, C 1 -C 4 Alkyl, phenyl, biphenyl, terphenyl or naphthyl.
Preferably, R 1 -R 6 Each independently selected from hydrogen, deuterium, C 1 -C 6 Alkyl, C of (2) 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, A is selected from 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 7 And R is 8 Each independently selected from C 1 -C 6 Alkyl, C of (2) 5 -C 18 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 9 Selected from hydrogen, deuterium, C 1 -C 6 Alkyl, C of (2) 6 -C 30 Aromatic groups or C of (2) 3 -C 30 The hydrogen atoms on the aryl and heteroaryl groups each independently may be substituted with Ra;
preferably L 1 And L 2 Each independently selected from chemical bonds, C 6 -C 18 Arylene group or C of (C) 3 -C 18 The hydrogen atoms on the arylene and heteroarylene groups may each independently be substituted with Ra.
More preferably, the R 1 -R 6 Each independently selected from hydrogen, deuterium, methyl, ethyl, isopropyl, the following groups unsubstituted or substituted with 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, arylamino, carbazolyl.
More preferably, said a is selected from the following groups, unsubstituted or substituted with 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, arylamino, carbazolyl.
More preferably, the R 7 And R is 8 Each independently selected from methyl, ethyl, cyclopentyl, cyclohexyl, the following groups unsubstituted or substituted with 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, arylamino, carbazolyl.
More preferably, the R 9 Selected from hydrogen, deuterium, methyl, ethyl, cyclopentyl, cyclohexyl, the following groups 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, arylamino, carbazolyl.
More preferably, the L 1 And L 2 Each independently selected from the group consisting of a bond, a subunit of the following compounds unsubstituted or substituted with Ra: benzene, biphenyl, terphenyl, naphthalene, phenanthrene, triphenylene, fluorene, pyridine, pyridazine, pyrimidine, pyrazine, quinoline, isoquinoline, quinazoline, quinoxaline, cinnoline, naphthyridine, triazine, pyridopyrazine, furan, benzofuran, dibenzofuran, aza-dibenzofuran, thienylene, benzothiophene, dibenzothiophene, aza-dibenzothiophene, 9-dimethylfluorene, spirofluorene, arylamine, carbazole.
For example, the compound of formula (I) is selected from the following compounds:
the second aspect of the present application provides an electron transport material comprising at least one of the above compounds of the present application.
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 application is not limited to this structure, and the electron transport material of the present application 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, and the like. In practical applications, these layers may be added or omitted as the case may be.
The compound adopted by the electron transport material has a parent structure of asymmetrically substituted dibenzoheterocycle, has high bond energy among atoms, good thermal stability, is favorable for solid accumulation among molecules, has strong electron transition capability, and can effectively reduce the driving voltage of an organic electroluminescent device, improve the current efficiency of the organic electroluminescent device and prolong the service life of the organic electroluminescent device when used as an electron transport layer material.
The derivative of the asymmetrically substituted dibenzoheterocycle provided by the application is applied to an electron transmission layer, has a proper energy level with adjacent layers, is favorable for electron injection and migration, can effectively reduce driving voltage, has a higher electron migration rate, and can realize good luminous efficiency in an organic electroluminescent device. The compound provided by the application has a larger conjugate plane, is favorable for molecular accumulation, shows good thermodynamic stability, and shows long service life in an organic electroluminescent device.
Meanwhile, the preparation process of the asymmetric substituted dibenzoheterocycle derivative is simple and feasible, raw materials are easy to obtain, and the asymmetric substituted dibenzoheterocycle derivative is suitable for industrial production.
The third aspect of the present application provides an organic electroluminescent device comprising at least one of the electron transport materials provided by the present application as an electron transport layer. In the present application, the kind and structure of the organic electroluminescent device are not particularly limited, and may be organic electroluminescent devices of different types and structures known in the art, as long as the electron transport material provided by the present application can be used.
The organic electroluminescent device of the present application may be a light emitting device having a top emission structure, and examples thereof include an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a transparent or semitransparent cathode in this order on a substrate.
The organic electroluminescent device of the present application may be a light emitting device having a bottom light emitting structure, and may include 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 in this order on a substrate.
The organic electroluminescent device of the present application may be a light emitting device having a double-sided light emitting structure, and may include a 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 in this order on a substrate.
In the organic electroluminescent device of the present application, various materials used for the layer in the prior art may be used for the other layers, except that the electron transport layer contains the electron transport material provided by the present application.
For convenience, the organic electroluminescent device of the present application will be described below with reference to fig. 1, but this is not meant to limit the scope of the present application in any way. It is understood that all organic electroluminescent devices capable of using the electron transport material of the present application are within the scope of the present application.
In the present application, the substrate 1 is not particularly limited, and 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 application, the reflective anode electrode 2 is not particularly limited, and may be selected from Indium Tin Oxide (ITO), indium Zinc Oxide (IZO), tin dioxide (SnO) 2 ) The transparent conductive material such as zinc oxide (ZnO) may be a metal material such as silver or an alloy thereof, aluminum or an alloy thereof, or an organic conductive material such as PEDOT (poly 3, 4-ethylenedioxythiophene) may be used, and a multilayer structure of the above materials may be used.
In the present application, the material of the hole injection layer 3 is not particularly limited, and may be made of a hole injection layer material known in the art, for example, a Hole Transport Material (HTM) is selected as the hole injection material.
In the present application, the hole injection layer 3 may further include a p-type dopant, the kind of which is not particularly limited, and various p-type dopants known in the art may be employed, for example, the following p-type dopants may be employed:
in the present application, the amount of the p-type dopant is not particularly limited, and may be an amount well known to those skilled in the art.
In the present application, the hole transport layer 4 is not particularly limited, and at least one of Hole Transport Materials (HTM) known in the art may be used.
For example, the material for the hole injection layer host and the material for the hole transport layer may be selected from at least one of the following HT-1 to HT-31 compounds:
In the present application, the light emitting material in the light emitting layer 5 is not particularly limited, and various light emitting materials known to those skilled in the art may be used, for example, the light emitting material may include a host material and a light emitting dye. The host material 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 application, the light emitting layer 5 employs a phosphorescent electroluminescence technique. The light emitting layer 5 thereof contains a phosphorescent dopant which may be selected from at least one of the following RPD-1 to RPD-28 compounds. The amount of the dopant is not particularly limited and may be an amount well known to those skilled in the art.
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In the present application, the electron transport layer 6 contains at least one of the electron transport materials of the present application, and the electron transport layer 6 may also contain at least one of the electron transport materials of the present application in combination with at least one of the following known electron transport materials ET-1 to ET-57:
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in the present application, the electron transport layer 6 may further include n-type dopants, the kind of which is not particularly limited, and various n-type dopants known in the art may be employed, for example, the following n-type dopants may be employed:
In the present application, the amount of the n-type dopant is not particularly limited, and may be an amount well known to those skilled in the art.
In the present application, the electron injection layer 7 is not particularly limited, and electron injection materials known in the art may be used, for example, may include, but not limited to, liQ, liF, naCl, csF, li in the prior art 2 O、Cs 2 CO 3 At least one of materials such as BaO, na, li, ca.
In the present application, the cathode electrode 8 is not particularly limited, and may be selected from, but not limited to, metals such as magnesium silver mixture, liF/Al, ITO, al, metal mixtures, oxides, and the like.
The fourth aspect of the application provides a display device comprising the organic electroluminescent device provided by the application. Including but not limited to displays, televisions, tablet computers, mobile communication terminals, etc.
The method of preparing the organic electroluminescent device of the present application is not particularly limited, and any method known in the art may be employed, for example, the present application may be prepared by the following preparation method:
(1) Cleaning a reflective anode electrode 2 on an OLED device substrate 1 for top 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 layer 3 on the reflective anode electrode 2, wherein the hole injection layer 3 comprises a main body material and a p-type dopant;
(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 application is not limited to such a structure. The electron transport material of the present application may be used for an organic electroluminescent device of any structure, 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 application 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 application is illustrated below.
Synthetic examples
Synthesis of compound A1:
into a reaction flask were charged 100mmol of 2-iodo-3-bromophenol, 100mmol of 2-fluoro-4-chlorobenzeneboronic acid, 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.
Into the reaction flask, 100mmol of M1, 300ml of Dimethylformamide (DMF), 41.4g of potassium carbonate (300 mmol) and 120℃were added and reacted for 12 hours. After the reaction, water is added, solid is separated out, and the intermediate M2 is obtained after filtration.
Into a reaction flask were charged 100mmol of M2, 110mmol of pinacol biborate, 41.4g of potassium acetate (300 mmol), 800ml of dioxane, and 1mol% of dichloro [1,1' -bis (diphenylphosphino) ferrocene]Palladium (Pd (dppf) Cl) 2 ). The reaction was carried out at 100℃for 12h. After the reaction, the reaction was stopped, the reaction mixture 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 M3. Wherein Pd (dppf) Cl 2 The amount of (2) added was 1mol% of M2.
Into a reaction flask were charged 100mmol of 2-chloro-4, 6-diphenyltriazine, 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 was charged 100mmol of 4- (4-phenylcyano) phenylboronic acid, 100mmol of M4, 41.4g of potassium carbonate (300 mmol), 800ml of THF and 200ml of water are added, 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 A1. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M4.
1 H NMR(400MHz,Chloroform)δ8.36(s,1H),7.99(s,1H),7.96(d,J＝12.4Hz,4H),7.80–7.63(m,5H),7.53(s,2H),7.48(d,J＝12.0Hz,4H),7.25-6.96(m,5H).
Synthesis of compound A6:
into a reaction flask were charged 100mmol of 2-iodo-3-bromophenol, 100mmol of 2-fluoro-4-chlorobenzeneboronic acid, 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.
Into the flask were charged 100mmol of M1, 300ml of DMF,41.4g of potassium carbonate (300 mmol) and reacted at 120℃for 12h. After the reaction, water is added, solid is separated out, and the intermediate M2 is obtained after filtration.
Into a reaction flask were charged 100mmol of M2, 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. After the reaction, the reaction was stopped, the reaction mixture 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 M3. Wherein Pd (dppf) Cl 2 The amount of (2) added was 1mol% of M2.
Into a reaction flask were charged 100mmol of 2-chloro-4, 6-diphenyltriazine, 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 2-cyano-7-bromo-9, 9-dimethylfluorene, 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. 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 M5. Wherein Pd (dppf) Cl 2 The amount of (2-cyano-7-bromo-9, 9-dimethylfluorene added was 1mol%.
Into a reaction flask were charged 100mmol of M5, 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 A6. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M4.
1 H NMR(400MHz,Chloroform)δ8.36(s,1H),8.19–8.04(m,3H),8.00(s,1H),7.99(d,J＝9.6Hz,2H),7.90–7.62(m,8H),7.55–7.52(m,2H),7.48(d,J＝12.0Hz,4H),1.69(s,6H).
Synthesis of compound a 12:
into a reaction flask were charged 100mmol of methyl 2-borate-5-chlorobenzoate, 100mmol of 2-bromoiodobenzene, 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 the catalyst was 1mol% based on 2-bromoiodobenzene.
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 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. 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 M4. Wherein Pd (dppf) Cl 2 The amount of (2) added was 1mol% of M5.
Into a reaction flask were charged 100mmol of 2-chloro-4, 6-diphenyltriazine, 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.
Into a reaction flask was charged 100mmol of 3- (3-phenylcyano) phenylboronAcid, 100mmol of M5, 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 A12. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M5.
1 H NMR(400MHz,Chloroform)δ8.36(s,1H),8.28–7.98(m,4H),7.77(dd,J＝12.8,8.8Hz,6H),7.69(d,J＝8.0Hz,4H),7.61(s,1H),7.50-7.43(m,6H),1.69(s,6H).
Synthesis of compound a 21:
into a reaction flask were charged 100mmol of 2-iodo-3-bromophenol, 100mmol of 2-fluoro-4-chlorobenzeneboronic acid, 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.
Into the flask were charged 100mmol of M1, 300ml of DMF,41.4g of potassium carbonate (300 mmol) and reacted at 120℃for 12h. After the reaction, water is added, solid is separated out, and the intermediate M2 is obtained after filtration.
Into a reaction flask were charged 100mmol of M2, 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. After the reaction, the reaction was stopped, the reaction mixture 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 M3. Wherein Pd is(dppf)Cl 2 The amount of (2) added was 1mol% of M2.
Into a reaction flask were charged 100mmol of 2-bromopyridine, 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 M4, 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. 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 M5. Wherein Pd (dppf) Cl 2 The amount of (2) added was 1mol% of M4.
Into a reaction flask were charged 100mmol of 3-iodo-5-bromochlorobenzene, 105mmol of phenylboronic acid, 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. 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 M6. Wherein Pd (dppf) Cl 2 The amount of the catalyst was 1mol% based on 3-iodo-5-bromochlorobenzene.
Into a reaction flask were charged 100mmol of M6, 100mmol of 4-cyanobenzeneboronic acid, 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 M7. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M6.
Into a reaction flask were charged 100mmol of M7, 100mmol of M5, 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 M7.
1 H NMR(400MHz,Chloroform)δ8.37(s,1H),8.28–8.08(m,4H),8.00–7.91(m,4H),7.62(d,J＝8.4Hz,2H),7.64–7.25(m,5H),7.39(d,J＝12.0Hz,2H),7.39(d,J＝10.0Hz,2H),7.14(s,1H),6.90(s,1H).
Synthesis of compound a 25:
into a reaction flask were charged 100mmol of 2-iodo-3-bromophenylthiophenol, 100mmol of 2-fluoro-4-chlorobenzeneboronic acid, 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.
Into the flask were charged 100mmol of M1, 300ml of DMF,41.4g of potassium carbonate (300 mmol) and reacted at 120℃for 12h. After the reaction, water is added, solid is separated out, and the intermediate M2 is obtained after filtration.
Into a reaction flask were charged 100mmol of M2, 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 is finished, cooling the reactant to room temperature, adding water, separating an organic phase, concentrating to obtain a white solid, and passingThe solid obtained was purified by recrystallization from toluene after filtration and washing with water to obtain white powder M3. Wherein Pd (dppf) Cl 2 The amount of (2) added was 1mol% of M2.
Into a reaction flask were charged 100mmol of 2-chloro-3-phenylquinoxaline, 100mmol of phenylboric acid, 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 2-chloro-3-phenylquinoxaline.
Into a reaction flask were charged 100mmol of M3, 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.
Into a reaction flask were charged 100mmol of 4-cyano-1, 1 '-biphenyl-4' -boronic acid, 100mmol of M5, 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 a25. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M5.
1 H NMR(400MHz,Chloroform)δ8.86(s,2H),8.36(s,1H),8.03(dd,J＝12.8,8.6Hz,3H),7.99(t,J＝12.0Hz,3H),7.97(dd,J＝10.8,8.0Hz,4H),7.84-7.67(m,5H),7.59(s,1H),7.50(s,2H),7.31(d,J＝12.0Hz,4H),7.25(s,2H).
Synthesis of compound a 26:
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.
Into the reaction flask, 100mmol of M1 and 200ml of THF were added, 220mmol of methyl magnesium bromide was added dropwise at 0℃and the reaction was carried out at room temperature for 12 hours after completion of the 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 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. 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 M4. Wherein Pd (dppf) Cl 2 The amount of (2) added was 1mol% of M3.
Into a reaction flask were charged 100mmol of 2-iodo-3-bromophenol, 100mmol of 2-fluoro-4-chlorobenzeneboronic acid, 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 finished, cooling the reactant to room temperature, adding water, concentrating the organic phase to obtain white solid, filtering, washing the white solid with water, and recrystallizing and purifying the obtained solid with toluene to obtain white powderLast M1'. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of 2-bromo-4-chlorophenol.
Into the flask were charged 100mmol of M1, 300ml of DMF,41.4g of potassium carbonate (300 mmol) and reacted at 120℃for 12h. After the reaction, water is added, solid is separated out, and the intermediate M2' is obtained by filtering.
Into a reaction flask were charged 100mmol of M2', 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.
Into a reaction flask were charged 100mmol of M5, 100mmol of 3-cyanobenzeneboronic acid, 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 M6. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M5.
100mmol of M6 and 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 M7, wherein the group OTf in the M7 is a trifluoromethanesulfonic group.
Into a reaction flask were charged 100mmol of M7, 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. 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 M8. Wherein Pd (d) ppf)Cl 2 The amount of (2) added was 1mol% of M7.
Into a reaction flask were charged 100mmol of M8, 100mmol of 2-chloro-4, 6-diphenyltriazine, 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 a26. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M5.
1 H NMR(400MHz,Chloroform)δ8.36(s,2H),8.12–7.94(m,4H),7.90(s,2H),7.87–7.73(m,4H),7.69(s,1H),7.62–7.55(m,4H),7.48(d,J＝12.0Hz,8H),7.34(s,1H),7.24(s,1H),1.69(s,6H).
Synthesis of compound a 27:
into the reaction flask were charged 100mmol of 3-bromonaphtho [2,3-b ] benzofuran, 300ml of DMF, NIS (N-iodosuccinimide) (100 mmol), and the reaction was carried out at 120℃for 12 hours. After the reaction, water is added, solid is separated out, and the intermediate M1 is obtained by filtering.
Into a reaction flask were charged 100mmol of M1, 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. After the reaction, the reaction was stopped, the reaction mixture 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 M3. Wherein Pd (dppf) Cl 2 The amount of (2) added was 1mol% of M2.
Into a reaction flask were charged 100mmol of M2, 100mmol of 2-chloro-4-phenylquinazoline, 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 reactingThe mixture was cooled to 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 M3. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M2.
Into a reaction flask were charged 100mmol of M3, 100mmol of 4- (4-phenylcyano) -1-naphthalene-4-boronic acid, 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 a27. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M3.
1 H NMR(400MHz,Chloroform)δ8.99(d,J＝12.0Hz,2H),7.99(s,1H),7.95(d,J＝8.8Hz,3H),7.92(d,J＝8.4Hz,3H),7.87–7.72(m,6H),7.56(d,J＝13.6Hz,3H),7.48(d,J＝10.0Hz,4H),7.33-7.21(m,4H).
Synthesis of compound a 28:
into a reaction flask were charged 100mmol of 2-iodo-3-bromophenylthiophenol, 100mmol of 2-fluoro-4-chlorobenzeneboronic acid, 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.
Into the flask were charged 100mmol of M1, 300ml of DMF,41.4g of potassium carbonate (300 mmol) and reacted at 120℃for 12h. After the reaction, water is added, solid is separated out, and the intermediate M2 is obtained after filtration.
Into a reaction flask was charged 100mmol of M2, 110mm2.4 g of potassium acetate (300 mmol), 800ml of dioxane and 1mol% of Pd (dppf) Cl 2 . The reaction was carried out at 100℃for 12h. After the reaction, the reaction was stopped, the reaction mixture 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 M3. Wherein Pd (dppf) Cl 2 The amount of (2) added was 1mol% of M2.
Into a reaction flask were charged 100mmol of 2-iodo-3-bromophenol, 100mmol of 2-fluoro-4-chlorobenzeneboronic acid, 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 2-bromo-4-chlorophenol.
Into the flask were charged 100mmol of M4, 300ml of DMF,41.4g of potassium carbonate (300 mmol) and reacted at 120℃for 12h. After the reaction, water is added, solid is separated out, and the intermediate M5 is obtained after filtration.
Into a reaction flask were charged 100mmol of M5, 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. After the reaction, the reaction was stopped, the reaction mixture 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 M3. Wherein Pd (dppf) Cl 2 The amount of (2) added was 1mol% of M6.
Into a reaction flask were charged 100mmol of 2-chloro-3-phenylquinoxaline, 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 finished, cooling the reactant to room temperature, adding water, concentrating the organic phase to obtain white solid, filtering, washing the obtained solid with water, and recrystallizing the obtained solid with toluene to obtain pure productThe mixture was converted to white powder M7. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of 2-chloro-3-phenylquinoxaline.
Into a reaction flask were charged 100mmol of M3, 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 M8. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M3.
Into a reaction flask were charged 100mmol of 4-cyanobenzeneboronic acid, 100mmol of M8, 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 a28. Wherein Pd (PPh) 3 ) 4 The amount of (2) added was 1mol% of M8. 1 H NMR (400 mhz, chloride) delta 8.38 (s, 1H), 8.15 (d, j=10.0 hz, 2H), 8.02 (d, j=7.6 hz, 3H), 7.99-7.91 (m, 4H), 7.84 (s, 1H), 7.79-7.62 (m, 5H), 7.58 (d, j=10.0 hz, 4H), 7.51 (d, j=8.0 hz, 3H), 7.32 (s, 1H) 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;
then placing the above-mentioned glass substrate with anode in vacuum cavity, vacuumizing to less than 10 -5 And vacuum evaporating a hole injection layer on the anode layer film, wherein the hole injection layer is made of HT-11 and 3% of p-type dopant (p-1) by mass ratio, the evaporation rate is 0.1nm/s, the evaporation film thickness is 10nm, and the hole injection layer is made of the following materials:
then, vacuum evaporation of a hole transport material HT-5 as a hole transport layer on the hole injection layer, wherein the evaporation rate is 0.1nm/s, the evaporation film thickness is 80nm, and the hole transport layer is made of the following materials:
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then, a luminescent layer is vacuum-evaporated on the hole transmission layer, the luminescent layer comprises a host material GHP-16 and a dye material RPD-1, evaporation is carried out by utilizing a multi-source co-evaporation method, wherein the evaporation rate of the host material GHP-16 is regulated to be 0.1nm/s, the evaporation rate of the dye RPD-1 is 3% of the evaporation rate of the host material, the total film thickness of the evaporation is 30nm, and the host material and the guest material are respectively the following materials:
Then, an electron transport layer including an electron transport material A1 is vacuum-deposited over the light-emitting layer. Wherein, the vapor deposition rate is 0.1nm/s, the vapor deposition film thickness is 30nm, and the selected electron transport material A1 has the following formula:
then, liF with the thickness of 0.5nm is vacuum evaporated on the electron transport layer to be used as an electron injection layer, wherein the evaporation rate is 0.1nm/s, and the thickness of the evaporation film is 10nm;
then, an Al layer having a thickness of 150nm was vacuum-deposited on the electron injection layer as a cathode electrode of the organic electroluminescent device, wherein the deposition rate was 1nm/s and the deposition film thickness was 50nm.
Examples 2 to 8
The procedure of example 1 was repeated except that A6, A12, A21, A25, A26, A27 and A28 were used in place of A1. See in particular table 1.
Comparative example 1
The procedure of example 1 was repeated except that ET-2 was used instead of A1.
Comparative example 2
The procedure of example 1 was repeated except that R was used in place of A1.
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 1 to 8 and comparative examples 1 to 2 were measured using a digital source meter and a luminance meter under the same luminance, specifically, the luminance of the organic electroluminescent devices was measured to reach 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 Table 1, the compounds A1, A6, A12, A21, A25, A26, A27 and A28 prepared by the application are used for the electron transport materials of the organic electroluminescent devices, can effectively reduce the driving voltage, improve the current efficiency, prolong the service life of the devices, and are the electron transport materials with good performance.
The foregoing description is only of the preferred embodiments of the present application and is not intended to limit the scope of the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application are included in the protection scope of the present application.

Claims (4)

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