CN113045553A - Aza-aromatic compound used as electron transport material and application thereof - Google Patents

Aza-aromatic compound used as electron transport material and application thereof Download PDF

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CN113045553A
CN113045553A CN202110340272.6A CN202110340272A CN113045553A CN 113045553 A CN113045553 A CN 113045553A CN 202110340272 A CN202110340272 A CN 202110340272A CN 113045553 A CN113045553 A CN 113045553A
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邢其锋
丰佩川
刘一帆
马艳
胡灵峰
陈跃
杨阳
张国选
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Yantai Xianhua Chem Tech Co ltd
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Abstract

The invention provides a class of aza-aromatic compounds, which can be used as electron transport materials. The compound has a parent structure of asymmetrically substituted dibenzo heterocycle, has high bond energy among atoms, good thermal stability, is favorable for solid-state accumulation among molecules, has strong transition capability of electrons, and can effectively reduce the driving voltage of an organic electroluminescent device, improve the current efficiency and prolong the service life when used as an electron transmission material. The invention also provides an organic electroluminescent device and a display device containing the compound.

Description

Aza-aromatic compound used as electron transport material and application thereof
Technical Field
The invention belongs to the technical field of organic photoelectric materials, and particularly relates to a nitrogen-doped aromatic compound used as an electron transport material and application thereof.
Background
Electroluminescence (EL) refers to a phenomenon in which a light emitting material emits light when excited by current and voltage under the action of an electric field, and is a light emitting process in which electric energy is directly converted into light energy. The organic electroluminescent display (hereinafter referred to as OLED) has a series of advantages of self-luminescence, low-voltage dc driving, full curing, wide viewing angle, light weight, simple composition and process, etc., and compared with the liquid crystal display, the organic electroluminescent display does not need a backlight source, and has a large viewing angle, low power, a response speed 1000 times that of the liquid crystal display, and a manufacturing cost lower than that of the liquid crystal display with the same resolution. Therefore, the organic electroluminescent device has very wide application prospect.
With the continuous advance of the OLED technology in the two fields of lighting and display, people pay more attention to the research on efficient organic materials affecting the performance of OLED devices, and an organic electroluminescent device with good efficiency and long service life is generally the result of the optimized matching of device structures and various organic materials, which provides great opportunities and challenges for chemists to design and develop functional materials with various structures.
Organic electroluminescent materials have many advantages over inorganic luminescent materials, such as: the processing performance is good, a film can be formed on any substrate by an evaporation or spin coating method, and flexible display and large-area display can be realized; the optical property, the electrical property, the stability and the like of the material can be adjusted by changing the structure of molecules, and the selection of the material has a large space. In the most common OLED device structures, the following classes of organic materials are typically included: hole injection materials, hole transport materials, electron transport materials, and light emitting materials (dyes or doped guest materials) and corresponding host materials of each color. At present, as an important functional material, an electron transport material has a direct influence on the mobility of electrons, and ultimately influences the luminous efficiency of an OLED. However, the electron transport materials currently used in OLEDs have low electron transfer rates and poor energy level matching with adjacent layers, which severely limits the light emitting efficiency of OLEDs and the display function of OLED display devices.
Disclosure of Invention
The invention provides a class of nitrogen-mixed aromatic compounds used as electron transport materials and application thereof, aiming at improving the luminous efficiency and prolonging the service life of an organic light-emitting electroluminescent device.
The invention discloses a nitrogen heteroaromatic compound, which has a structure shown as a general formula (I):
Figure BDA0002999292560000021
wherein the content of the first and second substances,
R1-R6each independently selected from hydrogen, deuterium, C1-C6Alkyl of (C)6-C30Aryl or C3-C30The hydrogen atoms on the aryl and heteroaryl groups may each independently be substituted by Ra, R1-R2Can be connected into a ring, R4And R5Can be connected into a ring;
a is selected from C6-C30Aryl or C3-C30The hydrogen atoms on the aryl and heteroaryl groups, each independently, may be substituted with Ra;
y is selected from O, S, CR7R8，R7And R8Each independently selected from C1-C6Alkyl of (C)5-C20Cycloalkyl of, C6-C30Aryl or C3-C30The hydrogen atoms on the aryl and heteroaryl groups may each independently be substituted by Ra, R7And R8Can be connected into a ring;
X1-X4each independently selected from CR9Or N, R9Selected from hydrogen, deuterium, C1-C6Alkyl of (C)6-C30Aryl or C3-C30The hydrogen atoms on the aryl and heteroaryl groups may each independently be replaced by Ra, and adjacent R9Can be connected into a ring;
L1and L2Each independently selected from the group consisting of a bond, C6-C30Arylene group of (A) or (C)3-C30The heteroarylene group of (a), wherein the hydrogen atoms on the arylene and heteroarylene groups, independently of each other, may be substituted with Ra;
each heteroatom on the heteroaryl or the heteroarylene is independently selected from O, S, N;
each Ra is independently selected from deuterium, halogen, nitro, cyano, C1-C4Alkyl, phenyl, biphenyl, terphenyl or naphthyl.
Preferably, R1-R6Each independently selected from hydrogen, deuterium, C1-C6Alkyl of (C)6-C18Aryl or C3-C18The hydrogen atoms on the aryl and heteroaryl groups, each independently, may be substituted with Ra;
preferably, A isFrom C6-C18Aryl or C3-C18The hydrogen atoms on the aryl and heteroaryl groups, each independently, may be substituted with Ra;
preferably, R7And R8Each independently selected from C1-C6Alkyl of (C)5-C18Cycloalkyl of, C6-C18Aryl or C3-C18The hydrogen atoms on the aryl and heteroaryl groups, each independently, may be substituted with Ra;
preferably, R9Selected from hydrogen, deuterium, C1-C6Alkyl of (C)6-C30Aryl or C3-C30The hydrogen atoms on the aryl and heteroaryl groups, each independently, may be substituted with Ra;
preferably, L1And L2Each independently selected from the group consisting of a bond, C6-C18Arylene group of (A) or (C)3-C18The heteroarylene group of (a), wherein the hydrogen atoms on the arylene and heteroarylene groups, independently of each other, may be substituted with Ra.
More preferably, said R1-R6Each independently selected from hydrogen, deuterium, methyl, ethyl, isopropyl, the following groups unsubstituted or substituted with Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolyl, isoquinolyl, 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 by Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, arylamino, carbazolyl.
More preferably, said R7And R8Each independently selected from methyl, ethyl, cyclopentyl, cyclohexyl, the following groups unsubstituted or substituted with Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, arylamino, carbazolyl.
More preferably, said R9Selected from hydrogen, deuterium, methyl, ethyl, cyclopentyl, cyclohexyl, the following groups unsubstituted or substituted by Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, arylamino, carbazolyl.
More preferably, said L1And L2Each 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.
More preferably, said azaaromatic compound of general formula (I) is selected from the following compounds:
Figure BDA0002999292560000051
the invention also provides an electron transport material comprising at least one of the azaaromatic compounds provided herein.
The invention also provides an organic electroluminescent device which comprises at least one of the electron transport materials provided by the invention.
Fig. 1 shows a schematic diagram of a typical organic electroluminescent device, in which a substrate 1, a reflective anode electrode 2, a hole injection layer 3, a hole transport layer 4, a light-emitting layer 5, an electron transport layer 6, an electron injection layer 7, and a cathode electrode 8 are sequentially disposed from bottom to top.
It is to be understood that fig. 1 schematically shows the structure of a typical organic electroluminescent device, and the present invention is not limited to this structure, and the electron 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, and the like. In practice, these layers may be added or omitted as the case may be. Also, the organic electroluminescent device may be manufactured using any manufacturing method known in the art.
The organic electroluminescent device of the present invention may be a light-emitting device having a top emission structure, and examples thereof include a light-emitting device comprising an anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a transparent or translucent cathode in this order on a substrate; a light-emitting device which may have a bottom emission structure includes a transparent or translucent anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a cathode structure in this order on a substrate; the light-emitting device may have a double-sided light-emitting structure, and may include a structure in which a transparent or translucent anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a transparent or translucent cathode are sequentially provided on a substrate.
In the organic electroluminescent device of the present invention, in addition to the electron transport layer comprising the electron transport material provided by the present invention, various materials used for the layer in the prior art can be used for the other layer.
For convenience, the organic electroluminescent device of the present invention will be described below with reference to fig. 1, but this is not intended to limit the scope of the present invention in any way. It is understood that all organic electroluminescent devices capable of using the electron transport material of the present invention are within the scope of the present invention.
Preferably, the substrate 1 is not particularly limited, and a conventional substrate used in the organic electroluminescent device in the related art, such as glass, polymer material, glass with TFT components, polymer material, and the like, may be used.
Preferably, 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) known in the art2) Transparent conductive materials such as zinc oxide (ZnO), metal materials such as silver and its alloys, aluminum and its alloys, organic conductive materials such as PEDOT (poly-3, 4-ethylenedioxythiophene), multilayer structures of the above materials, and the like may be used.
Preferably, 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.
Preferably, the hole injection layer 3 may further include a p-type dopant, the kind of the p-type dopant is not particularly limited, and various p-type dopants known in the art may be used, for example, the following p-type dopants may be used:
Figure BDA0002999292560000071
preferably, the amount of the p-type dopant is not particularly limited and may be an amount well known to those skilled in the art.
Preferably, the hole transport layer 4 is not particularly limited, and at least one of Hole Transport Materials (HTM) known in the art may be selected.
Preferably, 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:
Figure BDA0002999292560000072
Figure BDA0002999292560000081
Figure BDA0002999292560000091
preferably, 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:
Figure BDA0002999292560000092
Figure BDA0002999292560000101
Figure BDA0002999292560000111
Figure BDA0002999292560000121
preferably, the light-emitting layer 5 employs the technique of phosphorescent electroluminescence. The light-emitting layer 5 contains a phosphorescent dopant, and the dopant may be at least one selected from the following compounds RPD-1 to RPD-28. The amount of the dopant is not particularly limited and may be an amount known to those skilled in the art.
Figure BDA0002999292560000122
Figure BDA0002999292560000131
Preferably, the electron transport layer 6 comprises at least one of the electron transport materials of the present invention, and the electron transport layer 6 may also comprise a combination of at least one of the electron transport materials of the present invention with at least one of the following known electron transport materials ET-1 to ET-57:
Figure BDA0002999292560000132
Figure BDA0002999292560000141
Figure BDA0002999292560000151
Figure BDA0002999292560000161
preferably, the electron transport layer 6 may further include an n-type dopant, the kind of the n-type dopant is not particularly limited, and various n-type dopants known in the art may be employed, for example, the following n-type dopants may be employed:
Figure BDA0002999292560000162
preferably, the amount of the n-type dopant is not particularly limited and may be an amount well known to those skilled in the art.
Preferably, the electron injection layer 7 is not particularly limited, and an electron injection material known in the art may be used, and for example, at least one of LiQ, LiF, NaCl, CsF, Li2O, Cs2CO3, BaO, Na, Li, Ca, and the like in the prior art may be included, but not limited thereto.
Preferably, the cathode electrode 8 is not particularly limited, and may be selected from, but not limited to, magnesium silver mixture, LiF/Al, ITO, Al, and other metals, metal mixtures, oxides, and the like.
The invention also provides a display device which comprises the organic electroluminescent device provided by the invention. The display device includes, but is not limited to, a display, a television, a tablet computer, a mobile communication terminal, etc.
Preferably, 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 used, for example, the present invention may be prepared by the following preparation method:
(1) cleaning a reflective anode electrode 2 on an OLED device substrate 1 for top emission, respectively carrying out steps of medicinal washing, water washing, hairbrush, high-pressure water washing, air knife and the like in a cleaning machine, and then carrying out heat treatment;
(2) vacuum evaporating a hole injection layer 3 on the reflecting anode electrode 2, wherein the hole injection layer 3 contains a main body material and a p-type dopant;
(3) vacuum evaporating a hole transport material on the hole injection layer 3 to form a hole transport layer 4;
(4) a luminescent layer 5 is evaporated on the hole transport layer 4 in vacuum, wherein the luminescent layer 5 comprises a host material and a guest material;
(5) vacuum evaporating an electron transport material on the luminescent layer 5 to form an electron transport layer 6;
(6) vacuum evaporating an electron injection material as an electron injection layer 7 on the electron transport layer 6, wherein the electron injection material is selected from one or a combination of more of LiQ, LiF, NaCl, CsF, Li2O, Cs2CO3, BaO, Na, Li, Ca and the like;
(7) a cathode material is vacuum-deposited on the electron injection layer 7 as a cathode electrode 8.
The invention also provides a display device comprising the organic electroluminescent device, and the display device comprises but is not limited to a display, a television, a tablet computer, a mobile communication terminal and the like.
The invention has the beneficial effects that:
(1) the compound provided by the invention has a parent structure of an asymmetrically substituted dibenzoheterocycle, has high bond energy among atoms, good thermal stability, favorability for solid-state accumulation among molecules and strong transition capability of electrons. And the preparation process of the derivative asymmetrically substituted with the dibenzoheterocycle is simple and easy to implement, and raw materials are easy to obtain, so that the method is suitable for industrial production.
(2) When the compound provided by the invention is used as an electron transport material, the compound has a proper energy level with the adjacent layers, is beneficial to the injection and the migration of electrons, can effectively reduce the driving voltage, has a high electron migration rate, and can realize good luminous efficiency in an organic electroluminescent device.
(3) The organic electroluminescent device comprises the compound as an electron transport material, so that the driving voltage can be effectively reduced, the luminous efficiency is improved, and the service life of the organic electroluminescent device is prolonged. The display device provided by the invention has excellent display effect.
Of course, not all of the advantages described above need to be achieved at the same time in the practice of any one product or method of the invention.
Drawings
Fig. 1 is a schematic view of a typical organic electroluminescent device according to the present invention, and the parts are respectively:
1. substrate, 2, reflective anode electrode, 3, hole injection layer, 4, hole transport layer, 5, luminescent layer, 6, electron transport layer, 7, electron injection layer, 8, cathode electrode.
Detailed Description
The present invention is described below with reference to examples, which are provided for illustration only and are not intended to limit the scope of the present invention.
Synthesis of Electron transport Material
Example 1
The synthesis of A1 has the following reaction scheme:
Figure BDA0002999292560000181
the preparation process comprises the following steps:
into a reaction flask were charged 100mmol of 2-iodo-4-bromophenol, 100mmol of 2-fluoro-4-chlorobenzeneboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of Tetrahydrofuran (THF) and 200ml of water, and 1 mol% of tetrakis (triphenylphosphine) palladium (Pd (PPh) was added3)4). The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M1. Wherein, Pd (PPh)3)4The amount of (b) added was 1 mol% based on 2-iodo-4-bromophenol.
100mmol of M1, 300ml of Dimethylformamide (DMF), 41.4g of potassium carbonate (300mmol) were added to a reaction flask and reacted at 120 ℃ for 12 hours. After the reaction, water was added to precipitate a solid, which was then filtered to obtain intermediate M2.
100mmol of M2, 110mmol of pinacol diboron, 41.4g of potassium acetate (300mmol), 800ml of dioxane and 1 mol% of dichloro [1,1' -bis (diphenylphosphino) ferrocene are added to a reaction flask]Palladium (Pd (dppf) Cl2). The reaction was carried out at 100 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction was cooled to room temperature, water was added, the organic phase was separated, concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M3. Wherein Pd (dppf) Cl2Was added in an amount of 1 mol% based on M2.
Into a reaction flask were charged 100mmol of 2-chloro-4, 6-diphenyltriazine, 100mmol of M3, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. Reaction at 120 deg.CAnd (4) 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M4. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M3.
Into a reaction flask were charged 100mmol of 4- (4-cyanophenyl) phenylboronic acid, 100mmol of M4, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder a 1. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M4.
The hydrogen spectrum of a1 is characterized as follows:
1H 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,6H),7.25-6.96(m,5H).
example 2
The synthesis of A6 has the following reaction scheme:
Figure BDA0002999292560000201
the preparation process comprises the following steps:
into a reaction flask were charged 100mmol of 2-iodo-4-bromophenol, 100mmol of 2-fluoro-4-chlorobenzeneboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M1. Wherein, Pd (PPh)3)4The amount of (b) added was 1 mol% based on 2-iodo-4-bromophenol.
100mmol of M1, 300ml of DMF, 41.4g of potassium carbonate (300mmol) were added to a reaction flask and reacted at 120 ℃ for 12 hours. After the reaction, water was added to precipitate a solid, which was then filtered to obtain intermediate M2.
100mmol of M2, 110mmol of pinacol diborate, 41.4g of potassium acetate (300mmol), 800ml of dioxane and 1 mol% of Pd (dppf) Cl were charged in a reaction flask2. The reaction was carried out at 100 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction was cooled to room temperature, water was added, the organic phase was separated, concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M3. Wherein Pd (dppf) Cl2Was added in an amount of 1 mol% based on M2.
Into a reaction flask were charged 100mmol of 2-chloro-4, 6-diphenyltriazine, 100mmol of M3, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M4. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M3.
100mmol of 2-cyano-7-bromo-9, 9-dimethylfluorene, 110mmol of pinacol diboron, 41.4g of potassium acetate (300mmol), 800ml of dioxane and 1 mol% of Pd (dppf) Cl were charged in a reaction flask2. The reaction was carried out at 100 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction was cooled to room temperature, water was added, the organic phase was separated, concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M5. Wherein Pd (dppf) Cl2The amount of (A) added was 1 mol% of 2-cyano-7-bromo-9, 9-dimethylfluorene.
Into a reaction flask were charged 100mmol of M5, 100mmol of M4, 41.4g potassium carbonate (300mmol), 800ml THF and 200ml water, and 1 mol% Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. Stopping reaction after the reaction is finished, cooling the reactant to room temperature, adding water, concentrating an organic phase to obtain a white solid, filtering, washing with water, and recrystallizing and purifying the obtained solid with toluene to obtain the compoundWhite powder a 6. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M4.
The hydrogen spectrum of a6 is characterized as follows:
1H 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,3H),7.48(d,J＝12.0Hz,4H),1.69(s,6H).
example 3
The synthesis of A12 has the following reaction scheme:
Figure BDA0002999292560000221
the preparation process comprises the following steps:
into a reaction flask were charged 100mmol of methyl 2-borate-5-chlorobenzoate, 100mmol of 3-bromoiodobenzene, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M1. Wherein, Pd (PPh)3)4The amount of addition of (a) is 1 mol% of 3-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 temperature is raised to room temperature for reaction for 12 hours after the dropwise addition. After the reaction was completed, water was added, the organic phase was separated and concentrated to obtain intermediate M2.
100mmol of M2 and 200ml of trifluoromethanesulfonic anhydride were added to a reaction flask, heated to 120 ℃ and reacted for 12 hours. After the reaction, water was added to precipitate a solid, which was then filtered and dried to obtain intermediate M3.
100mmol of M3, 110mmol of pinacol diborate, 41.4g of potassium acetate (300mmol), 800ml of dioxane and 1 mol% of Pd (dppf) Cl were charged in a reaction flask2. The reaction was carried out at 100 ℃ for 12 h. Stopping reaction after the reaction is finished, cooling the reactant to room temperature, adding water, separating an organic phase, and concentrating to obtain a white solidThe solid was filtered and washed with water, and the obtained solid was purified by recrystallization from toluene to obtain white powder M4. Wherein Pd (dppf) Cl2Was added in an amount of 1 mol% based on M5.
Into a reaction flask were charged 100mmol of 2-chloro-4, 6-diphenyltriazine, 100mmol of M4, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M5. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M4.
Into a reaction flask were charged 100mmol of 3- (3-cyanophenyl) phenylboronic acid, 100mmol of M5, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder a 12. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M5.
The hydrogen spectrum of a12 is characterized as follows:
1H 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,8H),1.69(s,6H).
example 4
The synthesis of A21 has the following reaction scheme:
Figure BDA0002999292560000231
the preparation process comprises the following steps:
into a reaction flask were charged 100mmol of 2-iodo-4-bromophenol, 100mmol of 2-fluoro-4-chlorobenzeneboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. At 120 ℃ by reactionAnd the time is 12 hours. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M1. Wherein, Pd (PPh)3)4The amount of (b) added was 1 mol% based on 2-iodo-4-bromophenol.
100mmol of M1, 300ml of DMF, 41.4g of potassium carbonate (300mmol) were added to a reaction flask and reacted at 120 ℃ for 12 hours. After the reaction, water was added to precipitate a solid, which was then filtered to obtain intermediate M2.
100mmol of M2, 110mmol of pinacol diborate, 41.4g of potassium acetate (300mmol), 800ml of dioxane and 1 mol% of Pd (dppf) Cl were charged in a reaction flask2. The reaction was carried out at 100 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction was cooled to room temperature, water was added, the organic phase was separated, concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M3. Wherein Pd (dppf) Cl2Was added in an amount of 1 mol% based on M2.
Into a reaction flask were added 100mmol of 2-bromopyridine, 100mmol of M3, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M4. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M3.
100mmol of M4, 110mmol of pinacol diborate, 41.4g of potassium acetate (300mmol), 800ml of dioxane and 1 mol% of Pd (dppf) Cl were charged in a reaction flask2. The reaction was carried out at 100 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction was cooled to room temperature, water was added, the organic phase was separated, concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M5. Wherein Pd (dppf) Cl2Was added in an amount of 1 mol% based on M4.
100mmol of 3-iodine-5-bromochlorobenzene, 105mmol of phenylboronic acid, 41.4g of potassium acetate (300mmol), 800ml of dioxane, and 1 mol% of Pd (dppf) Cl2. The reaction was carried out at 100 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction was cooled to room temperature, water was added, the organic phase was separated, concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M6. Wherein Pd (dppf) Cl2The amount of the compound (A) added is 1 mol% of 3-iodo-5-bromochlorobenzene.
Into a reaction flask were charged 100mmol of M6, 100mmol of 4-cyanophenylboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M7. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M6.
Into a reaction flask were charged 100mmol of M7, 100mmol of M5, 41.4g potassium carbonate (300mmol), 800ml THF and 200ml water, and 1 mol% Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder a 21. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M7.
The hydrogen spectrum of a21 is characterized as follows:
1H 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).
example 5
The synthesis of A25 has the following reaction scheme:
Figure BDA0002999292560000251
the preparation process comprises the following steps:
into a reaction flask were charged 100mmol of 2-iodo-4-bromophenylthiol, 100mmol of 2-fluoro-4-chlorobenzeneboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M1. Wherein, Pd (PPh)3)4The amount of the compound (b) is 1 mol% of 2-iodo-4-bromophenylthiophenol.
100mmol of M1, 300ml of DMF, 41.4g of potassium carbonate (300mmol) were added to a reaction flask and reacted at 120 ℃ for 12 hours. After the reaction, water was added to precipitate a solid, which was then filtered to obtain intermediate M2.
100mmol of M2, 110mmol of pinacol diborate, 41.4g of potassium acetate (300mmol), 800ml of dioxane and 1 mol% of Pd (dppf) Cl were charged in a reaction flask2. The reaction was carried out at 100 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction was cooled to room temperature, water was added, the organic phase was separated, concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M3. Wherein Pd (dppf) Cl2Was added in an amount of 1 mol% based on M2.
Into a reaction flask were charged 100mmol of 2-chloro-3-phenylquinoxaline, 100mmol of phenylboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M4. Wherein, Pd (PPh)3)4Is added in an amount of 1 mol% based on the 2-chloro-3-phenylquinoxaline.
Into a reaction flask were charged 100mmol of M3, 100mmol of M4, 41.4g potassium carbonate (300mmol), 800ml THF and 200ml water, and 1 mol% Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction is finishedThe reaction was stopped and the reaction was cooled to room temperature, water was added and the organic phase was concentrated to give a white solid which was filtered, washed with water and the solid obtained was purified by recrystallization from toluene to give M5 as a white powder. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M4.
Into a reaction flask were added 100mmol of 4-cyano-1, 1 '-biphenyl-4' -boronic acid, 100mmol of M5, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder a 25. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M5.
The hydrogen spectrum of a25 is characterized as follows:
1H 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).
example 6
The synthesis of A26 has the following reaction scheme:
Figure BDA0002999292560000271
the preparation process comprises the following steps:
into a reaction flask were charged 100mmol of methyl 2-borate benzoate, 100mmol of 2-bromo-4-chlorophenol, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M1. Wherein, Pd (PPh)3)4The amount of (A) added was 1 mol% based on 2-bromo-4-chlorophenol.
100mmol of M1 and 200ml of THF are added into a reaction flask, 220mmol of methyl magnesium bromide is added dropwise at 0 ℃, and the temperature is raised to room temperature for reaction for 12 hours after the dropwise addition. After the reaction was completed, water was added, the organic phase was separated and concentrated to obtain intermediate M2.
100mmol of M2 and 200ml of trifluoromethanesulfonic anhydride were added to a reaction flask, heated to 120 ℃ and reacted for 12 hours. After the reaction, water was added to precipitate a solid, which was then filtered and dried to obtain intermediate M3.
100mmol of M3, 110mmol of pinacol diborate, 41.4g of potassium acetate (300mmol), 800ml of dioxane and 1 mol% of Pd (dppf) Cl were charged in a reaction flask2. The reaction was carried out at 100 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction was cooled to room temperature, water was added, the organic phase was separated, concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M4. Wherein Pd (dppf) Cl2Was added in an amount of 1 mol% based on M3.
Into a reaction flask were charged 100mmol of 2-iodo-4-bromophenol, 100mmol of 2-fluoro-4-chlorobenzeneboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M1'. Wherein, Pd (PPh)3)4The amount of (b) added was 1 mol% based on 2-iodo-4-bromophenol.
100mmol of M1, 300ml of DMF, 41.4g of potassium carbonate (300mmol) were added to a reaction flask and reacted at 120 ℃ for 12 hours. After the reaction, water was added to precipitate a solid, which was then filtered to obtain intermediate M2'.
Into a reaction flask were charged 100mmol of M2', 100mmol of M4, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M5. Wherein，Pd(PPh3)4Was added in an amount of 1 mol% based on M4.
Into a reaction flask were charged 100mmol of M5, 100mmol of 3-cyanophenylboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M6. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M5.
Adding 100mmol of M6, 300ml of dichloromethane and 20ml of triethylamine into a reaction bottle, cooling to 0 ℃, dropwise adding 110mmol of trifluoromethanesulfonic anhydride, stirring at normal temperature, and reacting for 12 h. After the reaction is finished, water is added, an organic phase is separated, concentrated and dried to obtain an intermediate M7, wherein the OTf group in M7 is trifluoromethanesulfonic group.
100mmol of M7, 110mmol of pinacol diborate, 41.4g of potassium acetate (300mmol), 800ml of dioxane and 1 mol% of Pd (dppf) Cl were charged in a reaction flask2. The reaction was carried out at 100 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction was cooled to room temperature, water was added, the organic phase was separated, concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M8. Wherein Pd (dppf) Cl2Was added in an amount of 1 mol% based on M7.
Into a reaction flask were added 100mmol of M8, 100mmol of 2-chloro-4, 6-di-phenyltriazine, 41.4g potassium carbonate (300mmol), 800ml THF and 200ml water, and 1 mol% Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder a 26. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M5.
The hydrogen spectrum of a26 is characterized as follows:
1H 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).
example 7
The synthesis of A27 has the following reaction scheme:
Figure BDA0002999292560000301
the preparation process comprises the following steps:
100mmol of 3-bromonaphtho [2,3-b ] benzofuran and 300ml of DMF (N-iodosuccinimide) (100mmol) were charged in a reaction flask, and reacted at 120 ℃ for 12 hours. After the reaction, water was added to precipitate a solid, which was then filtered to obtain intermediate M1.
100mmol of M1, 110mmol of pinacol diborate, 41.4g of potassium acetate (300mmol), 800ml of dioxane and 1 mol% of Pd (dppf) Cl were charged in a reaction flask2. The reaction was carried out at 100 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction was cooled to room temperature, water was added, the organic phase was separated, concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M3. Wherein Pd (dppf) Cl2Was added in an amount of 1 mol% based on M2.
Into a reaction flask were charged 100mmol of M2, 100mmol of 2-chloro-4-phenylquinazoline, 41.4g potassium carbonate (300mmol), 800ml THF and 200ml water, and 1 mol% Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M3. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M2.
Into a reaction flask were charged 100mmol of M3, 100mmol of 4- (4-cyanophenyl) -1-naphthalene-4-boronic acid, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. Stopping the reaction after the reaction is finished, cooling the reactant to room temperature,water was added to concentrate the organic phase to give a white solid, which was filtered and washed with water, and the obtained solid was purified by recrystallization from toluene to give a white powder A27. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M3.
The hydrogen spectrum of a27 is characterized as follows:
1H 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,5H).
example 8
The synthesis of A28 has the following reaction scheme:
Figure BDA0002999292560000311
the preparation process comprises the following steps:
into a reaction flask were charged 100mmol of 2-iodo-4-bromophenylthiol, 100mmol of 2-fluoro-4-chlorobenzeneboronic acid, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M1. Wherein, Pd (PPh)3)4The amount of the compound (b) is 1 mol% of 2-iodo-4-bromophenylthiophenol.
100mmol of M1, 300ml of DMF, 41.4g of potassium carbonate (300mmol) were added to a reaction flask and reacted at 120 ℃ for 12 hours. After the reaction, water was added to precipitate a solid, which was then filtered to obtain intermediate M2.
100mmol of M2, 110mmol of pinacol diborate, 41.4g of potassium acetate (300mmol), 800ml of dioxane and 1 mol% of Pd (dppf) Cl were charged in a reaction flask2. The reaction was carried out at 100 ℃ for 12 h. Stopping reaction after the reaction is finished, cooling the reactant to room temperature, adding water, separating an organic phase, concentrating to obtain a white solid, filtering, washing with water, and recrystallizing and purifying the obtained solid with toluene to obtain white solidPowder M3. Wherein Pd (dppf) Cl2Was added in an amount of 1 mol% based on 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 (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M4. Wherein, Pd (PPh)3)4The amount of (A) added was 1 mol% based on 2-bromo-4-chlorophenol.
100mmol of M4, 300ml of DMF, 41.4g of potassium carbonate (300mmol) were added to a reaction flask and reacted at 120 ℃ for 12 hours. After the reaction, water was added to precipitate a solid, which was then filtered to obtain intermediate M5.
100mmol of M5, 110mmol of pinacol diborate, 41.4g of potassium acetate (300mmol), 800ml of dioxane and 1 mol% of Pd (dppf) Cl were charged in a reaction flask2. The reaction was carried out at 100 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction was cooled to room temperature, water was added, the organic phase was separated, concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M3. Wherein Pd (dppf) Cl2Was added in an amount of 1 mol% based on M6.
Into a reaction flask were charged 100mmol of 2-chloro-3-phenylquinoxaline, 100mmol of M6, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder M7. Wherein, Pd (PPh)3)4Is added in an amount of 1 mol% based on the 2-chloro-3-phenylquinoxaline.
Into a reaction flask were charged 100mmol of M3, 100mmol of M7, 41.4g potassium carbonate (300mmol), 800ml THF and 200ml water, and 1 mol% Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. Reaction ofAfter completion of the reaction, the reaction was stopped, and the reaction mass was cooled to room temperature, water was added, the organic phase was concentrated to give a white solid, which was filtered, washed with water, and the obtained solid was purified by recrystallization from toluene to give white powder M8. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M3.
Into a reaction flask were added 100mmol of 4-cyanophenylboronic acid, 100mmol of M8, 41.4g of potassium carbonate (300mmol), 800ml of THF and 200ml of water, and 1 mol% of Pd (PPh) was added3)4. The reaction was carried out at 120 ℃ for 12 h. After the reaction was completed, the reaction was stopped, and the reaction mixture was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered and washed with water, and the obtained solid was recrystallized from toluene to obtain a white powder a 28. Wherein, Pd (PPh)3)4Was added in an amount of 1 mol% based on M8.
The hydrogen spectrum of a28 is characterized as follows:
1H NMR(400MHz,Chloroform)δ8.38(s,1H),8.15(d,J＝10.0Hz,2H),8.02(d,J＝7.6Hz,3H),7.99–7.91(m,4H),7.84(s,1H),7.79–7.62(m,5H),7.58(d,J＝10.0Hz,4H),7.51(d,J＝8.0Hz,4H),7.32(s,1H).
application example of organic electroluminescent device
The structure of the organic electroluminescent device in the application example is shown in fig. 1, and comprises 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 which are sequentially arranged.
The preparation method of the organic electroluminescent device in the application example comprises the following steps:
application example 1
(1) Carrying out ultrasonic treatment on the glass plate coated with the ITO transparent conductive layer in a commercial cleaning agent, washing in deionized water, carrying out ultrasonic oil removal in an acetone-ethanol mixed solvent, baking in a clean environment until the water is completely removed, cleaning by using ultraviolet light and ozone, and bombarding the surface by using low-energy solar beams;
(2) placing the glass substrate with the anode in a vacuum chamber, vacuumizing to less than 10 < -5 > Torr, and performing vacuum evaporation on the anode layer film to form a hole injection layer, wherein the hole injection layer is made of HT-11 and 3% p-type dopant (p-1) by mass, the evaporation rate is 0.1nm/s, the evaporation film thickness is 10nm, and the material of the hole injection layer and the p-type dopant are as follows:
Figure BDA0002999292560000341
(3) and vacuum evaporating a hole transport material HT-5 material on the hole injection layer to form a hole transport 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:
Figure BDA0002999292560000342
(4) and (2) vacuum evaporating a luminescent layer on the hole transport layer, wherein the luminescent layer comprises a host material GHP-16 and a dye material RPD-1, and evaporation is carried out by using a multi-source co-evaporation method, wherein the evaporation rate of the host material GHP-16 is adjusted to be 0.1nm/s, the evaporation rate of the dye RPD-1 is 3% of the evaporation rate of the host material, the total film thickness of evaporation is 30nm, and the host material and the guest material are respectively the following materials:
Figure BDA0002999292560000351
(5) an electron transport layer containing an electron transport material a1 was vacuum-evaporated over the light-emitting layer. Wherein, the evaporation rate is 0.1nm/s, the evaporation film thickness is 30nm, and the selected electron transport material A1 has the following formula:
Figure BDA0002999292560000352
(6) vacuum evaporating LiF with the thickness of 0.5nm on the electron transport layer to form an electron injection layer, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 10 nm;
(7) and (3) performing vacuum evaporation on the electron injection layer to form an Al layer with the thickness of 150nm as a cathode electrode of the organic electroluminescent device, wherein the evaporation rate is 1nm/s, and the evaporation film thickness is 50 nm.
Application examples 2 to 8
The procedure was as in example 1 except that A6, A12, A21, A25, A26, A27 and A28 were used in place of A1. See table 1 for details.
Comparative example 1
The procedure was as in example 1 except that ET-2 was used in place of A1.
Figure BDA0002999292560000361
Comparative example 2
The procedure was as in example 1 except that A1 was replaced with R.
Figure BDA0002999292560000362
The following performance measurements were made for the organic electroluminescent devices of application examples 1 to 8 and comparative examples 1 to 2:
the driving voltage and current efficiency of the organic electroluminescent devices prepared in examples 1 to 8 and comparative examples 1 to 2 and the lifetime of the devices were measured at the same luminance using a digital source meter and a luminance meter, and specifically, the luminance of the organic electroluminescent devices reached 5000cd/m as measured by increasing the voltage at a rate of 0.1V/sec2The current density is measured at the same time as the driving voltage; the ratio of the brightness to the current density is the current efficiency; the life test of LT95 is as follows: using a luminance meter at 5000cd/m2The luminance drop of the organic electroluminescent device was measured to be 4750cd/m by maintaining a constant current at luminance2Time in hours. The results are shown in Table 1.
TABLE 1 organic electroluminescent device Performance results
Figure BDA0002999292560000371
As can be seen from Table 1, the compounds A1, A6, A12, A21, A25, A26, A27 and A28 prepared by the invention are used for the electron transport materials of the organic electroluminescent devices, can effectively reduce the driving voltage, improve the current efficiency and prolong the service life of the devices, and are electron transport materials with good performance.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.

Claims (10)

1. The aza-aromatic compound is characterized by having a structure shown as a formula (I):
Figure FDA0002999292550000011
wherein the content of the first and second substances,
R1-R6each independently selected from hydrogen, deuterium, C1-C6Alkyl of (C)6-C30Aryl or C3-C30The hydrogen atoms on the aryl and heteroaryl groups may each independently be substituted by Ra, R1-R2Can be connected into a ring, R4And R5Can be connected into a ring;
a is selected from C6-C30Aryl or C3-C30The hydrogen atoms on the aryl and heteroaryl groups, each independently, may be substituted with Ra;
y is selected from O, S, CR7R8，R7And R8Each independently selected from C1-C6Alkyl of (C)5-C20Cycloalkyl of, C6-C30Aryl or C3-C30The hydrogen atoms on the aryl and heteroaryl groups may each independently be substituted by Ra, R7And R8Can be connected into a ring;
X1-X4each independently selected from CR9Or N, R9Selected from hydrogen, deuterium, C1-C6Alkyl of (C)6-C30Aryl or C3-C30The hydrogen atoms on the aryl and heteroaryl groups may each independently be replaced by Ra, and adjacent R9Can be connected into a ring;
L1and L2Each independently selected from the group consisting of a bond, C6-C30Arylene group of (A) or (C)3-C30The heteroarylene group of (a), wherein the hydrogen atoms on the arylene and heteroarylene groups, independently of each other, may be substituted with Ra;
each heteroatom on the heteroaryl or the heteroarylene is independently selected from O, S, N;
ra is independently selected from deuterium, halogen, nitro, cyano, C1-C4Alkyl, phenyl, biphenyl, terphenyl or naphthyl.
2. An azaaromatic compound according to claim 1,
R1-R6each independently selected from hydrogen, deuterium, C1-C6Alkyl of (C)6-C18Aryl or C3-C18The hydrogen atoms on the aryl and heteroaryl groups, each independently, may be substituted with Ra;
a is selected from C6-C18Aryl or C3-C18The hydrogen atoms on the aryl and heteroaryl groups, each independently, may be substituted with Ra;
R7and R8Each independently selected from C1-C6Alkyl of (C)5-C18Cycloalkyl of, C6-C18Aryl or C3-C18The hydrogen atoms on the aryl and heteroaryl groups, each independently, may be substituted with Ra;
R9selected from hydrogen, deuterium, C1-C6Alkyl of (C)6-C30Aryl or C3-C30The heteroaryl group of (1), the aryl group and the heteroaryl groupThe hydrogen atoms on the radicals may each independently be substituted by Ra;
L1and L2Each independently selected from the group consisting of a bond, C6-C18Arylene group of (A) or (C)3-C18The heteroarylene group of (a), wherein the hydrogen atoms on the arylene and heteroarylene groups, independently of each other, may be substituted with Ra.
3. An azaaromatic compound as claimed in claim 1 wherein R is1-R6Each independently selected from hydrogen, deuterium, methyl, ethyl, isopropyl, the following groups unsubstituted or substituted with Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, arylamino, carbazolyl.
4. An azaaromatic compound according to claim 1, wherein a is selected from the following unsubstituted or substituted with Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, arylamino, carbazolyl.
5. An azaaromatic compound as claimed in claim 1 wherein R is7And R8Each independently selected from methyl, ethyl, cyclopentyl, cyclohexyl, the following groups unsubstituted or substituted with Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthrylTriphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, arylamine, carbazolyl;
R9selected from hydrogen, deuterium, methyl, ethyl, cyclopentyl, cyclohexyl, the following groups unsubstituted or substituted by Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, triazinyl, pyridopyrazinyl, furanyl, benzofuranyl, dibenzofuranyl, aza-dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, aza-dibenzothienyl, 9-dimethylfluorenyl, arylamino, carbazolyl.
6. An azaaromatic compound as claimed in claim 1 wherein L is1And L2Each 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.
7. An azaaromatic compound according to claim 1, having the structure shown in formula a1-a 30:
Figure FDA0002999292550000041
8. an electron transport material comprising at least one compound according to any one of claims 1 to 7.
9. An organic electroluminescent device, characterized in that it comprises at least one of the electron transport materials of claim 8.
10. A display device characterized in that it comprises the organic electroluminescent device according to claim 9.
CN202110340272.6A 2021-03-30 2021-03-30 Aza-aromatic compound used as electron transport material and application thereof Withdrawn CN113045553A (en)

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Publication number Priority date Publication date Assignee Title
WO2023177176A1 (en) * 2022-03-15 2023-09-21 주식회사 엘지화학 Compound and organic light-emitting element comprising same

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023177176A1 (en) * 2022-03-15 2023-09-21 주식회사 엘지화학 Compound and organic light-emitting element comprising same

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