Heterocyclic compound and organic light emitting device including the same
阅读说明：本技术 杂环化合物及包含其的有机发光器件 (Heterocyclic compound and organic light emitting device including the same ) 是由 朴瑟灿 李东勳 张焚在 郑珉祐 李征夏 韩修进 于 2019-01-25 设计创作，主要内容包括：本发明提供新型杂环化合物及利用其的有机发光器件。(The present invention provides a novel heterocyclic compound and an organic light emitting device using the same.)
1. A compound represented by the following chemical formula 1:
chemical formula 1
Wherein, in the chemical formula 1,
y is S, O or CR'2，
R' is each independently substituted or unsubstituted C1-60Alkyl, substituted or unsubstituted C1-60Alkoxy, substituted or unsubstituted C3-60Cycloalkyl, substituted or unsubstituted C6-60Aryl, substituted or unsubstituted C6-60Aryloxy group, or substituted or unsubstituted C containing 1 or more of O, N, Si and S2-60(ii) a heteroaryl group, wherein,
R1to R7Each independently is halogenElements, hydroxy, cyano, nitrile, nitro, amino, substituted or unsubstituted C1-60Alkyl, substituted or unsubstituted C1-60Haloalkyl, substituted or unsubstituted C1-60Thioalkyl, substituted or unsubstituted C1-60Alkoxy, substituted or unsubstituted C1-60Haloalkoxy, substituted or unsubstituted C3-60Cycloalkyl, substituted or unsubstituted C1-60Alkenyl, substituted or unsubstituted C6-60Aryl, substituted or unsubstituted C6-60Aryloxy group, or substituted or unsubstituted C containing 1 or more of O, N, Si and S2-60(ii) a heteroaryl group, wherein,
a. e and g are each independently 0 to 4,
b. d and f are each independently 0 to 3,
c is 0 to 5.
2. The compound of claim 1, wherein R' is methyl.
3. The compound of claim 1, wherein a, b, c, d, e, and f are 0.
4. The compound of claim 1, wherein R1To R7At least 1 of which is cyano.
5. The compound according to claim 1, wherein the compound represented by the chemical formula 1 is represented by any one selected from the group consisting of:
the description of Y is the same as defined in claim 1.
6. The compound according to claim 1, wherein the compound represented by the chemical formula 1 is any one selected from the group consisting of:
7. an organic light emitting device, comprising: a first electrode, a second electrode provided so as to face the first electrode, and one or more organic layers provided between the first electrode and the second electrode, wherein one or more of the organic layers contain the compound according to any one of claims 1 to 6.
8. The organic light emitting device according to claim 7, wherein the organic layer containing the compound is an electron injection layer, an electron transport layer, an electron injection and transport layer, or a light emitting layer.
9. The organic light-emitting device according to claim 8, wherein the light-emitting layer contains 2 or more kinds of hosts, and 1 of the hosts is the compound.
Technical Field
Cross reference to related applications
The present application claims priority based on korean patent application No. 10-2018-0010013, 26.1.2018, the entire contents of which are incorporated herein by reference.
The present invention relates to a novel heterocyclic compound and an organic light emitting device including the same.
Background
In general, the organic light emitting phenomenon refers to a phenomenon of converting electric energy into light energy using an organic substance. An organic light emitting device using an organic light emitting phenomenon has a wide viewing angle, excellent contrast, a fast response time, and excellent luminance, driving voltage, and response speed characteristics, and thus a great deal of research is being conducted.
An organic light emitting device generally has a structure including an anode and a cathode, and an organic layer located between the anode and the cathode. In order to improve the efficiency and stability of the organic light emitting device, the organic layer is often formed of a multilayer structure formed of different materials, and may be formed of, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, or the like. With the structure of such an organic electroluminescent device, if a voltage is applied between both electrodes, holes are injected from the anode to the organic layer, electrons are injected from the cathode to the organic layer, excitons (exiton) are formed when the injected holes and electrons meet, and light is emitted when the excitons are transitioned to the ground state again.
For organic materials used for the organic light emitting devices as described above, development of new materials is continuously demanded.
Disclosure of Invention
Problems to be solved
The present invention relates to a novel heterocyclic compound and an organic light emitting device including the same.
Means for solving the problems
The present invention provides a compound represented by the following chemical formula 1:
[ chemical formula 1]
In the above-described chemical formula 1,
y is S, O or CR'2，
R' is each independently substituted or unsubstituted C1-60Alkyl, substituted or unsubstituted C1-60Alkoxy, substituted or unsubstituted C3-60Cycloalkyl, substituted or unsubstituted C6-60Aryl, substituted or unsubstituted C6-60Aryloxy group, or substituted or unsubstituted C containing 1 or more of O, N, Si and S2-60(ii) a heteroaryl group, wherein,
R1to R7Each independently is halogen, hydroxy, cyano, nitrile, nitro, amino, substituted or unsubstituted C1-60Alkyl, substituted or unsubstituted C1-60Haloalkyl, substituted or unsubstituted C1-60Thioalkyl, substituted or unsubstituted C1-60Alkoxy, substituted or unsubstituted C1-60Haloalkoxy, substituted or unsubstituted C3-60Cycloalkyl, substituted or unsubstituted C1-60Alkenyl, substituted or unsubstituted C6-60Aryl, substituted or unsubstituted C6-60Aryloxy group, or substituted or unsubstituted C containing 1 or more of O, N, Si and S2-60(ii) a heteroaryl group, wherein,
a. e and g are each independently 0 to 4,
b. d and f are each independently 0 to 3,
c is 0 to 5.
The present invention also provides an organic light-emitting device including a first electrode, a second electrode provided so as to face the first electrode, and 1 or more organic layers provided between the first electrode and the second electrode, wherein 1 or more of the organic layers include a compound represented by chemical formula 1.
Effects of the invention
The compound represented by the above chemical formula 1 may be used as a material of an organic layer of an organic light emitting device in which improvement of efficiency, lower driving voltage, and/or improvement of life span characteristics can be achieved. In particular, the compound represented by the above chemical formula 1 may be used as a material for hole injection, hole transport, hole injection and transport, light emission.
Drawings
Fig. 1 illustrates an example of an organic light-emitting device composed of a substrate 1, an anode 2, a light-emitting layer 3, and a cathode 4.
Fig. 2 illustrates an example of an organic light-emitting device composed of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 7, a light-emitting layer 8, an electron transport layer 9, an electron injection layer 10, and a cathode 4.
Fig. 3 illustrates an example of an organic light-emitting device composed of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light-emitting layer 8, an electron transport layer 9, an electron injection and transport layer 11, and a cathode 4.
Detailed Description
Hereinafter, the present invention will be described in more detail to assist understanding thereof.
The present invention provides a compound represented by the above chemical formula 1.
In the context of the present specification,
In the present specification, the term "substituted or unsubstituted" means substituted with a substituent selected from deuterium; a halogen group; a nitrile group; a nitro group; a hydroxyl group; a carbonyl group; an ester group; an imide group; an amino group; a phosphine oxide group; an alkoxy group; an aryloxy group; alkylthio radicals (A), (B), (C), (D), (
In the present specification, the number of carbon atoms of the carbonyl group is not particularly limited, but is preferably 1 to 40. Specifically, the compound may have the following structure, but is not limited thereto.
In the ester group, in the present specification, the oxygen of the ester group may be substituted with a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms. Specifically, the compound may be a compound of the following structural formula, but is not limited thereto.
In the present specification, the number of carbon atoms in the imide group is not particularly limited, but is preferably 1 to 25. Specifically, the compound may have the following structure, but is not limited thereto.
In the present specification, specific examples of the silyl group include, but are not limited to, a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, and a phenylsilyl group.
In the present specification, the boron group includes specifically a trimethylboron group, a triethylboron group, a t-butyldimethylboron group, a triphenylboron group, a phenylboron group and the like, but is not limited thereto.
In the present specification, examples of the halogen group include fluorine, chlorine, bromine, and iodine.
In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the alkyl group has 1 to 20 carbon atoms. According to another embodiment, the alkyl group has 1 to 10 carbon atoms. According to another embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an n-propyl group, an isopropyl group, a butyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a sec-butyl group, a 1-methylbutyl group, a 1-ethylbutyl group, a pentyl group, an n-pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a hexyl group, a n-hexyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 4-methyl-2-pentyl group, a3, 3-dimethylbutyl group, a 2-ethylbutyl group, a heptyl group, a n-heptyl group, a 1-methylhexyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, an octyl group, a n-octyl group, a tert-octyl group, a 1-methylheptyl group, a 2-ethylhexyl group, a 2-propyl, Isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but are not limited thereto.
In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the number of carbon atoms of the alkenyl group is 2 to 20. According to another embodiment, the number of carbon atoms of the alkenyl group is 2 to 10. According to another embodiment, the number of carbon atoms of the above alkenyl group is 2 to 6. Specific examples thereof include, but are not limited to, vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-methyl-1-butenyl, 1, 3-butadienyl, allyl, 1-phenylethen-1-yl, 2-diphenylethen-1-yl, 2-phenyl-2- (naphthalen-1-yl) ethen-1-yl, 2-bis (biphenyl-1-yl) ethen-1-yl, stilbenyl, and styryl.
In the present specification, the cycloalkyl group is not particularly limited, but is preferably a cycloalkyl group having 3 to 60 carbon atoms. According to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another embodiment, the number of carbon atoms of the above cycloalkyl group is 3 to 6. Specifically, there may be mentioned, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2, 3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2, 3-dimethylcyclohexyl, 3,4, 5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl and the like.
In the present specification, the aryl group is not particularly limited, but is preferably an aryl group having 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to one embodiment, the aryl group has 6 to 20 carbon atoms. With respect to the above aryl radicals, asThe monocyclic aryl group may be phenyl, biphenyl, terphenyl, etc., but is not limited thereto. The polycyclic aromatic group may be a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a perylene group,
In the present specification, the fluorenyl group may be substituted, and 2 substituents may be combined with each other to form a spiro structure. In the case where the above-mentioned fluorenyl group is substituted, it may be
In the present specification, the heterocyclic group is a heterocyclic group containing at least 1 of O, N, Si and S as a heteroatom, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60. Examples of the heterocyclic group include thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, and the like,
In the present specification, the aryl group in the aralkyl group, aralkenyl group, alkylaryl group, and arylamine group is the same as the above-mentioned examples of the aryl group. In the present specification, the alkyl group in the aralkyl group, the alkylaryl group, and the alkylamino group is the same as the above-mentioned examples of the alkyl group. In the present specification, the heteroaryl group in the heteroarylamine can be applied to the above-mentioned description of the heterocyclic group. In the present specification, the alkenyl group in the aralkenyl group is the same as the above-mentioned examples of the alkenyl group. In the present specification, the arylene group is a 2-valent group, and the above description of the aryl group can be applied thereto. In the present specification, a heteroarylene group is a 2-valent group, and in addition to this, the above description about a heterocyclic group can be applied. In the present specification, the hydrocarbon ring is not a 1-valent group but is formed by combining 2 substituents, and in addition to this, the above description about the aryl group or the cycloalkyl group can be applied. In the present specification, the heterocyclic group is not a 1-valent group but a combination of 2 substituents, and the above description of the heterocyclic group can be applied.
On the other hand, in the chemical formula 1, R' is preferably a methyl group.
In the above chemical formula 1, a, b, c, d, e and f may be 0.
In the above chemical formula 1, R1To R7At least 1 of which may be cyano.
The chemical formula 1 may be any one selected from the following compounds.
In the above 1-1 to 1-16, Y may be S, O or CR'2。
The above definition of R' is the same as that mentioned previously.
Preferably, the compound represented by the above chemical formula 1 may be any one selected from the following compounds.
The compound represented by the above chemical formula 1 can be produced by the production method of the following reaction formula 1. The above-described manufacturing method can be further embodied in the manufacturing examples described later.
[ reaction formula 1]
In the above reaction formula 1, the description of Y is the same as that in the above chemical formula 1.
The compound represented by the above chemical formula 1 can be produced by referring to the above reaction formula 1 and appropriately replacing the starting material corresponding to the structure of the compound to be produced.
In addition, the present invention provides an organic light emitting device comprising the compound represented by the above chemical formula 1. As an example, the present invention provides an organic light emitting device, comprising: the organic light emitting device includes a first electrode, a second electrode provided to face the first electrode, and one or more organic layers provided between the first electrode and the second electrode, wherein one or more of the organic layers include a compound represented by the chemical formula 1.
The organic layer of the organic light-emitting device of the present invention may be formed of a single layer structure, or may be formed of a multilayer structure in which two or more organic layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like as an organic layer. However, the structure of the organic light emitting device is not limited thereto, and a smaller number of organic layers may be included.
In addition, the organic layer may include a hole injection layer, a hole transport layer, or a hole injection and transport layer (a layer that simultaneously performs hole injection and transport), which includes the compound represented by the above chemical formula 1.
In addition, the organic layer may include a light emitting layer including the compound represented by the chemical formula 1.
In addition, the light emitting layer includes 2 or more hosts, and 1 of the hosts includes the compound represented by the chemical formula 1.
In addition, the organic layer may include an electron transport layer, an electron injection layer, or an electron injection and transport layer (a layer that performs electron injection and transport simultaneously), and the electron transport layer, the electron injection layer, or the electron injection and transport layer includes the compound represented by the above chemical formula 1.
In addition, the electron transport layer, the electron injection layer, or the electron transport and injection layer includes the compound represented by the above chemical formula 1.
In addition, the organic layer may include a light emitting layer and an electron transport layer, and the electron transport layer may include a compound represented by the chemical formula 1.
In addition, the organic light emitting device according to the present invention may be an organic light emitting device having a structure (normal type) in which an anode, 1 or more organic layers, and a cathode are sequentially stacked on a substrate. In addition, the organic light emitting device according to the present invention may be an inverted (inverted) type organic light emitting device in which a cathode, 1 or more organic layers, and an anode are sequentially stacked on a substrate. For example, a structure of an organic light emitting device according to an embodiment of the present invention is illustrated in fig. 1 and 2.
Fig. 1 illustrates an example of an organic light-emitting device composed of a substrate 1, an anode 2, a light-emitting layer 3, and a cathode 4. In the structure as described above, the compound represented by the above chemical formula 1 may be included in the above light emitting layer.
Fig. 2 illustrates an example of an organic light-emitting device composed of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 7, a light-emitting layer 8, an electron transport layer 9, an electron injection layer 10, and a cathode 4. In the structure as described above, the compound represented by the above chemical formula 1 may be contained in 1 or more layers among the above hole injection layer, hole transport layer, electron blocking layer, light emitting layer, electron transport layer, and electron injection layer.
Fig. 3 illustrates an example of an organic light-emitting device composed of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light-emitting layer 8, an electron transport layer 9, an electron injection and transport layer 11, and a cathode 4. In the structure as described above, the compound represented by the above chemical formula 1 may be contained in 1 or more layers among the above hole injection layer, hole transport layer, light emitting layer, electron transport layer, and electron injection and transport layer.
The organic light emitting device according to the present invention may be manufactured using materials and methods well known in the art, except that 1 or more of the above organic layers include the compound represented by the above chemical formula 1. In addition, in the case where the organic light emitting device includes a plurality of organic layers, the organic layers may be formed of the same substance or different substances.
For example, the organic light emitting device according to the present invention may be manufactured by sequentially stacking a first electrode, an organic layer, and a second electrode on a substrate. This can be produced as follows: the organic el device is manufactured by depositing a metal, a metal oxide having conductivity, or an alloy thereof on a substrate by a PVD (physical Vapor Deposition) method such as a sputtering method or an electron beam evaporation method (e-beam evaporation) method to form an anode, forming an organic layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer on the anode, and then depositing a substance that can be used as a cathode on the organic layer. In addition to this method, a cathode material, an organic layer, and an anode material may be sequentially deposited on a substrate to manufacture an organic light-emitting device.
In addition, the compound represented by the above chemical formula 1 may be formed into an organic layer not only by a vacuum evaporation method but also by a solution coating method in the manufacture of an organic light emitting device. Here, the solution coating method refers to spin coating, dip coating, blade coating, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited thereto.
In addition to these methods, an organic light-emitting device can be manufactured by depositing a cathode material, an organic material layer, and an anode material on a substrate in this order (WO 2003/012890). However, the production method is not limited thereto.
In one example, the first electrode is an anode and the second electrode is a cathode, or the first electrode is a cathode and the second electrode is an anode.
The anode material is preferably a material having a large work function in order to smoothly inject holes into the organic layer. Specific examples of the anode material include metals such as vanadium, chromium, copper, zinc, and gold, and alloys thereof; metal oxides such as zinc oxide, Indium Tin Oxide (ITO), and Indium Zinc Oxide (IZO); ZnO: al or SNO2: a combination of a metal such as Sb and an oxide; poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxy) thiophene]Conductive polymers such as (PEDOT), polypyrrole, and polyaniline, but the present invention is not limited thereto.
The cathode material is preferably a material having a small work function in order to easily inject electrons into the organic layer. Specific examples of the cathode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, and alloys thereof; LiF/Al or LiO2And a multilayer structure material such as Al, but not limited thereto.
The hole injection material is a layer for injecting holes from the electrode, and the following compounds are preferable as the hole injection material: the organic light-emitting device has an ability to transport holes, has a hole injection effect from an anode, has an excellent hole injection effect for a light-emitting layer or a light-emitting material, prevents excitons generated in the light-emitting layer from migrating to an electron injection layer or an electron injection material, and has excellent thin film formation ability. Preferably, the HOMO (highest occupied molecular orbital) of the hole injecting substance is between the work function of the anode substance and the HOMO of the surrounding organic layer. Specific examples of the hole injecting substance include, but are not limited to, metalloporphyrin (porphyrin), oligothiophene, arylamine-based organic substances, hexanitrile-hexaazatriphenylene-based organic substances, quinacridone-based organic substances, perylene-based organic substances, anthraquinone, polyaniline, and polythiophene-based conductive polymers.
The hole transport layer is a layer that receives holes from the hole injection layer and transports the holes to the light-emitting layer, and the hole transport material is a material that can receive holes from the anode or the hole injection layer and transport the holes to the light-emitting layer, and is preferably a material having a high mobility to holes. Specific examples thereof include, but are not limited to, arylamine-based organic materials, conductive polymers, and block copolymers in which a conjugated portion and a non-conjugated portion are present simultaneously.
The light-emitting substance is a substance that can receive holes and electrons from the hole-transporting layer and the electron-transporting layer, respectively, and combine them to emit light in the visible light region, and a substance having a high quantum efficiency with respect to fluorescence or phosphorescence is preferable. As a specific example, there is an 8-hydroxyquinoline aluminum complex (Alq)3) (ii) a A carbazole-based compound; dimeric styryl (dimerizedstyryl) compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; benzo (b) is
The light emitting layer may include a host material and a dopant material. The host material includes aromatic fused ring derivatives, heterocyclic compounds, and the like. Specifically, the aromatic condensed ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, and the like, and the heterocyclic ring-containing compounds include carbazole derivatives, dibenzofuran derivatives, and ladder-type furan compounds
As the dopant material, there are aromatic amine derivatives and styryl amine compoundsBoron complexes, fluoranthene compounds, metal complexes, and the like. Specifically, the aromatic amine derivative is an aromatic fused ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, or the like having an arylamino group,
The electron transporting material is a layer which receives electrons from the electron injecting layer and transports the electrons to the light emitting layer, and is a material which can satisfactorily receive electrons from the cathode and transfer the electrons to the light emitting layer, and is preferably a material having a high mobility to electrons. Specific examples thereof include Al complexes of 8-hydroxyquinoline and Al complexes containing Alq3Organic radical compounds, hydroxyl brass-metal complexes, etc., but are not limited thereto. The electron transport layer may be used with any desired cathode material as used in the art. Examples of suitable cathode substances are, in particular, the usual substances having a low work function and accompanied by an aluminum or silver layer. In particular cesium, barium, calcium, ytterbium and samarium, in each case accompanied by an aluminum or silver layer.
The electron injection layer is a layer for injecting electrons from the electrode, and is preferably a compound of: has an ability to transport electrons, an electron injection effect from a cathode, an excellent electron injection effect with respect to a light-emitting layer or a light-emitting material, prevents excitons generated in the light-emitting layer from migrating to a hole-injecting layer, and is excellent in thin-film formability. Specifically, there are fluorenone, anthraquinone dimethane (Anthraquinodimethane), diphenoquinone, thiopyran dioxide, and,
Examples of the metal complex include lithium 8-quinolinolato, zinc bis (8-quinolinolato), copper bis (8-quinolinolato), manganese bis (8-quinolinolato), aluminum tris (2-methyl-8-quinolinolato), and gallium tris (8-quinolinolato), bis (10-hydroxybenzo [ h ] quinoline) beryllium, bis (10-hydroxybenzo [ h ] quinoline) zinc, bis (2-methyl-8-quinoline) gallium chloride, bis (2-methyl-8-quinoline) (o-cresol) gallium, bis (2-methyl-8-quinoline) (1-naphthol) aluminum, bis (2-methyl-8-quinoline) (2-naphthol) gallium, and the like, but are not limited thereto.
The organic light emitting device according to the present invention may be a top emission type, a bottom emission type, or a bi-directional emission type, depending on the material used.
In addition, the compound represented by the above chemical formula 1 may be included in an organic solar cell or an organic transistor, in addition to the organic light emitting device.
In the following, preferred embodiments are presented to aid in the understanding of the invention. However, the following examples are only for illustrating the present invention and the present invention is not limited thereto.
[ production example ]
Production example 1: production of intermediate A1
2-chloro-4- (4-chlorophenyl) -6-phenyl-1, 3, 5-triazine (15.0g, 49.64mmol), dibenzo [ b, d ] in a 500ml round-bottomed flask under a nitrogen atmosphere]After thiophen-4-ylboronic acid (11.3g, 49.64mmol) was completely dissolved in 210ml of tetrahydrofuran, 1M potassium carbonate solution (150ml) was added, tetrakis (triphenylphosphine) palladium (1.7g, 1.49mmol) was added,the mixture was stirred with heating for 6 hours. The temperature was lowered to room temperature, the aqueous layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized from 250ml of ethanol to produce the above-mentioned Compound A1(21.1g, yield: 94%) (MS [ M + H ])]+＝450)。
Production example 2: production of intermediate A2
Intermediate A1(21.1g, 46.89mmol), bis (pinacolato) diboron (13.1g, 51.58mmol), Pd (dba) in a 1L round bottom flask under nitrogen2(0.8g，1.41mmol)、PCy3(0.8g,2.81mmol) and KOAc (13.8g, 140.68mmol) were added to 300mL of bis
Production example 3: production of intermediate A3
In a 1L round-bottomed flask under nitrogen atmosphere, after completely dissolving Compound A2(21.1g, 38.97mmol) and 1-bromo-2-nitrobenzene (8.7g,42.86mmol) in 200ml of tetrahydrofuran, 2M aqueous potassium carbonate (60ml) was added, tetrakis (triphenylphosphine) palladium (1.4g, 1.17mmol) was added, and the mixture was stirred under heating for 24 hours. The temperature was lowered to room temperature, the aqueous layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized from 250ml of ethanol to obtain the above-mentioned Compound A3(17.4g, yield: 83%) (MS [ M + H ])]+＝537)。
Production example 4: production of intermediate A4
Triethyl phosphite (100mL, 580.3mmol) was added to compound A3(17.4g, 32.43mmol) in a 1L round bottom flask under nitrogen and stirred for 3 hours under heating. The temperature was reduced to normal temperature and filtered to give a solid which was washed with water. The obtained compound was dried to obtain Compound A4(11.3g, yield: 69%) (MS [ M + H ]]+＝505)。