WO2020085740A1 - Novel heterocyclic compound and organic light emitting diode using same - Google Patents

Abstract

The present invention provides a novel heterocyclic compound and an organic light emitting diode using same.

Description

Novel heterocyclic compound and organic light emitting device using same

Cross-citation with relevant application (s)

This application claims the benefit of priority based on Korean Patent Application No. 10-2018-0125898 filed on October 22, 2018, and Korean Patent Application No. 10-2019-0130597 filed on October 21, 2019. All content disclosed in the documents of is included as part of the present specification.

The present invention relates to a novel heterocyclic compound and an organic light emitting device comprising the same.

In general, the organic light emitting phenomenon refers to a phenomenon that converts electrical energy into light energy using an organic material. The organic light emitting device using the organic light emitting phenomenon has a wide viewing angle, excellent contrast, and fast response time, and has excellent luminance, driving voltage, and response speed characteristics, and thus many studies have been conducted.

The organic light emitting device generally has a structure including an anode and a cathode and an organic material layer between the anode and the cathode. In order to increase the efficiency and stability of the organic light emitting device, the organic material layer is often formed of a multi-layered structure composed of different materials, for example, may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. When a voltage is applied between the two electrodes in the structure of the organic light emitting device, holes are injected at the anode, and electrons are injected at the cathode, and an exciton is formed when the injected holes meet the electrons. When it falls to the ground again, it will shine.

The development of new materials for organic materials used in the organic light emitting device as described above is continuously required.

[Advanced technical literature]

[Patent Document]

(Patent Document 0001) Korean Patent Publication No. 10-2000-0051826

The present invention relates to a novel heterocyclic compound and an organic light emitting device comprising the same.

The present invention provides a compound represented by Formula 1 below.

[Formula 1]

In Chemical Formula 1,

Y ₁ is O or S,

One of Ar ₁ to Ar ₃ is represented by the following Chemical Formula 2, and the other is hydrogen,

One of Ar ₄ to Ar ₇ is substituted or unsubstituted dibenzofuran; Or substituted or unsubstituted dibenzothiophene, the rest being hydrogen,

When Ar ₁ is represented by the following Chemical Formula 2, Ar ₇ is hydrogen,

[Formula 2]

In Chemical Formula 2,

X is each independently N or CH, two or more of X is N,

Y ₂ is O or S,

R ₁ to R ₃ are each independently hydrogen; heavy hydrogen; halogen; Hydroxy; Cyano; Nitrile; Nitro; Amino; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _1-60 haloalkyl; Substituted or unsubstituted C _1-60 thioalkyl; Substituted or unsubstituted C _1-60 alkoxy; Substituted or unsubstituted C _1-60 haloalkoxy; Substituted or unsubstituted C _3-60 cycloalkyl; Or substituted or unsubstituted C _1-60 alkenyl,

a is an integer from 1 to 3,

b is an integer from 1 to 4,

c is an integer from 1 to 5.

In addition, the present invention is a first electrode; A second electrode provided to face the first electrode; And an organic light emitting device including at least one layer of an organic material provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes a compound represented by Chemical Formula 1, and provides an organic light emitting device. do.

The compound represented by Chemical Formula 1 may be used as a material of an organic material layer of an organic light emitting device, and may improve efficiency, low driving voltage, and / or life characteristics in the organic light emitting device. In particular, the compound represented by Formula 1 may be used as a hole injection, hole transport, hole injection and transport, light emission, electron transport, or electron injection material.

FIG. 1 shows an example of an organic light emitting device including a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4.

Figure 2 is a substrate (1), anode (2), hole injection layer (5), hole transport layer (6), electron blocking layer (7), light emitting layer (3), electron transport layer (8), electron injection layer (9) And an example of an organic light-emitting device comprising the cathode 4.

Hereinafter, the present invention will be described in more detail to help understanding.

The present invention provides a compound represented by Formula 1 above.

및

는 다른 치환기에 연결되는 결합을 의미한다.In this specification,

And

Means a linkage to another substituent.

The term "substituted or unsubstituted" as used herein refers to deuterium; Halogen group; Nitrile group; Nitro group; Hydroxy group; Carbonyl group; Ester groups; Imide group; Amino group; Phosphine oxide group; Alkoxy groups; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy group; Aryl sulfoxyl group; Silyl group; Boron group; Alkyl groups; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; An alkenyl group; Alkyl aryl groups; Alkylamine groups; Aralkylamine group; Heteroarylamine group; Arylamine group; Arylphosphine group; Or substituted or unsubstituted with one or more substituents selected from the group consisting of heterocyclic groups containing one or more of N, O and S atoms, or substituted or unsubstituted with two or more substituents among the exemplified substituents above . For example, "a substituent having two or more substituents" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent to which two phenyl groups are connected.

In the present specification, the number of carbon atoms of the carbonyl group is not particularly limited, but is preferably 1 to 40 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the oxygen of the ester group may be substituted with a straight chain, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In this specification, the number of carbon atoms of the imide group is not particularly limited, but is preferably 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the silyl group is specifically trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, etc. However, it is not limited thereto.

In the present specification, the boron group is specifically a trimethyl boron group, a triethyl boron group, a t-butyldimethyl boron group, a triphenyl boron group, a phenyl boron group, and the like, but is not limited thereto.

In the present specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.

In the present specification, the alkyl group may be straight chain or branched chain, and carbon number is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group are methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -Pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but is 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 carbon number of the alkenyl group is 2 to 20. According to another exemplary embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2- ( Naphthyl-1-yl) vinyl-1-yl, 2,2-bis (diphenyl-1-yl) vinyl-1-yl, steelbenyl group, styrenyl group, and the like, but are not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, 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, but is not limited thereto.

In the present specification, the aryl group is not particularly limited, but is preferably 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the carbon number of the aryl group is 6 to 30. According to one embodiment, the carbon number of the aryl group is 6 to 20. The aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc., as a monocyclic aryl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto.

In the present specification, the fluorenyl group may be substituted, and two substituents may combine with each other to form a spiro structure. When the fluorenyl group is substituted,

It can be back. However, it is not limited thereto.

In the present specification, the heterocyclic group is a heterocyclic group containing one or more of O, N, Si, and S as heterogeneous elements, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include thiophene group, furan group, pyrrol group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, acridil group , Pyridazine group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyridopyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group , Carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, isooxazolyl group, tiadiia A sleepy group, a phenothiazinyl group and a dibenzofuranyl group, and the like, but are not limited thereto.

In the present specification, an aryl group in an aralkyl group, an alkenyl group, an alkylaryl group, and an arylamine group is the same as the exemplified aryl group described above. In the present specification, the alkyl group among the aralkyl group, alkylaryl group, and alkylamine group is the same as the above-described alkyl group. In the present specification, the description of the heteroaryl group among heteroarylamines may be applied. In the present specification, the alkenyl group in the alkenyl group is the same as the exemplified alkenyl group. In the present specification, the description of the aryl group described above may be applied, except that the arylene is a divalent group. In the present specification, the description of the heterocyclic group described above may be applied, except that the heteroarylene is a divalent group. In the present specification, the hydrocarbon ring is not a monovalent group, and a description of the aryl group or cycloalkyl group described above may be applied, except that two substituents are formed by bonding. In the present specification, the heterocycle is not a monovalent group, and the description of the aforementioned heterocyclic group may be applied, except that two substituents are formed by bonding.

Preferably, the formula 1 may be any one selected from compounds represented by the following formulas 1-1 to 1-5.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

In Chemical Formulas 1-1 to 1-5,

Y ₁ , Y ₂ , The description of X, R ₁ to R ₃ , a, b and c is as defined above,

Y ₃ is O or S,

R ₄ and R ₅ are each independently hydrogen; heavy hydrogen; halogen; Hydroxy; Cyano; Nitrile; Nitro; Amino; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _1-60 haloalkyl; Substituted or unsubstituted C _1-60 thioalkyl; Substituted or unsubstituted C _1-60 alkoxy; Substituted or unsubstituted C _1-60 haloalkoxy; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _1-60 alkenyl; Substituted or unsubstituted C _6-60 aryl; Substituted or unsubstituted C _6-60 aryloxy; Or a substituted or unsubstituted C _2-60 heteroaryl containing one or more of O, N, Si and S,

d is an integer from 1 to 3,

e is an integer from 1 to 4.

Preferably, X is all N.

Preferably, R ₁ to R ₃ may each independently be hydrogen or deuterium.

Preferably, the compound represented by Formula 1 may be selected from the group consisting of the following compounds.

The compound represented by Chemical Formula 1 may be prepared by the following Reaction Scheme 1. The manufacturing method may be more specific in the manufacturing examples to be described later.

[Scheme 1]

In Reaction Scheme 1, the definitions other than X 'are as defined above, and X' is halogen and more preferably bromo or chloro. The reaction is a Suzuki coupling reaction, and is preferably performed in the presence of a palladium catalyst and a base, and the reactor for the Suzuki coupling reaction can be modified as known in the art. The manufacturing method may be more specific in the manufacturing examples to be described later.

In addition, the present invention provides an organic light emitting device comprising the compound represented by the formula (1). In one example, the present invention is a first electrode; A second electrode provided to face the first electrode; And an organic light emitting device including at least one layer of an organic material provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes a compound represented by Chemical Formula 1, and provides an organic light emitting device. do.

The organic material layer of the organic light emitting device of the present invention may have a single layer structure, but may have a multi-layer structure in which two or more organic material 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 as an organic material layer. However, the structure of the organic light emitting device is not limited thereto, and may include a smaller number of organic layers.

In addition, the organic material layer may include a hole injection layer, a hole transport layer, or a layer that simultaneously performs hole injection and transport, and the hole injection layer, a hole transport layer, or a layer that simultaneously performs hole injection and transport is represented by Formula 1 It includes the compound displayed.

Further, the organic material layer may include a light emitting layer, and the light emitting layer includes a compound represented by Chemical Formula 1.

Further, the organic material layer may include an electron transport layer or an electron injection layer, and the electron transport layer or the electron injection layer includes a compound represented by Chemical Formula 1.

In addition, the electron transport layer, the electron injection layer, or a layer that simultaneously performs electron transport and electron injection includes a compound represented by Chemical Formula 1.

In addition, the organic material layer includes a light emitting layer and an electron transport layer, and the electron transport layer may include a compound represented by Chemical Formula 1.

Further, the organic light emitting device according to the present invention may be an organic light emitting device having a structure in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate. Further, the organic light emitting device according to the present invention may be an organic light emitting device of an inverted type in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate. For example, the structure of the organic light emitting device according to an embodiment of the present invention is illustrated in FIGS. 1 and 2.

FIG. 1 shows an example of an organic light emitting device including a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4. In such a structure, the compound represented by Chemical Formula 1 may be included in the light emitting layer.

Figure 2 is a substrate (1), anode (2), hole injection layer (5), hole transport layer (6), electron blocking layer (7), light emitting layer (3), electron transport layer (8), electron injection layer (9) And an example of an organic light-emitting device comprising the cathode 4. In such a structure, the compound represented by Formula 1 may be included in one or more of the hole injection layer, hole transport layer, electron blocking layer, light emitting layer, electron transport layer, and electron injection layer.

Specifically, the organic material layer may include a light emitting layer, and the light emitting layer may include two or more host materials.

At this time, the two or more host materials may include a compound represented by Chemical Formula 1.

The organic light emitting device according to the present invention may be manufactured by materials and methods known in the art, except that at least one layer of the organic material layer includes the compound represented by Chemical Formula 1. In addition, when the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.

For example, the organic light emitting device according to the present invention may be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate. At this time, a positive electrode is formed by depositing a metal or conductive metal oxide or an alloy thereof on a substrate using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation. Then, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer is formed thereon, and a material that can be used as a cathode is deposited thereon. In addition to this method, an organic light emitting device may be formed by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate.

In addition, the compound represented by Chemical Formula 1 may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light emitting device. Here, the solution application method means spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited to these.

In addition to this method, an organic light emitting device may be manufactured by sequentially depositing an organic material layer and a cathode material from a cathode material on a substrate (WO 2003/012890). However, the manufacturing method is not limited thereto.

In one example, the first electrode is an anode, the second electrode is a cathode, or the first electrode is a cathode, and the second electrode is an anode.

The positive electrode material is preferably a material having a large work function so that hole injection into the organic material layer is smooth. Specific examples of the positive electrode material include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); A combination of metal and oxide such as ZnO: Al or SNO ₂ : Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole, and polyaniline, but are not limited thereto.

The cathode material is preferably a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof; There is a multilayer structure material such as LiF / Al or LiO ₂ / Al, but is not limited thereto.

The hole injection material is a layer for injecting holes from an electrode, and the hole injection material has the ability to transport holes, and thus has a hole injection effect at an anode, an excellent hole injection effect for a light emitting layer or a light emitting material, and is produced in a light emitting layer A compound that prevents migration of the excited excitons to the electron injection layer or the electron injection material, and has excellent thin film formation ability is preferred. It is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic matter, hexanitrile hexaazatriphenylene-based organic matter, quinacridone-based organic matter, and perylene-based Organic materials, anthraquinones, and polyaniline and polythiophene-based conductive polymers, but are not limited thereto.

The hole transport layer is a layer that receives holes from the hole injection layer and transports holes from the hole injection layer to the light emitting layer. A material capable of transporting holes from the anode or the hole injection layer to the light emitting layer as a hole transport material and having a large mobility for holes This is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion, but are not limited thereto.

As the light-emitting material, a material capable of emitting light in the visible light region by receiving and bonding holes and electrons from the hole transport layer and the electron transport layer, respectively, is preferably a material having good quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compound; Benzoxazole, benzthiazole and benzimidazole compounds; Poly (p-phenylenevinylene) (PPV) polymers; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited to these.

The light emitting layer may include a host material and a dopant material. The host material may be a condensed aromatic ring derivative or a heterocyclic compound. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc., and heterocyclic compounds include carbazole derivatives, dibenzofuran derivatives, and ladder types Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Examples of the dopant material include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes arylamino groups such as pyrene, anthracene, chrysene, periplanten, and the substituted or unsubstituted styrylamine compound. A compound in which at least one arylvinyl group is substituted with the arylamine, a substituent selected from 1 or 2 or more from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamino group is substituted or unsubstituted. Specifically, styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but are not limited thereto. In addition, examples of the metal complex include an iridium complex and a platinum complex, but are not limited thereto.

The electron transporting material is a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer. As the electron transporting material, a material capable of receiving electrons from the cathode and transferring them to the light emitting layer, a material having high mobility for electrons This is suitable. Specific examples include the Al complex of 8-hydroxyquinoline; Complexes including Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited to these. The electron transport layer can be used with any desired cathode material as used according to the prior art. In particular, examples of suitable cathode materials are those that have a low work function and are followed by an aluminum or silver layer. Specifically, cesium, barium, calcium, ytterbium and samarium, each case followed by an aluminum layer or a silver layer.

The electron injection layer is a layer that injects electrons from an electrode, has the ability to transport electrons, has an electron injection effect from a cathode, has an excellent electron injection effect on a light emitting layer or a light emitting material, and injects holes generated in the light emitting layer A compound that prevents migration to the layer and has excellent thin film forming ability is preferred. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone and the like and their derivatives, metal Complex compounds, nitrogen-containing 5-membered ring derivatives, and the like, but are not limited thereto.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinato) copper, bis (8-hydroxyquinolinato) manganese, Tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8-hydroxyquinolinato) gallium, bis (10-hydroxybenzo [h] Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) ( There are o-cresolato) gallium, bis (2-methyl-8-quinolinato) (1-naphtholato) aluminum, bis (2-methyl-8-quinolinato) (2-naphtholato) gallium, It is not limited to this.

The organic light emitting device according to the present invention may be a front emission type, a back emission type, or a double-sided emission type depending on the material used.

In addition, the compound represented by Chemical Formula 1 may be included in an organic solar cell or an organic transistor in addition to the organic light emitting device.

The preparation of the compound represented by Chemical Formula 1 and the organic light emitting device including the same will be described in detail in the following Examples. However, the following examples are intended to illustrate the invention, and the scope of the invention is not limited by them.

Preparation Example 1 Preparation of Intermediate Compound Q-4

(a) Preparation of compound Q-1

Bromo-3-fluoro-4-iodobenzene (50 g, 166.6 mmol), 5-chloro-2-methoxyphenylboronic acid ((5-chloro- 2-methoxyphenyl) boronic acid) (31.1 g, 166.6 mmol) was dissolved in tetrahydrofuran (THF) (800 mL). Add sodium carbonate (Na ₂ CO ₃ ) 2 M solution (250 mL), tetrakis (triphenylphosphine) palladium (0) [Pd (PPh ₃ ) ₄ ] (3.8 g, 3 mol%), and reflux for 12 hours. Ordered. After the reaction was completed, the mixture was cooled to room temperature, and the resulting mixture was extracted three times with water and toluene. After separating the toluene layer and drying with magnesium sulfate, the filtrate was distilled under reduced pressure, and the mixture obtained was recrystallized three times using chloroform and ethanol to yield compound Q-1 (27.5 g, yield 51%, MS: [ M + H] ⁺ = 314).

(b) Preparation of compound Q-2

Compound Q-1 (25.0 g, 150 mmol) was dissolved in dichlorometahne (300 mL) and cooled to 0 ° C. Boron tribromide (7.9 mL, 83.2 mmol) was slowly added dropwise and stirred for 12 hours. After the reaction was completed, the mixture was washed three times with water, dried over magnesium sulfate, and filtered filtrate was distilled under reduced pressure, and purified by column chromatography to obtain compound Q-2 (23.7 g, yield 99%, MS: [M + H] ⁺ = 300).

(c) Preparation of compound Q-3

Compound Q-2 (20.0 g, 66.4 mmol) is dissolved in distilled dimethylformamide (DMF) (200 mL). It was cooled to 0 ° C., and sodium hydride (1.8 g, 72.9 mmol) was slowly added dropwise thereto. After stirring for 20 minutes, the mixture was stirred at 100 ° C for 1 hour. After the reaction was completed, the mixture was cooled to room temperature, and ethanol (Ethanol) (100 mL) was slowly added. The mixture obtained by distilling the above mixture under reduced pressure was recrystallized from chloroform and ethyl acetate to obtain compound Q-3 (15.2 g, yield 81%, MS: [M + H] ⁺ = 280).

(d) Preparation of compound Q-4

After dissolving compound Q-3 (15.0 g, 53.3 mmol) in tetrahydrofuran (150 mL), the temperature was lowered to -78 ° C and 1.7 M tertiary-butyllithium (t-BuLi) (31.8 mL, 53.3 mmol) was added. Apply slowly. After stirring at the same temperature for 1 hour, triisopropyl borate (B (OiPr) ₃ ) (14.2 mL, 107.0 mmol) was added, and the mixture was stirred for 3 hours while gradually raising the temperature to room temperature. A 2 N aqueous hydrochloric acid solution (100 mL) was added to the reaction mixture, and the mixture was stirred for 1.5 hours at room temperature. The resulting precipitate was filtered, washed sequentially with water and ethyl ether, and then dried under vacuum. After drying, dispersed in ethyl ether, stirred for 2 hours, filtered and dried to prepare compound Q-4 (12.2 g, yield 93%, MS: [M + H] ⁺ = 247).

Preparation Example 2: Preparation of intermediate compound R-4

(a) Preparation of compound R-1

R-1 (27.5 g, yield) in the same manner as in the manufacturing method of Q-1 in Preparation Example 1, except that 4-chloro-2-methoxyphenylboronic acid was used instead of 5-chloro-2-methoxyphenylboronic acid 51%, MS: [M + H] ⁺ = 314).

(b) Preparation of compound R-2

R-2 (23.7 g, yield 99%, MS: [M + H] ⁺ = 300) in the same manner as in the preparation method of Q-2 in Preparation Example 1, except that Compound R-1 was used instead of Compound Q-1. Was prepared.

(c) Preparation of compound R-3

R-3 (15.2 g, yield 81%, MS: [M + H] ⁺ = 280) in the same manner as in the preparation method of Q-3 of Preparation Example 1, except that Compound R-2 was used instead of Compound Q-2. Was prepared.

(d) Preparation of compound R-4

R-4 (12.2 g, yield 93%, MS: [M + H] ⁺ = 247) in the same manner as in the preparation method of Q-4 in Preparation Example 1, except that Compound R-3 was used instead of Compound Q-3. Was prepared.

Preparation Example 3: Preparation of intermediate compound P-4

(a) Preparation of compound P-1

Tetrahydrofuran (500 mL) with 4-bromoresorcinol (50 g, 0.26 mol) and 3-chloro-2-fluorophenylboronic acid (46.1 g, 0.21 mol) in a 2000 mL round bottom flask in a nitrogen atmosphere. After dissolving in, 1.5 M potassium carbonate aqueous solution (400 mL) was added, bis (tri-tert-butylphosphine) palladium (0) (1.35 g, 2.36 mmol) was added, followed by heating and stirring for 1 hour. The temperature was lowered to room temperature, the water layer was separated and removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, recrystallized using hexane, and then dried to obtain compound P-1 (49.8 g, yield 79%, MS: [M + H]) ⁺ = 239).

(b) Preparation of compound P-2

Compound P-1 (49.8 g, 0.21 mol) and calcium carbonate (57.7 g, 0.42 mol) were dissolved in N-methyl-2-pyrrolidone (200 mL) in a 500 mL round-bottom flask, followed by heating and stirring for 2 hours. . It was filtered by lowering the temperature to room temperature and reprecipitating in water. After completely dissolved in dichloromentan, washed with water, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, recrystallized using ethanol, and then dried to give compound P-2 (31.8 g, yield 70%, MS: [M + H] ⁺ = 219).

(c) Preparation of compound P-3

In a 500 mL round-bottom flask, dissolve compound P-2 (31.8 g, 0.15 mol) in acetonitrile (150 mL), dissolve calcium carbonate (33.1 g, 0.24 mol) in water (150 mL), and add it at 0 ° C. Nonafluorobutanesulfonyl fluoride (28.7 mL, 0.16 mol) was slowly added dropwise over 30 minutes. Then, it was stirred at room temperature for 3 hours. When the reaction is complete, filter, completely dissolve in dichloromentan, wash with water, dry with anhydrous magnesium sulfate, concentrate under reduced pressure, recrystallize using ethanol, and then dry to give compound P-3 (53.3 g, yield 73%, MS: [M + H] ⁺ = 501).

(d) Preparation of compound P-4

Compound P-3 (53.3 g, 0.11 mol), 4,4,5,5-tetramethyl- [1,3,2] -dioxaborolane (28.4 g, 17.85 mol), [1,1'- bis (Diphenylphosphino) ferrocene] palladium (II) dichloride (Pd (dppf) Cl ₂ ) (0.78 g, 1.06 mmol), potassium acetate (KOAc) (31.3 g, 0.32 mol) in dioxane (650 mL) Put and stirred under reflux for 8 hours. The temperature was reduced to room temperature and the solvent was concentrated under reduced pressure. This concentrate was completely dissolved in chloroform (CHCl ₃ ), washed with water, and the solution in which the product was dissolved was concentrated under reduced pressure and purified using column chromatography. Compound P-4 (30.1 g, yield 86%, MS: [M + H] ] ⁺ = 329).

Preparation Example 4: Preparation of intermediate compound S2

(a) Preparation of compound S1

Dissolve 4-chlorodibenzofuran (75 g, 0.37 mol) in dimethylformamide (DMF) (700 mL) in a 1000 mL round bottom flask in a nitrogen atmosphere, then N-bromosuccinimide (NBS) at 0 ° C. (69.2 g, 0.39 mol) was added in 5 portions, followed by stirring at room temperature for 3 hours. After that, the solution was decompressed, dissolved in ethyl acetate, washed with water, and the organic layer was separated and decompressed to remove all of the solvent. This was subjected to column chromatography to obtain compound S1 (92.5 g, yield 89%, MS: [M + H] ⁺ = 280).

(b) Preparation of compound S2

Compound S1 (92.5 g, 0.33 mol), 4,4,5,5-tetramethyl- [1,3,2] -dioxaborolane (87.9 g, 0.35 mol), [1,1'-bis (di Phenylphosphino) ferrocene] palladium (II) dichloride (Pd (dppf) Cl ₂ ) (2.41 g, 3.30 mmol), potassium acetate (KOAc) (97.1 g, 0.99 mol) in dioxane (1000 mL) and refluxed The mixture was stirred for 9 hours. The temperature was reduced to room temperature and the solvent was concentrated under reduced pressure. The concentrated solution was completely dissolved in chloroform (CHCl ₃ ), washed with water, and the solution in which the product was dissolved was concentrated under reduced pressure, recrystallized using ethanol, dried and purified to give Compound S2 (115 g, yield 67%, MS: [ M + H] ⁺ = 329).

Preparation Example 5 Preparation of Intermediate Compound U-4

(a) Preparation of 3-bromo-2-methoxyphenylboronic acid

After dissolving 1,3-dibromo-2-methoxybenzene (113.2 g, 426.4 mmol) in tetrahydrofuran (1000 mL), the temperature was lowered to -78 ° C and 1.7 M tertiary-butyllithium (t-BuLi) ) (251.7 mL, 426.4 mmol) was added slowly. After stirring at the same temperature for 1 hour, triisopropyl borate (B (OiPr) ₃ ) (113.2 mL, 852.4 mmol) was added, and the mixture was stirred for 3 hours while gradually raising the temperature to room temperature. To the reaction mixture, 2 N aqueous hydrochloric acid solution (800 mL) was added and stirred at room temperature for 1.5 hours. The resulting precipitate was filtered, washed sequentially with water and ethyl ether, and then dried under vacuum. After drying, chloroform and ethyl acetate were recrystallized and dried to prepare 3-bromo-2-methoxyphenylboronic acid (89.6 g, yield 91%, MS: [M + H] ⁺ = 230).

(b) Preparation of compound U-1

4-chloro-1-fluoro-2-iodobenzene is used instead of bromo-3-fluoro-4-iodobenzene, and 3-bromo-2-me instead of 5-chloro-2-methoxyphenylboronic acid. U-1 (55.8 g, yield 53%, MS: [M + H] ⁺ = 314) was prepared in the same manner as in the preparation method of Q-1 in Preparation Example 1, except that methoxyphenylboronic acid was used.

(c) Preparation of compound U-2

U-2 (39.7 g, yield 83%, MS: [M + H] ⁺ = 300) in the same manner as in the preparation method of Q-2 in Preparation Example 1, except that Compound U-1 was used instead of Compound Q-1. Was prepared.

(d) Preparation of compound U-3

U-3 (31.4 g, yield 84%, MS: [M + H] ⁺ = 280) in the same manner as in the preparation method of Q-3 of Preparation Example 1, except that Compound U-2 was used instead of Compound Q-2. Was prepared.

(e) Preparation of compound U-4

U-4 (25.5 g, Yield 97%, MS: [M + H] ⁺ = 247) in the same manner as in the manufacturing method of Q-4 in Preparation Example 1, except that Compound U-3 was used instead of Compound Q-3. Was prepared.

Preparation Example 6: Preparation of intermediate compound A1

2,4-dichloro-6- (dibenzo [b, d] furan-4-yl) -1,3,5-triazine (50.0 g, 158.7 mmol) and phenyl-d5-boronic acid (20.2 g, 158.7 mmol) was dispersed in tetrahydrofuran (500 mL), 2M aqueous potassium carbonate solution (aq. K ₂ CO ₃ ) (238 mL, 476.2 mmol) was added, and tetrakistriphenylphosphinopalladium [Pd (PPh ₃ ) ₄ ] (5.5 g, 3 mol%) was added thereto, followed by reflux with stirring for 5 hours. The temperature was reduced to room temperature and the resulting solid was filtered. The filtered solid was recrystallized from chloroform and ethyl acetate, filtered, and dried to prepare compound A1 (39.1 g, yield 68%, MS: [M + H] ⁺ = 363).

Preparation Example 7: Preparation of intermediate compound A2

2,4-dichloro-6- (dibenzo [b, d] furan- instead of 2,4-dichloro-6- (dibenzo [b, d] furan-4-yl) -1,3,5-triazine 3-day) A2 (42.5 g, yield 74%, MS: [M + H] ⁺ = 363) in the same manner as in the production method A1 in Preparation Example 6, except that 1,3,5-triazine was used. Was prepared.

Preparation Example 8: Preparation of intermediate compound A4

2,4-dichloro-6- (dibenzo [b, d] furan- instead of 2,4-dichloro-6- (dibenzo [b, d] furan-4-yl) -1,3,5-triazine 1-day) A4 (33.9 g, yield 59%, MS: [M + H] ⁺ = 363) in the same manner as in the production method of A1 in Preparation Example 6, except that 1,3,5-triazine was used. Was prepared.

Preparation Example 9: Preparation of intermediate compound A5

2,4-dichloro-6- (dibenzo [b, d] thiophene instead of 2,4-dichloro-6- (dibenzo [b, d] furan-4-yl) -1,3,5-triazine A5 (42.8 g, yield 75%, MS: [M + H] ⁺ = 379) in the same manner as in the A1 preparation method of Preparation Example 6, except that -4-yl) -1,3,5-triazine was used. ).

Preparation Example 10 Preparation of Intermediate Compound B1

In a nitrogen atmosphere, 2,4-dichloro-6-phenyl-1,3,5-triazine (20 g, 88.9 mmol) and dibenzo [b, d] furan-4-ylboronic acid (18.9 g, 88.9 mmol) were added. It was added to tetrahydrofuran (400 mL), stirred and refluxed. Subsequently, potassium carbonate (36.9 g, 266.7 mmol) was dissolved in water (37 mL), stirred thoroughly, and then tetrakistriphenylphosphino palladium (3.1 g, 2.7 mmol) was added. After the reaction for 2 hours, after cooling to room temperature, the organic layer and the water layer were separated and the organic layer was distilled. This was again dissolved in chloroform (635 mL) 20 times the theoretical yield of compound B1, washed twice with water to separate the organic layer, added anhydrous magnesium sulfate, stirred and filtered to distill the filtrate under reduced pressure. The concentrated compound was white solid compound B1 (20.6 g, yield 65%, MS: [M + H] ⁺ = 358.1) by recrystallization of chloroform and ethyl acetate.

Preparation Example 11: Preparation of intermediate compound B2

B2 (18.4 g, yield in the same manner as in the manufacturing method of B1 in Preparation Example 10, except that dibenzo [b, d] furan-3-ylboronic acid was used instead of dibenzo [b, d] furan-4-ylboronic acid 58%, MS: [M + H] ⁺ = 358.1).

Preparation Example 12 Preparation of Intermediate Compound B3

B3 (24.4 g, yield) in the same manner as in the manufacturing method of B1 in Preparation Example 10, except that dibenzo [b, d] furan-2-ylboronic acid was used instead of dibenzo [b, d] furan-4-ylboronic acid 77%, MS: [M + H] ⁺ = 358.1).

Preparation Example 13 Preparation of Intermediate Compound B4

B4 (21.9 g, yield) in the same manner as in the manufacturing method of B1 in Preparation Example 10, except that dibenzo [b, d] furan-1-ylboronic acid was used instead of dibenzo [b, d] furan-4-ylboronic acid 69%, MS: [M + H] ⁺ = 358.1).

Preparation Example 14 Preparation of Intermediate Compound B5

B5 (21.6 g, in the same manner as in the manufacturing method of B1 in Preparation Example 10, except that dibenzo [b, d] thiophen-4-ylboronic acid was used instead of dibenzo [b, d] furan-4-ylboronic acid. Yield 65%, MS: [M + H] ⁺ = 374).

Example 1: Preparation of compound 1

(a) Preparation of Intermediate 1-1

In a nitrogen atmosphere, Compound A1 (20 g, 55.2 mmol) and Compound Q-4 (13.6 g, 55.2 mmol) were added to tetrahydrofuran (400 mL), stirred and refluxed. Subsequently, potassium carbonate (22.9 g, 165.7 mmol) was dissolved in water (23 mL), stirred thoroughly, and then tetrakistriphenylphosphino palladium (1.9 g, 1.7 mmol) was added. After the reaction was allowed to cool to room temperature for 1 hour, the organic layer and the water layer were separated and the organic layer was distilled. This was again dissolved in 20 times chloroform (583 mL) compared to the theoretical water measurement of intermediate 1-1, washed twice with water to separate the organic layer, added anhydrous magnesium sulfate, stirred and filtered to distill the filtrate under reduced pressure. The concentrated compound was prepared by recrystallizing chloroform and ethyl acetate to prepare a white solid intermediate 1-1 (18.4 g, yield 63%, MS: [M + H] ⁺ = 529.1).

(b) Preparation of Intermediate 1-2

In a nitrogen atmosphere, intermediate 1-1 (15 g, 28.4 mmol) and bis (pinacolato) diboron (11.2 g, 28.4 mmol) were added to dioxane (300 mL), stirred and refluxed. After this, potassium triphosphate (18.1 g, 85.2 mmol) was added and stirred sufficiently, followed by palladium dibenzylidene acetone palladium (0.5 g, 0.9 mmol) and tricyclohexylphosphine (0.5 g, 1.7 mmol). After the reaction for 5 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and then the filtered organic layer was distilled. This was again dissolved in 10 times chloroform (176 mL) compared to the theoretical yield of Intermediate 1-2, washed twice with water to separate the organic layer, added anhydrous magnesium sulfate, stirred, filtered and distilled the filtrate under reduced pressure. The concentrated compound was prepared through chloroform and ethanol recrystallization to prepare a white solid compound, Intermediate 1-2 (12.7 g, yield 72%, MS: [M + H] ⁺ = 621.2).

(c) Preparation of compound 1

In a nitrogen atmosphere, intermediate 1-2 (10 g, 16.1 mmol) and 4-bromodibenzo [b, d] thiophene (4.2 g, 16.1 mmol) were added to tetrahydrofuran (200 mL), stirred and refluxed. Subsequently, potassium carbonate (6.7 g, 48.4 mmol) was dissolved in water (7 mL), stirred thoroughly, and then tetrakistriphenylphosphino palladium (0.6 g, 0.5 mmol) was added. After the reaction was allowed to cool to room temperature for 1 hour, the organic layer and the water layer were separated and the organic layer was distilled. This was again dissolved in chloroform (218 mL) of 20 times the theoretical yield of compound 1, washed twice with water to separate the organic layer, added anhydrous magnesium sulfate, stirred and filtered to distill the filtrate under reduced pressure. The concentrated compound was white solid compound 1 (7.2 g, yield 66%, MS: [M + H] ⁺ = 677.2) through chloroform and ethyl acetate recrystallization.

Example 2: Preparation of compound 2

(a) Preparation of Intermediate 2-1

Intermediate 2-1 (21.6 g, yield 74%, MS: [M + H] ⁺ = 529.1) was prepared in the same manner as in Example 1, except that Compound A2 was used instead of Compound A1. Did.

(b) Preparation of Intermediate 2-2

Intermediate 2-2 (13.6 g, yield 77%, MS: [M + H] ⁺ =) in the same manner as in Intermediate 1-2 preparation method of Example 1, except that Intermediate 2-1 was used instead of Intermediate 1-1. 621.2).

(c) Preparation of compound 2

Compound 2 (8.7 g, yield 80%, MS: [M + H] ⁺ = 677.2) was prepared by the same method as the method for preparing compound 1 of Example 1, except that intermediate 2-2 was used instead of intermediate 1-2. Did.

Example 3: Preparation of compound 3

(a) Preparation of intermediate 3-1

Intermediate 3-1 (20.4 g, yield 70%, MS: [M + H] ⁺ = 529.1) was prepared in the same manner as in Example 1, except that Compound A4 was used instead of Compound A1. Did.

(b) Preparation of Intermediate 3-2

Intermediate 3-2 (10.6 g, yield 60%, MS: [M + H] ⁺ =) in the same manner as in Intermediate 1-2 preparation method of Example 1, except that Intermediate 3-1 was used instead of Intermediate 1-1. 621.2).

(c) Preparation of compound 3

Compound 3 (5.7 g, yield 52%, MS: [M + H] ⁺ = 677.2) was prepared by the same method as the method for preparing compound 1 of Example 1, except that intermediate 3-2 was used instead of intermediate 1-2. Did.

Example 4: Preparation of compound 4

(a) Preparation of Intermediate 4-1

Intermediate 4-1 (19.8 g, yield 68%, MS: [M + H] ⁺ = 529.1) was prepared in the same manner as in Example 1, except that Compound A5 was used instead of Compound A1. Did.

(b) Preparation of Intermediate 4-2

Intermediate 4-2 (10.2 g, yield 58%, MS: [M + H] ⁺ =) in the same manner as in Intermediate 1-2 preparation method of Example 1, except that Intermediate 4-1 was used instead of Intermediate 1-1. 621.2).

(c) Preparation of compound 4

Compound 4 (6.5 g, yield 60%, MS: [M + H] ⁺ = 693.2) was prepared by the same method as the method for preparing compound 1 of Example 1, except that intermediate 4-2 was used instead of intermediate 1-2. Did.

Example 5: Preparation of compound 5

(a) Preparation of Intermediate 5-1

Intermediate 5-1 (17.2 g, yield 59%, MS: [M + H] ⁺ = 529.1) was prepared in the same manner as in Example 1, except that Compound B1 was used instead of Compound A1. Did.

(b) Preparation of Intermediate 5-2

Intermediate 5-2 (11.3 g, yield 64%, MS: [M + H] ⁺ =) in the same manner as in Intermediate 1-2 preparation method of Example 1, except that Intermediate 5-1 was used instead of Intermediate 1-1. 616.2).

(c) Preparation of compound 5

Compound 5 (6.4 g, yield 60%, MS: [M + H] ⁺ = 656.2) was prepared by the same method as the method for preparing compound 1 of Example 1, except that intermediate 5-2 was used instead of intermediate 1-2. Did.

Example 6: Preparation of compound 6

(a) Preparation of Intermediate 6-1

Intermediate 6-1 (22.5 g, yield 77%, MS: [M + H] ⁺ = 529.1) was prepared in the same manner as in Example 1, except that Compound B2 was used instead of Compound A1. Did.

(b) Preparation of Intermediate 6-2

Intermediate 6-2 (11.8 g, yield 67%, MS: [M + H] ⁺ =) in the same manner as in Intermediate 1-2 preparation method of Example 1, except that Intermediate 6-1 was used instead of Intermediate 1-1. 616.2).

(c) Preparation of compound 6

Compound 6 (5.9 g, yield 55%, MS: [M + H] ⁺ = 656.2) was prepared by the same method as the method for preparing compound 1 of Example 1, except that intermediate 6-2 was used instead of intermediate 1-2. Did.

Example 7: Preparation of compound 7

(a) Preparation of Intermediate 7-1

Intermediate 7-1 (20.4 g, yield 70%, MS: [M + H] ⁺ = 529.1) was prepared in the same manner as in Example 1, except that Compound B3 was used instead of Compound A1. Did.

(b) Preparation of Intermediate 7-2

Intermediate 7-2 (10.4 g, yield 59%, MS: [M + H] ⁺ =) in the same manner as in Intermediate 1-2 preparation method of Example 1, except that Intermediate 7-1 was used instead of Intermediate 1-1. 616.2).

(c) Preparation of compound 7

Compound 7 (6.5 g, yield 61%, MS: [M + H] ⁺ = 656.2) was prepared by the same method as the method for preparing compound 1 of Example 1, except that intermediate 7-2 was used instead of intermediate 1-2. Did.

Example 8: Preparation of compound 8

(a) Preparation of Intermediate 8-1

Intermediate 8-1 (19 g, yield 65%, MS: [M + H] ⁺ = 529.1) was prepared in the same manner as in Example 1, except that Compound B4 was used instead of Compound A1. Did.

(b) Preparation of Intermediate 8-2

Intermediate 8-2 (9.7 g, yield 55%, MS: [M + H] ⁺ =) in the same manner as in Intermediate 1-2 preparation method of Example 1, except that Intermediate 8-1 was used instead of Intermediate 1-1. 616.2).

(c) Preparation of compound 8

Compound 8 (5.4 g, yield 51%, MS: [M + H] ⁺ = 656.2) was prepared by the same method as the method for preparing compound 1 of Example 1, except that intermediate 8-2 was used instead of intermediate 1-2. Did.

Example 9: Preparation of compound 9

(a) Preparation of Intermediate 9-1

Intermediate 9-1 (14.6 g, yield 52%, MS: [M + H] ⁺ = 545.1) was prepared in the same manner as in Example 1, except that Compound B5 was used instead of Compound A1. Did.

(b) Preparation of Intermediate 9-2

Intermediate 9-2 (12.1 g, yield 69%, MS: [M + H] ⁺ =) in the same manner as in Intermediate 1-2 preparation method of Example 1, except that Intermediate 9-1 was used instead of Intermediate 1-1. 632.2).

(c) Preparation of compound 9

Compound 9 (7.3 g, yield 69%, MS: [M + H] ⁺ = 672.2) was prepared in the same manner as in Example 1, except that Intermediate 9-2 was used instead of Intermediate 1-2. Did.

Example 10: Preparation of compound 10

(a) Preparation of Intermediate 10-1

In a nitrogen atmosphere, compound R-4 (20 g, 81.3 mmol) and compound B2 (29 g, 81.3 mmol) were added to tetrahydrofuran (400 mL), stirred and refluxed. Subsequently, potassium carbonate (33.7 g, 243.9 mmol) was dissolved in water (34 mL), stirred thoroughly, and then tetrakistriphenylphosphino palladium (2.8 g, 2.4 mmol) was added. After the reaction was allowed to cool to room temperature for 1 hour, the organic layer and the water layer were separated and the organic layer was distilled. This was again dissolved in 20 times chloroform (850 mL) compared to the theoretical yield of Intermediate 10-1, washed twice with water to separate the organic layer, added anhydrous magnesium sulfate, stirred and filtered to distill the filtrate under reduced pressure. The concentrated compound was prepared as a white solid compound 10-1 (28.1 g, yield 66%, MS: [M + H] ⁺ = 524.1) by recrystallization of chloroform and ethyl acetate.

(b) Preparation of Intermediate 10-2

In a nitrogen atmosphere, intermediate 10-1 (15 g, 28.4 mmol) and bis (pinacolato) diboron (7.2 g, 28.4 mmol) were added to dioxane (300 mL), stirred and refluxed. Subsequently, potassium phosphate (18.1 g, 85.2 mmol) was added and stirred sufficiently, followed by palladium dibenzylidene acetone palladium (0.5 g, 0.9 mmol) and tricyclohexylphosphine (0.5 g, 1.7 mmol). After the reaction for 5 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and then the filtered organic layer was distilled. This was again dissolved in 10 times chloroform (175 mL) compared to the theoretical yield of Intermediate 10-2, washed twice with water to separate the organic layer, added anhydrous magnesium sulfate, stirred and filtered to distill the filtrate under reduced pressure. The concentrated compound was prepared by recrystallizing chloroform and ethanol to prepare a white solid compound 10-2 (11.7 g, yield 67%, MS: [M + H] ⁺ = 616.2).

(c) Preparation of compound 10

In a nitrogen atmosphere, intermediate 10-2 (20 g, 32.7 mmol) and 4-bromodibenzo [b, d] furan (8 g, 32.7 mmol) were added to tetrahydrofuran (400 mL), stirred and refluxed. Thereafter, potassium carbonate (13.5 g, 98 mmol) was dissolved in water (14 mL), stirred thoroughly, and then tetrakistriphenylphosphino palladium (1.1 g, 1 mmol) was added. After the reaction was allowed to cool to room temperature for 1 hour, the organic layer and the water layer were separated and the organic layer was distilled. This was again dissolved in chloroform (428 mL) of 20 times the theoretical yield of compound 10, washed twice with water to separate the organic layer, added anhydrous magnesium sulfate, stirred and filtered to distill the filtrate under reduced pressure. The concentrated compound was white solid compound 10 (16.7 g, yield 78%, MS: [M + H] ⁺ = 656.2) by recrystallization of chloroform and ethyl acetate.

Example 11: Preparation of compound 11

(a) Preparation of intermediate 11-1

Intermediate 11-1 (21.7 g, yield 51%, MS: [M + H] ⁺ =) in the same manner as in the preparation method of Intermediate 10-1 of Example 10, except that Compound P-4 was used instead of Compound R-4. 524.1).

(b) Preparation of Intermediate 11-2

Intermediate 11-2 (8.7 g, yield 50%, MS: [M + H] ⁺ =) in the same manner as in Example 10, Intermediate 10-2 preparation method, except that Intermediate 11-1 was used instead of Intermediate 10-1. 616.2).

(c) Preparation of compound 11

Compound 11 (27.6 g, yield 65%, MS: [M + H] ⁺ = 524.1) was prepared by the same method as the method for preparing compound 10 of Example 10, except that intermediate 11-2 was used instead of intermediate 10-2. Did.

Example 12: Preparation of compound 12

(a) Preparation of Intermediate 12-1

Intermediate 12-1 (34 g, yield 80%, MS: [M + H] ⁺ = 524.1) in the same manner as in the preparation method of Intermediate 10-1 of Example 10, except that Compound S2 was used instead of Compound R-4. Was prepared.

(b) Preparation of Intermediate 12-2

Intermediate 12-2 (11 g, yield 63%, MS: [M + H] ⁺ =) in the same manner as in Intermediate 10-2 preparation method of Example 10, except that Intermediate 12-1 was used instead of Intermediate 10-1. 616.2).

(c) Preparation of compound 12

Compound 12 (30.2 g, yield 71%, MS: [M + H] ⁺ = 524.1) was prepared by the same method as the method for preparing compound 10 of Example 10, except that intermediate 12-2 was used instead of intermediate 10-2. Did.

Example 13: Preparation of compound 13

(a) Preparation of Intermediate 13-1

Intermediate 13-1 (29.8 g, yield 70%, MS: [M + H] ⁺ =) in the same manner as in the preparation method of Intermediate 10-1 of Example 10, except that Compound U-4 was used instead of Compound R-4. 524.1).

(b) Preparation of Intermediate 13-2

Intermediate 13-2 (9.1 g, yield 53%, MS: [M + H] ⁺ =) in the same manner as in the preparation method of Intermediate 10-2 of Example 10, except that Intermediate 13-1 was used instead of Intermediate 10-1. 616.2).

(c) Preparation of compound 13

Compound 13 (31.5 g, yield 74%, MS: [M + H] ⁺ = 524.1) was prepared by the same method as the method for preparing compound 10 of Example 10, except that intermediate 13-2 was used instead of intermediate 10-2. Did.

Example 14: Preparation of compound 14

In a nitrogen atmosphere, intermediate 6-2 (20 g, 32.7 mmol) and 3-bromodibenzo [b, d] furan (8 g, 32.7 mmol) were added to tetrahydrofuran (400 mL), stirred and refluxed. Thereafter, potassium carbonate (13.5 g, 98 mmol) was dissolved in water (14 mL), stirred thoroughly, and then tetrakistriphenylphosphino palladium (1.1 g, 1 mmol) was added. After the reaction for 2 hours, after cooling to room temperature, the organic layer and the water layer were separated and the organic layer was distilled. This was again dissolved in chloroform (428 mL) 20 times the theoretical yield of compound 14, washed twice with water to separate the organic layer, added anhydrous magnesium sulfate, stirred and filtered to distill the filtrate under reduced pressure. The concentrated compound was white solid compound 14 (15 g, yield 70%, MS: [M + H] ⁺ = 656.2) by recrystallization of chloroform and ethyl acetate.

Example 15: Preparation of compound 15

In a nitrogen atmosphere, intermediate 6-2 (10 g, 40.6 mmol) and 2-bromodibenzo [b, d] furan (10 g, 40.6 mmol) were added to tetrahydrofuran (200 mL), stirred and refluxed. Then, potassium carbonate (16.9 g, 121.9 mmol) was dissolved in water (17 mL), stirred thoroughly, and then tetrakistriphenylphosphino palladium (1.4 g, 1.2 mmol) was added. After the reaction was allowed to cool to room temperature for 1 hour, the organic layer and the water layer were separated and the organic layer was distilled. This was again dissolved in chloroform (425 mL) 20 times the theoretical yield of compound 15, washed twice with water to separate the organic layer, added anhydrous magnesium sulfate, stirred and filtered to distill the filtrate under reduced pressure. The concentrated compound was white solid compound 15 (15.3 g, yield 72%, MS: [M + H] ⁺ = 524.1) by recrystallization of chloroform and ethyl acetate.

Example 16: Preparation of compound 16

Compound 16 (11.7 g, yield 55%) in the same manner as in the method for preparing compound 15 of Example 15, except that 1-bromodibenzo [b, d] furan was used instead of 2-bromodibenzo [b, d] furan , MS: [M + H] ⁺ = 524.1).

<Experimental Example 1>

A glass substrate coated with a thin film of ITO (indium tin oxide) at a thickness of 1,300 에 was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, Fischer Co. was used as the detergent, and distilled water filtered secondarily by a filter of Millipore Co. was used as the distilled water. After washing the ITO for 30 minutes, ultrasonic washing was repeated for 2 minutes with distilled water twice. After washing with distilled water, ultrasonic cleaning was performed with a solvent of isopropyl alcohol, acetone, and methanol, followed by drying and transporting to a plasma cleaner. In addition, the substrate was washed for 5 minutes using oxygen plasma, and then transferred to a vacuum evaporator.

On the ITO transparent electrode prepared as above, the following HI-1 compound was thermally vacuum-deposited to a thickness of 50 Å to form a hole injection layer. The following HT-1 compound was thermally vacuum-deposited to a thickness of 250 위에 on the hole injection layer to form a hole transport layer, and the following HT-2 compound was vacuum-deposited to a thickness of 50 위에 on the HT-1 deposition film to form an electron blocking layer. . As a light emitting layer on the HT-2 deposited film, the compound 1 prepared in Example 1, the following YGH-1 compound, and the phosphorescent dopant YGD-1 were co-deposited in a weight ratio of 44:44:12 to form a 400 mm thick light emitting layer. . An electron transport layer is formed by vacuum-depositing the following ET-1 compound with a thickness of 250 위에 on the light emitting layer, and the following ET-2 compound and Li are vacuum-deposited with a weight ratio of 98: 2 on the electron transport layer to inject electrons having a thickness of 100 Å. A layer was formed. On the electron injection layer, aluminum was deposited to a thickness of 1000 Å to form a cathode.

In the above process, the deposition rate of the organic material was maintained at 0.4 to 0.7 Å / sec, and the aluminum was maintained at the deposition rate of 2 Å / sec, and the vacuum degree during deposition was maintained at 1 × 10 ^-7 to 5 × 10 ^-8 torr. Did.

<Experimental Examples 2 to 17 and Comparative Experimental Examples 1 to 5>

An organic light emitting diode was manufactured according to the same method as Experimental Example 1 except for using the compound described in Table 1 below instead of the compound 1 of Example 1 in Experimental Example 1. The compounds of CE1 to CE5 in Table 1 are as follows.

In the Experimental Example and Comparative Experimental Example, the voltage and efficiency of the organic light emitting diode were measured at a current density of 10 mA / cm ² , and the life was measured at a current density of 50 mA / cm ² , and the results are shown in Table 1 below. . At this time, LT ₉₅ means the time to be 95% of the initial luminance.

As shown in Table 1, when the compound of the present invention is used as a light emitting layer material, it was confirmed that it exhibits excellent efficiency and lifespan compared to Comparative Experimental Examples. It seems that the electrical stability is increased as the continuous bond of triazine and dibenzofuran substituents and the dibenzofuran group dibenzothiophene group are substituted next to the triazine group.

[Description of codes]

1: substrate 2: anode

3: light emitting layer 4: cathode

5: hole injection layer 6: hole transport layer

7: electron blocking layer 8: electron transport layer

9: Electronic injection layer

Claims (8)

Compound represented by the formula (1): [Formula 1]

In Chemical Formula 1, Y ₁ is O or S, One of Ar ₁ to Ar ₃ is represented by the following Chemical Formula 2, and the other is hydrogen, One of Ar ₄ to Ar ₇ is substituted or unsubstituted dibenzofuran; Or substituted or unsubstituted dibenzothiophene, the rest being hydrogen, When Ar ₁ is represented by the following Chemical Formula 2, Ar ₇ is hydrogen, [Formula 2]

In Chemical Formula 2, X is each independently N or CH, two or more of X is N, Y ₂ is O or S, R ₁ to R ₃ are each independently hydrogen; heavy hydrogen; halogen; Hydroxy; Cyano; Nitrile; Nitro; Amino; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _1-60 haloalkyl; Substituted or unsubstituted C _1-60 thioalkyl; Substituted or unsubstituted C _1-60 alkoxy; Substituted or unsubstituted C _1-60 haloalkoxy; Substituted or unsubstituted C _3-60 cycloalkyl; Or substituted or unsubstituted C _1-60 alkenyl, a is an integer from 1 to 3, b is an integer from 1 to 4, c is an integer from 1 to 5. According to claim 1, Formula 1 is any one selected from compounds represented by the following Formulas 1-1 to 1-5, the compound: [Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

In Chemical Formulas 1-1 to 1-5, Y ₁ , Y ₂ , The description of X, R ₁ to R ₃ , a, b and c is as defined in claim 1, Y ₃ is O or S, R ₄ and R ₅ are each independently hydrogen; heavy hydrogen; halogen; Hydroxy; Cyano; Nitrile; Nitro; Amino; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _1-60 haloalkyl; Substituted or unsubstituted C _1-60 thioalkyl; Substituted or unsubstituted C _1-60 alkoxy; Substituted or unsubstituted C _1-60 haloalkoxy; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _1-60 alkenyl; Substituted or unsubstituted C _6-60 aryl; Substituted or unsubstituted C _6-60 aryloxy; Or a substituted or unsubstituted C _2-60 heteroaryl containing one or more of O, N, Si and S, d is an integer from 1 to 3, e is an integer from 1 to 4. According to claim 1, A compound in which X is all N. According to claim 1, R ₁ to R ₃ are each independently hydrogen or deuterium. According to claim 1, Compound represented by Formula 1 is characterized in that any one selected from the group consisting of the following compounds, compounds:

A first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes the compound according to any one of claims 1 to 5. That is, an organic light emitting device. The method of claim 6, The organic material layer includes a light emitting layer, and the light emitting layer comprises two or more host materials, an organic light emitting device. The method of claim 7, The two or more host materials include the compound, an organic light emitting device.

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