WO2023085834A1 - Novel compound and organic light-emitting device comprising same - Google Patents

Abstract

The present invention provides a novel compound and an organic light-emitting device comprising same.

Description

Novel compound and organic light emitting device including the same

Cross-citation with related application(s)

This application claims the benefit of priority based on Korean Patent Application No. 10-2021-0155894 dated November 12, 2021 and Korean Patent Application No. 10-2022-0148521 dated November 9, 2022, and the All material disclosed in the literature is incorporated as part of this specification.

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

In general, the organic light emitting phenomenon refers to a phenomenon in which electrical energy is converted into light energy using an organic material. An organic light emitting device using an organic light emitting phenomenon has a wide viewing angle, excellent contrast, and a fast response time, and has excellent luminance, driving voltage, and response speed characteristics, and thus many studies are being conducted.

An organic light emitting device generally has a structure including an anode, 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 composed of a multi-layered structure composed of different materials, and may include, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. In the structure of this organic light emitting device, when a voltage is applied between the two electrodes, holes are injected from the anode and electrons from the cathode are injected into the organic material layer, and when the injected holes and electrons meet, excitons are formed. When it falls back to the ground state, it glows.

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

[Prior art literature]

[Patent Literature]

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

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

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

[Formula 1]

In Formula 1,

X ₁ to X ₉ are each independently N or CR ₁ , but at least one of X ₁ to X ₉ is N;

R ₁ is any one or more selected from the group consisting of hydrogen, deuterium, substituted or unsubstituted C _1-60 alkyl, substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted N, O and S; A C _2-60 heteroaryl containing a heteroatom,

L is each independently a single bond or a substituted or unsubstituted C _6-60 arylene;

Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C _6-60 aryl, or a substituted or unsubstituted C _2- including any one or more heteroatoms selected from the group consisting of N, O and S; ₆₀ heteroaryl.

In addition, the present invention is 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 of the organic material layers includes the compound represented by Chemical Formula 1. do.

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

1 shows 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.

2 shows 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 3, a hole blocking layer 8, an electron injection and transport layer ( 9) and an example of an organic light emitting element composed of a cathode 4 is shown.

Hereinafter, in order to aid understanding of the present invention, it will be described in more detail.

In this specification,

or

means a bond connected to another substituent.

In this specification, the term "substituted or unsubstituted" means deuterium; halogen group; nitrile group; nitro group; hydroxy group; carbonyl group; ester group; imide group; amino group; phosphine oxide group; alkoxy group; aryloxy group; Alkyl thioxy group; Arylthioxy group; an alkyl sulfoxy group; aryl sulfoxy group; silyl group; boron group; an alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; Aralkenyl group; Alkyl aryl group; Alkylamine group; Aralkylamine group; heteroarylamine group; Arylamine group; Arylphosphine group; Or substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing at least one of N, O, and S atoms, or substituted or unsubstituted with two or more substituents linked to each other among the substituents exemplified above. . For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in 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 substituent having the following structure, but is not limited thereto.

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

In the present 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 substituent having the following structure, but is not limited thereto.

In the present specification, the silyl group is specifically a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, and the like. but not limited to

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

In this 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 the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the number of carbon atoms of the alkyl group is 1 to 20. According to another exemplary embodiment, the number of carbon atoms of the alkyl group is 1 to 10. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include 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, etc., 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 alkenyl group has 2 to 20 carbon atoms. 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, stilbenyl group, styrenyl group, etc., but is 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 number of carbon atoms of the cycloalkyl group is 3 to 20. According to another exemplary embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 6. 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 are not limited thereto.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the number of carbon atoms of the aryl group is 6 to 30. According to one embodiment, the number of carbon atoms 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 be bonded to each other to form a spiro structure. When the fluorenyl group is substituted,

etc. However, it is not limited thereto.

In the present specification, the heterocyclic group is a heterocyclic group containing at least one of O, N, Si, and S as heterogeneous elements, and the number of carbon atoms is not particularly limited, but preferably has 2 to 60 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazine group, and an acridyl group. , pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyridopyrimidinyl group, pyridopyrazinyl group, pyrazinopyrazinyl group, isoquinoline group, indole group , carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, isoxazolyl group, thiadia A zolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but are not limited thereto.

In the present specification, an aralkyl group, an aralkenyl group, an alkylaryl group, and an aryl group among arylamine groups are the same as the examples of the aryl group described above. In the present specification, the alkyl group among the aralkyl group, the alkylaryl group, and the alkylamine group is the same as the examples of the above-mentioned alkyl group. In the present specification, the description of the heterocyclic group described above may be applied to the heteroaryl of the heteroarylamine. In the present specification, the alkenyl group among the aralkenyl groups is the same as the examples of the alkenyl group described above. 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 the description of the aryl group or cycloalkyl group described above may be applied, except that the hydrocarbon ring is formed by combining two substituents. In the present specification, the heterocyclic group is not a monovalent group, and the description of the above-described heterocyclic group may be applied, except that it is formed by combining two substituents.

(compound)

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

Preferably, one of X ₁ to X ₉ is N.

Preferably, Formula 1 is represented by any one of the following Formulas 1-1 to 1-9:

In Formulas 1-1 to 1-9,

X ₁ to X ₉ , R ₁ , L, Ar ₁ and Ar ₂ are as defined above,

n is an integer from 1 to 8;

Preferably, R ₁ is hydrogen or deuterium.

Preferably, L is a single bond, phenylene, or naphthylene; The phenylene and naphthylene are unsubstituted or substituted with one or more deuterium atoms.

Preferably, L is a single bond or any one selected from the group consisting of:

Preferably, Ar ₁ and Ar ₂ are each independently selected from phenyl, naphthyl, biphenylyl, terphenylyl, phenanthrenyl, phenyl naphthyl, naphthyl phenyl, dibenzofuranyl, dibenzothiophenyl, 9 -phenyl-carbazolyl, carbazol-9-yl, benzophenanthrenyl, or chrysenyl; Ar ₁ and Ar ₂ are unsubstituted or substituted with one or more deuterium atoms.

Representative examples of the compound represented by Formula 1 are as follows:

In addition, the present invention provides a method for preparing the compound represented by Formula 1 as shown in Reaction Scheme 1 below.

[Scheme 1]

In Scheme 1, everything except Y is as defined above, and Y is halogen, preferably bromo or chloro.

The reaction is preferably carried out in the presence of a palladium catalyst and a base, and the reactor for the reaction can be changed as known in the art. The manufacturing method may be more specific in Preparation Examples to be described later.

(organic light emitting device)

In addition, the present invention provides an organic light emitting device including the compound represented by Formula 1 above. In one example, the present invention provides 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 of the organic material layers includes the compound represented by Chemical Formula 1. do.

The organic material layer of the organic light emitting device of the present invention may have a single-layer structure, or 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, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and the like as organic layers. However, the structure of the organic light emitting device is not limited thereto and may include fewer organic layers.

In addition, the organic material layer may include a hole injection layer, a hole transport layer, or a layer that simultaneously injects and transports holes, and the hole injection layer, the hole transport layer, or a layer that simultaneously injects and transports holes is represented by Formula 1 above. may contain the indicated compounds.

Also, the organic material layer may include a light emitting layer, and the light emitting layer may include the compound represented by Chemical Formula 1. In particular, the compound according to the present invention can be used as a dopant of the light emitting layer.

In addition, the organic material layer may include an electron transport layer, an electron injection layer, or a layer that simultaneously transports and injects electrons, and the electron transport layer, the electron injection layer, or a layer that simultaneously transports and injects electrons has the formula The compound represented by 1 may be included.

Also, the organic light emitting device according to the present invention may be a normal type organic light emitting device in which an anode, one or more organic material 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 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 an organic light emitting device according to an embodiment of the present invention is illustrated in FIGS. 1 and 2 .

1 shows 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 this structure, the compound represented by Chemical Formula 1 may be included in the light emitting layer.

2 shows 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 3, a hole blocking layer 8, an electron injection and transport layer ( 9) and an example of an organic light emitting element composed of a cathode 4 is shown. In this structure, the compound represented by Chemical Formula 1 may be included in the light emitting layer.

The organic light emitting device according to the present invention may be manufactured using materials and methods known in the art, except that at least one of the organic layers includes the compound represented by Chemical Formula 1. Also, 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, by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation, depositing a metal or a metal oxide having conductivity or an alloy thereof on the substrate to form an anode After forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer thereon, and depositing a material that can be used as a cathode thereon, it can be prepared. In addition to this method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode 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 coating method means spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, etc., 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 an anode material on a substrate from a cathode material (WO 2003/012890). However, the manufacturing 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.

As the anode material, a material having a high work function is generally preferred so that holes can be smoothly injected into the organic layer. Specific examples of the cathode 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); combinations of metals and oxides 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 so as to easily inject electrons into the organic material layer. Specific examples of the anode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; There are multi-layered materials such as LiF/Al or LiO ₂ /Al, but are not limited thereto.

The hole injection layer is a layer for injecting holes from the electrode, and the hole injection material has the ability to transport holes and has a hole injection effect at the anode, an excellent hole injection effect for the light emitting layer or the light emitting material, and generated in the light emitting layer A compound that prevents migration of excitons to the electron injecting layer or electron injecting 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 anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injection material include metal porphyrins, oligothiophenes, arylamine-based organic materials, hexanitrilehexaazatriphenylene-based organic materials, quinacridone-based organic materials, and perylene-based organic materials. of organic materials, anthraquinone, 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 the holes to the light emitting layer. As a hole transport material, a material capable of receiving holes from the anode or the hole injection layer and transferring them to the light emitting layer is a material having high hole mobility. this is suitable Specific examples include, but are not limited to, arylamine-based organic materials, conductive polymers, and block copolymers having both conjugated and non-conjugated parts.

The electron blocking layer is formed on the hole transport layer, and is preferably provided in contact with the light emitting layer to control hole mobility and prevent excessive movement of electrons to increase the probability of hole-electron coupling, thereby increasing the efficiency of the organic light emitting device. means a layer that serves to improve The electron blocking layer includes an electron blocking material, and an example of such an electron blocking material may be an arylamine-based organic material, but is not limited thereto.

The light emitting material is a material capable of emitting light in the visible ray region by receiving and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); carbazole-based compounds; dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; compounds of the benzoxazole, benzthiazole and benzimidazole series; poly(p-phenylenevinylene) (PPV)-based polymers; spiro compounds; Polyfluorene, rubrene, etc., but are not limited thereto.

The light emitting layer may include a host material and a dopant material. The host material includes a condensed aromatic ring derivative or a compound containing a hetero ring. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc., and heterocyclic-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type furan compounds, pyrimidine derivatives, etc., but are not limited thereto.

Dopant materials include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like. Specifically, aromatic amine derivatives are condensed aromatic ring derivatives having a substituted or unsubstituted arylamino group, such as pyrene, anthracene, chrysene, periplanthene, etc. having an arylamino group, and styrylamine compounds include substituted or unsubstituted arylamine is substituted with at least one arylvinyl group, wherein one or two or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, etc., but is not limited thereto. In addition, metal complexes include, but are not limited to, iridium complexes and platinum complexes.

The hole blocking layer is formed on the light emitting layer, preferably provided in contact with the light emitting layer, to improve the efficiency of the organic light emitting device by controlling electron mobility and preventing excessive movement of holes to increase the probability of hole-electron coupling layers that play a role. The hole blocking layer includes a hole blocking material, and examples of the hole blocking material include azine derivatives including triazine; triazole derivatives; oxadiazole derivatives; phenanthroline derivatives; A compound having an electron withdrawing group such as a phosphine oxide derivative may be used, but is not limited thereto.

The electron injection and transport layer is a layer that simultaneously serves as an electron transport layer and an electron injection layer for injecting electrons from an electrode and transporting the received electrons to the light emitting layer, and is formed on the light emitting layer or the hole blocking layer. As such an electron injecting and transporting material, a material capable of receiving electrons from the cathode and transferring them to the light emitting layer is suitable. Examples of specific electron injection and transport materials include Al complexes of 8-hydroxyquinoline; Complexes containing Alq ₃ ; organic radical compounds; hydroxyflavone-metal complexes; triazine derivatives, etc., but are not limited thereto. Or fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidene methane, anthrone, etc. and their derivatives, metal complex compounds , or may be used together with nitrogen-containing 5-membered ring derivatives, etc., but is not limited thereto.

The electron injection and transport layer may also be formed as a separate layer such as an electron injection layer and an electron transport layer. In this case, the electron transport layer is formed on the light emitting layer or the hole blocking layer, and the above-described electron injection and transport material may be used as an electron transport material included in the electron transport layer. In addition, the electron injection layer is formed on the electron transport layer, and examples of electron injection materials included in the electron injection layer include LiF, NaCl, CsF, Li ₂ O, BaO, fluorenone, anthraquinodimethane, diphenoquinone, Thiophyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, fluorenylidene methane, anthrone, etc. and their derivatives, metal complex compounds, nitrogen-containing 5-membered ring derivatives, and the like can be used.

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-hydroxyquinolinato)chlorogallium, bis(2-methyl-8-hydroxyquine nolinato)(o-cresolato)gallium, bis(2-methyl-8-hydroxyquinolinato)(1-naphtolato)aluminum, bis(2-methyl-8-hydroxyquinolinato)(2- Naphtolato) 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 double side emission type depending on the material used.

In addition, the compound according to the present invention may be included in an organic solar cell or an organic transistor in addition to an organic light emitting device.

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 present invention, and the scope of the present invention is not limited thereto.

[Example]

Preparation Example 1

3-bromo-4-chloropyridin-2-amine (15g, 72.3mmol) and (1-methoxynaphthalen-2-yl)boronic acid (15.3g, 75.9mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (30g, 216.9mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.4g, 0.7mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.7 g of compound A-1_P1. (Yield 62%, MS: [M+H] ⁺ = 285)

Compound A-1_P1 (15g, 52.7mmol) and HBF ₄ (9.3g, 105.4mmol) were added to 150ml of Acetonitrile and stirred. After that, NaNO ₂ (14.6g, 105.4mmol) was dissolved in 30ml of water and added slowly at 0 ^o C. After reacting for 9 hours, the temperature was raised to room temperature, and diluted with 300 ml of water. After dissolving in chloroform and washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8 g of compound A-1_P2. (Yield 60%, MS: [M+H] ⁺ = 254)

Compound A-1_P2 (15g, 59.1mmol) and bis(pinacolato)diboron (16.5g, 65mmol) were stirred while refluxing in 300ml of 1,4-dioxane. After that, potassium acetate (8.7g, 88.7mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (1g, 1.8mmol) and tricyclohexylphosphine (1g, 3.5mmol) were added. After reacting for 6 hours, cooling to room temperature and separating the organic layer using chloroform and water, the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.1 g of Compound A-1. (Yield 79%, MS: [M+H] ⁺ = 346)

Preparation Example 2

Compound A-2 was prepared in the same manner as in Preparation Example 1, except that 4-bromo-5-chloropyridin-3-amine was used instead of 3-bromo-4-chloropyridin-2-amine.

Preparation Example 3

Compound A-3 was prepared in the same manner as in Preparation Example 1, except that 3-bromo-2-chloropyridin-4-amine was used instead of 3-bromo-4-chloropyridin-2-amine.

Production Example 4

2-bromo-3-chloroaniline (15g, 72.6mmol) and (4-methoxyquinolin-3-yl)boronic acid (15.5g, 76.3mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (30.1g, 217.9mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.4g, 0.7mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14 g of compound B-1_P1. (Yield 68%, MS: [M+H] ⁺ = 285)

Compound B-1_P1 (15g, 52.7mmol) and HBF ₄ (9.3g, 105.4mmol) were added to 150ml of Acetonitrile and stirred. After that, NaNO ₂ (14.6g, 105.4mmol) was dissolved in 30ml of water and added slowly at 0 ^o C. After reacting for 8 hours, the temperature was raised to room temperature, and diluted with 300 ml of water. After dissolving in chloroform and washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 6.8 g of compound B-1_P2. (Yield 51%, MS: [M+H] ⁺ = 254)

Compound B-1_P2 (15g, 59.1mmol) and bis(pinacolato)diboron (16.5g, 65mmol) were stirred while refluxing in 300ml of 1,4-dioxane. After that, potassium acetate (8.7g, 88.7mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (1g, 1.8mmol) and tricyclohexylphosphine (1g, 3.5mmol) were added. After reacting for 5 hours, cooling to room temperature and separating the organic layer using chloroform and water, the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.9 g of Compound B-1. (Yield 68%, MS: [M+H] ⁺ = 346)

Preparation Example 5

Compound B-2 was prepared in the same manner as in Preparation Example 4, except that (4-methoxyisoquinolin-3-yl)boronic acid was used instead of (4-methoxyquinolin-3-yl)boronic acid.

Preparation Example 6

Compound B-3 was prepared in the same manner as in Preparation Example 4, except that (5-methoxyquinolin-6-yl)boronic acid was used instead of (4-methoxyquinolin-3-yl)boronic acid.

Preparation Example 7

Compound B-4 was prepared in the same manner as in Preparation Example 4, except that (5-methoxyisoquinolin-6-yl)boronic acid was used instead of (4-methoxyquinolin-3-yl)boronic acid.

Preparation Example 8

Compound B-5 was prepared in the same manner as in Preparation Example 4, except that (8-methoxyisoquinolin-7-yl)boronic acid was used instead of (4-methoxyquinolin-3-yl)boronic acid.

Preparation Example 9

2-bromo-3-chloroaniline (15g, 72.6mmol) and (8-methoxyquinolin-7-yl)boronic acid (15.5g, 76.3mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (30.1g, 217.9mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.4g, 0.7mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.1 g of compound B-6_P1. (Yield 73%, MS: [M+H] ⁺ = 285)

Compound B-6_P1 (15g, 52.7mmol) and HBF ₄ (9.3g, 105.4mmol) were added to 150ml of Acetonitrile and stirred. After that, NaNO ₂ (14.6g, 105.4mmol) was dissolved in 30ml of water and added slowly at 0 ^o C. After reacting for 9 hours, the temperature was raised to room temperature, and diluted with 300 ml of water. After dissolving in chloroform and washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 7.9 g of compound B-6_P2. (Yield 59%, MS: [M+H] ⁺ = 254)

Compound B-6_P2 (15g, 59.1mmol) and bis(pinacolato)diboron (16.5g, 65mmol) were stirred while refluxing in 300ml of 1,4-dioxane. After that, potassium acetate (8.7g, 88.7mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (1g, 1.8mmol) and tricyclohexylphosphine (1g, 3.5mmol) were added. After reacting for 5 hours, cooling to room temperature and separating the organic layer using chloroform and water, the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.4 g of compound B-6. (Yield 61%, MS: [M+H] ⁺ = 346)

Synthesis Example 1

Trz1 (15g, 40.8mmol) and Compound A-1 (14.8g, 42.8mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (16.9g, 122.3mmol) was dissolved in 100mlml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 2 hours, it was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.9 g of Compound 1. (Yield 80%, MS: [M+H] ⁺ = 551)

Synthesis Example 2

Trz2 (15g, 38.1mmol) and Compound A-1 (13.8g, 40mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (15.8g, 114.3mmol) was dissolved in 100mlml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.6 g of Compound 2. (Yield 71%, MS: [M+H] ⁺ = 577)

Synthesis Example 3

Trz3 (15g, 34.6mmol) and Compound A-1 (12.5g, 36.3mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (14.3g, 103.7mmol) was dissolved in 100mlml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.3 g of Compound 3. (Yield 67%, MS: [M+H] ⁺ = 617)

Synthesis Example 4

Trz4 (15g, 35.9mmol) and Compound A-2 (13g, 37.7mmol) were added to 300ml of THF and stirred and refluxed. After that, potassium carbonate (14.9g, 107.7mmol) was dissolved in 100mlml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.9 g of Compound 4. (Yield 69%, MS: [M+H] ⁺ = 601)

Synthesis Example 5

Trz5 (15g, 38.1mmol) and Compound A-2 (13.8g, 40mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (15.8g, 114.3mmol) was dissolved in 100mlml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 2 hours, it was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.6 g of Compound 5. (Yield 80%, MS: [M+H] ⁺ = 577)

Synthesis Example 6

Trz6 (15g, 35.9mmol) and Compound A-2 (13g, 37.7mmol) were added to 300ml of THF, stirred and refluxed. After that, potassium carbonate (14.9g, 107.7mmol) was dissolved in 100mlml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.2 g of Compound 6. (Yield 66%, MS: [M+H] ⁺ = 601)

Synthesis Example 7

Trz7 (15g, 38.1mmol) and Compound A-2 (13.8g, 40mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (15.8g, 114.3mmol) was dissolved in 100mlml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.9 g of Compound 7. (Yield 77%, MS: [M+H] ⁺ = 577)

Synthesis Example 8

Trz8 (15g, 36.8mmol) and compound A-3 (13.3g, 38.6mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (15.2g, 110.3mmol) was dissolved in 100mlml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 2 hours, it was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13 g of Compound 8. (Yield 60%, MS: [M+H] ⁺ = 591)

Synthesis Example 9

Trz9 (15g, 33.8mmol) and Compound A-3 (12.2g, 35.5mmol) were added to 300ml of THF, stirred and refluxed. After that, potassium carbonate (14g, 101.4mmol) was dissolved in 100mlml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 2 hours, it was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.9 g of Compound 9. (Yield 61%, MS: [M+H] ⁺ = 627)

Synthesis Example 10

Trz10 (15g, 33.3mmol) and Compound A-3 (12.1g, 35mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (13.8g, 100mmol) was dissolved in 100mlml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.9 g of Compound 10. (Yield 61%, MS: [M+H] ⁺ = 633)

Synthesis Example 11

Trz11 (15g, 35.9mmol) and Compound A-3 (13g, 37.7mmol) were added to 300ml of THF, stirred and refluxed. After that, potassium carbonate (14.9g, 107.7mmol) was dissolved in 100mlml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.8 g of Compound 11. (Yield 64%, MS: [M+H] ⁺ = 601)

Synthesis Example 12

Trz12 (15g, 35.7mmol) and compound B-2 (12.9g, 37.5mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (14.8g, 107.2mmol) was dissolved in 100mlml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 2 hours, it was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.3 g of Compound 12. (Yield 62%, MS: [M+H] ⁺ = 603)

Synthesis Example 13

Trz13 (15g, 38.1mmol) and compound B-2 (13.8g, 40mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (15.8g, 114.3mmol) was dissolved in 100mlml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.1 g of Compound 13. (Yield 69%, MS: [M+H] ⁺ = 577)

Synthesis Example 14

Trz14 (15g, 35.9mmol) and compound B-2 (13g, 37.7mmol) were added to 300ml of THF and stirred and refluxed. After that, potassium carbonate (14.9g, 107.7mmol) was dissolved in 100mlml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14 g of Compound 14. (Yield 65%, MS: [M+H] ⁺ = 601)

Synthesis Example 15

Trz15 (15g, 36.8mmol) and Compound B-1 (13.3g, 38.6mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (15.2g, 110.3mmol) was dissolved in 100mlml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.2 g of Compound 15. (Yield 61%, MS: [M+H] ⁺ = 591)

Synthesis Example 16

Trz16 (15g, 40.8mmol) and Compound B-1 (14.8g, 42.8mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (16.9g, 122.3mmol) was dissolved in 100mlml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 2 hours, it was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.5 g of Compound 16. (Yield 78%, MS: [M+H] ⁺ = 551)

Synthesis Example 17

Trz17 (15g, 38.1mmol) and Compound B-1 (13.8g, 40mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (15.8g, 114.3mmol) was dissolved in 100mlml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.7 g of Compound 17. (Yield 67%, MS: [M+H] ⁺ = 577)

Synthesis Example 18

Trz18 (15g, 35.9mmol) and compound B-3 (13g, 37.7mmol) were added to 300ml of THF and stirred and refluxed. After that, potassium carbonate (14.9g, 107.7mmol) was dissolved in 100mlml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.8 g of Compound 18. (Yield 78%, MS: [M+H] ⁺ = 601)

Synthesis Example 19

Trz19 (15g, 43.6mmol) and compound B-3 (15.8g, 45.8mmol) were added to 300ml of THF and stirred and refluxed. After that, potassium carbonate (18.1g, 130.9mmol) was dissolved in 100mlml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.9 g of Compound 19. (Yield 78%, MS: [M+H] ⁺ = 527)

Synthesis Example 20

Trz20 (15g, 38.1mmol) and compound B-3 (13.8g, 40mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (15.8g, 114.3mmol) was dissolved in 100mlml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.7 g of Compound 20. (Yield 76%, MS: [M+H] ⁺ = 577)

Synthesis Example 21

Trz21 (15g, 35.9mmol) and compound B-4 (13g, 37.7mmol) were added to 300ml of THF and stirred and refluxed. After that, potassium carbonate (14.9g, 107.7mmol) was dissolved in 100mlml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.2 g of Compound 21. (Yield 66%, MS: [M+H] ⁺ = 601)

Synthesis Example 22

Trz22 (15g, 34.6mmol) and compound B-4 (12.6g, 36.4mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (14.4g, 103.9mmol) was dissolved in 100mlml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16 g of Compound 22. (Yield 75%, MS: [M+H] ⁺ = 616)

Synthesis Example 23

Trz23 (15g, 38.1mmol) and compound B-4 (13.8g, 40mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (15.8g, 114.3mmol) was dissolved in 100mlml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 2 hours, it was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.7 g of Compound 23. (Yield 67%, MS: [M+H] ⁺ = 577)

Synthesis Example 24

Trz24 (15g, 33.8mmol) and compound B-5 (12.2g, 35.5mmol) were added to 300ml of THF and stirred and refluxed. After that, potassium carbonate (14g, 101.4mmol) was dissolved in 100mlml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 4 hours, it was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.7 g of Compound 24. (Yield 79%, MS: [M+H] ⁺ = 627)

Synthesis Example 25

Trz25 (15g, 33.8mmol) and compound B-5 (12.2g, 35.5mmol) were added to 300ml of THF and stirred and refluxed. After that, potassium carbonate (14g, 101.4mmol) was dissolved in 100mlml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.2 g of Compound 25. (Yield 72%, MS: [M+H] ⁺ = 627)

Synthesis Example 26

Trz26 (15g, 33.8mmol) and compound B-5 (12.2g, 35.5mmol) were added to 300ml of THF and stirred and refluxed. After that, potassium carbonate (14g, 101.4mmol) was dissolved in 100mlml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.7 g of Compound 26. (Yield 60%, MS: [M+H] ⁺ = 627)

Synthesis Example 27

Trz27 (15g, 40.8mmol) and compound B-6 (14.8g, 42.8mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (16.9g, 122.3mmol) was dissolved in 100mlml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.2 g of Compound 27. (Yield 72%, MS: [M+H] ⁺ = 551)

Synthesis Example 28

Trz28 (15g, 36.8mmol) and compound B-6 (13.3g, 38.6mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (15.2g, 110.3mmol) was dissolved in 100mlml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 2 hours, it was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.3 g of Compound 28. (Yield 75%, MS: [M+H] ⁺ = 591)

Synthesis Example 29

Trz29 (15g, 38.1mmol) and compound B-6 (13.8g, 40mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (15.8g, 114.3mmol) was dissolved in 100mlml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.6 g of Compound 29. (Yield 62%, MS: [M+H] ⁺ = 577)

Example 1

A glass substrate coated with ITO (indium tin oxide) to a thickness of 1,000 Å was put in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, a Fischer Co. product was used as the detergent, and distilled water filtered through a second filter of a Millipore Co. product was used as the distilled water. After washing the ITO for 30 minutes, it was repeated twice with distilled water and ultrasonic cleaning was performed for 10 minutes. After washing with distilled water, ultrasonic cleaning was performed with solvents such as isopropyl alcohol, acetone, and methanol, dried, and transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transferred to a vacuum deposition machine.

The following compound HI-1 was formed to a thickness of 1150 Å as a hole injection layer on the prepared ITO transparent electrode, but the following compound A-1 was p-doped at a concentration of 1.5%. On the hole injection layer, the following HT-1 compound was vacuum deposited to form a hole transport layer having a thickness of 800 Å. Subsequently, an electron blocking layer was formed by vacuum depositing the following EB-1 compound to a film thickness of 150 Å on the hole transport layer. Then, on the EB-1 deposited film, compound 1 as a host and compound Dp-7 as a dopant were vacuum-deposited at a weight ratio of 98:2 to form a red light emitting layer having a thickness of 400 Å. A hole blocking layer was formed on the light emitting layer by vacuum depositing the following HB-1 compound to a film thickness of 30 Å. Subsequently, the following ET-1 compound and the following LiQ compound were vacuum deposited at a weight ratio of 2:1 on the hole blocking layer to form an electron injection and transport layer with a thickness of 300 Å. A negative electrode was formed by sequentially depositing lithium fluoride (LiF) to a thickness of 12 Å and aluminum to a thickness of 1,000 Å on the electron injection and transport layer.

In the above process, the deposition rate of the organic material was maintained at 0.4 ~ 0.7Å / sec, the deposition rate of lithium fluoride on the cathode was 0.3Å / sec, and the deposition rate of aluminum was 2Å / sec, and the vacuum level during deposition was 2x10 ^-7 ~ Maintaining 5x10 ^-6 torr, an organic light emitting device was manufactured.

Examples 2 to 29

An organic light emitting device was manufactured in the same manner as in Example 1, except that the compounds listed in Table 1 were used in the organic light emitting device of Example 1.

Comparative Examples 1 to 10

An organic light emitting device was manufactured in the same manner as in Example 1, except that the compounds listed in Table 1 were used in the organic light emitting device of Example 1. In Table 1 below, compounds B-1 to B-10 are as follows.

When current was applied to the organic light emitting devices prepared in Examples 1 to 29 and Comparative Examples 1 to 10, voltage and efficiency were measured (based on 15 mA/cm ² ) and the results are shown in Table 1 below. . The lifetime T95 means the time required for the luminance to decrease from the initial luminance (6,000 nit) to 95%.

division	host	Driving voltage (V)	Efficiency (cd/A)	Lifetime T95(hr)	luminescent color
Example 1	compound 1	3.29	22.61	184	Red
Example 2	compound 2	3.30	22.59	191	Red
Example 3	compound 3	3.35	22.28	209	Red
Example 4	compound 4	3.36	22.58	197	Red
Example 5	compound 5	3.32	20.96	203	Red
Example 6	compound 6	3.32	21.46	193	Red
Example 7	compound 7	3.34	20.20	215	Red
Example 8	compound 8	3.44	22.00	186	Red
Example 9	compound 9	3.56	21.63	188	Red
Example 10	compound 10	3.40	22.38	184	Red
Example 11	compound 11	3.56	21.66	178	Red
Example 12	compound 12	3.56	20.97	175	Red
Example 13	compound 13	3.58	20.79	165	Red
Example 14	compound 14	3.54	20.23	163	Red
Example 15	compound 15	3.37	22.83	211	Red
Example 16	compound 16	3.42	22.56	191	Red
Example 17	compound 17	3.41	23.00	199	Red
Example 18	compound 18	3.41	22.25	186	Red
Example 19	compound 19	3.46	21.29	174	Red
Example 20	compound 20	3.46	22.35	180	Red
Example 21	compound 21	3.30	20.50	187	Red
Example 22	compound 22	3.28	21.12	210	Red
Example 23	compound 23	3.39	20.85	211	Red
Example 24	compound 24	3.55	20.64	162	Red
Example 25	compound 25	3.55	20.56	154	Red
Example 26	compound 26	3.55	20.78	155	Red
Example 27	compound 27	3.67	20.48	155	Red
Example 28	compound 28	3.68	19.54	150	Red
Example 29	compound 29	3.62	19.49	163	Red
Comparative Example 1	Compound B-1	4.27	14.30	94	Red
Comparative Example 2	Compound B-2	4.14	15.87	71	Red
Comparative Example 3	Compound B-3	4.09	15.93	82	Red
Comparative Example 4	Compound B-4	3.87	17.62	137	Red
Comparative Example 5	Compound B-5	3.81	17.87	122	Red
Comparative Example 6	Compound B-6	4.02	16.70	78	Red
Comparative Example 7	Compound B-7	3.94	15.06	106	Red
Comparative Example 8	Compound B-8	3.92	16.38	84	Red
Comparative Example 9	Compound B-9	4.03	15.77	71	Red
Comparative Example 10	Compound B-10	4.06	16.13	108	Red

When current was applied to the organic light emitting devices manufactured in Examples 1 to 29 and Comparative Examples 1 to 10, the results shown in Table 1 were obtained. The red organic light emitting device of Example 1 used materials widely used in the prior art, and had a structure using compound EB-1 as an electron blocking layer and Dp-7 as a red dopant.

When the compound of the present invention is used as a red light emitting layer, the driving voltage is reduced and the efficiency and lifetime are increased compared to the compound of Comparative Example. It was found that the energy transfer was well done. It can be determined that this is because electrons and holes combine to form excitons through a more stable balance into the light emitting layer compared to the comparative compound.

In conclusion, it can be confirmed that the driving voltage, luminous efficiency and lifetime characteristics of the organic light emitting device can be improved when the compound of the present invention is used as a host of the red light emitting layer.

[Description of code]

1: substrate 2: anode

3: light emitting layer 4: cathode

5: hole injection layer 6: hole transport layer

7: electron blocking layer 8: hole blocking layer

9: electron injection and transport layer

Claims (10)

1. A compound represented by Formula 1 below:

   [Formula 1]

   

   In Formula 1,

   X ₁ to X ₉ are each independently N or CR ₁ , but at least one of X ₁ to X ₉ is N;

   R ₁ is any one or more selected from the group consisting of hydrogen, deuterium, substituted or unsubstituted C _1-60 alkyl, substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted N, O and S; A C _2-60 heteroaryl containing a heteroatom,

   L is each independently a single bond or a substituted or unsubstituted C _6-60 arylene;

   Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C _6-60 aryl, or a substituted or unsubstituted C _2- including any one or more heteroatoms selected from the group consisting of N, O and S; ₆₀ heteroaryl.
2. According to claim 1,

   wherein one of X ₁ to X ₉ is N;

   compound.
3. According to claim 1,

   Chemical Formula 1 is represented by any one of the following Chemical Formulas 1-1 to 1-9,

   compound:

   

   In Formulas 1-1 to 1-9,

   X ₁ to X ₉ , R ₁ , L, Ar ₁ and Ar ₂ are as defined in claim 1,

   n is an integer from 1 to 8;
4. According to claim 1,

   R ₁ is hydrogen or deuterium;

   compound.
5. According to claim 1,

   L is a single bond, phenylene, or naphthylene;

   The phenylene and naphthylene are unsubstituted or substituted with one or more deuterium,

   compound.
6. According to claim 1,

   L is a single bond, or any one selected from the group consisting of

   compound:

   
7. According to claim 1,

   Ar ₁ and Ar ₂ are each independently phenyl, naphthyl, biphenylyl, terphenylyl, phenanthrenyl, phenyl naphthyl, naphthyl phenyl, dibenzofuranyl, dibenzothiophenyl, 9-phenyl-carba zolyl, carbazol-9-yl, benzophenanthrenyl, or chrysenyl;

   Wherein Ar ₁ and Ar ₂ are unsubstituted or substituted with one or more deuterium,

   compound.
8. According to claim 1,

   The compound represented by Formula 1 is any one selected from the group consisting of the following compounds,

   compound:

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   
9. 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 of the organic material layers includes the compound according to any one of claims 1 to 8. , an organic light emitting device.
10. According to claim 9

    The organic material layer containing the compound is a light emitting layer,

    organic light emitting device.

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