KR20200127885A - Organic light emitting device - Google Patents

Abstract

The present invention provides an organic light emitting element capable of improving efficiency, driving voltage, and lifespan characteristics. According to an embodiment of the present invention, the organic light emitting element comprises: an anode; a cathode provided to face the anode; and an organic material layer having one or more layers provided between the anode and the cathode.

Description

Organic light emitting device {ORGANIC LIGHT EMITTING DEVICE}

The present invention relates to an organic light emitting device.

In general, the organic light emission phenomenon refers to a phenomenon in which electrical energy is converted into light energy using an organic material. An 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 are being 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. The organic material layer is often made of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light emitting device.For example, it 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. In the structure of such an 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 excitons are formed when the injected holes and electrons meet. It glows when it falls back to the ground.

Development of new materials for organic materials used in organic light emitting devices as described above is continuously required.

Korean Patent Publication No. 10-2000-0051826

The present invention provides an organic light emitting device.

The present invention is a positive electrode; A cathode provided to face the anode; And one or more organic material layers provided between the anode and the cathode, wherein the organic material layer includes a compound represented by Formula 1 below and a compound represented by Formula 2 below.

[Formula 1]

In Formula 1,

X ₁ to X ₃ are each independently N or CR ₅ , but at least any one is N,

Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted aryl having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl having 2 to 60 carbon atoms including at least one of O, N, Si and S,

R ₁ to R ₅ are each independently hydrogen; heavy hydrogen; halogen; Hydroxy; Nitrile; Nitro; Amino; Substituted or unsubstituted C2 to C60 alkyl; Substituted or unsubstituted 2 to 60 alkoxy; Substituted or unsubstituted 2 to 60 alkenyl; Substituted or unsubstituted 6 to 60 aryl; A substituted or unsubstituted heteroaryl having 2 to 60 carbon atoms including at least one of O, N, Si and S, or R ₁ to R ₃ are bonded to adjacent groups to form a condensed ring,

One of A and B is a substituent represented by the following formula 1-1, and the other is hydrogen or deuterium,

[Formula 1-1]

In Formula 1-1,

R ₆ to R ₁₀ are each independently hydrogen; heavy hydrogen; halogen; Hydroxy; Nitrile; Nitro; Amino; Substituted or unsubstituted C2 to C60 alkyl; Substituted or unsubstituted 2 to 60 alkoxy; Substituted or unsubstituted 2 to 60 alkenyl; Substituted or unsubstituted 6 to 60 aryl; A substituted or unsubstituted heteroaryl having 2 to 60 carbon atoms including one or more of O, N, Si and S, or R ₆ to R ₉ are bonded to adjacent groups to form a condensed ring,

a is an integer from 1 to 6,

[Formula 2]

In Chemical Formula 2,

Ar ₃ and Ar ₄ are each independently substituted or unsubstituted aryl having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl having 2 to 60 carbon atoms including at least one of O, N, Si and S,

L ₁ and L ₂ are each independently a single bond; Or a substituted or unsubstituted arylene having 6 to 60 carbon atoms,

R ₁₁ to R ₁₄ are each independently hydrogen; heavy hydrogen; halogen; Hydroxy; Nitrile; Nitro; Amino; Substituted or unsubstituted C2 to C60 alkyl; Substituted or unsubstituted 2 to 60 alkoxy; Substituted or unsubstituted 2 to 60 alkenyl; Substituted or unsubstituted 6 to 60 aryl; Or a substituted or unsubstituted heteroaryl having 2 to 60 carbon atoms including at least one of O, N, Si and S,

b and e are each independently an integer of 1 to 4

c and d are each independently an integer of 1 to 3.

By using the compound represented by Formula 1 and Formula 2 as host materials for the emission layer, it is possible to improve efficiency, low driving voltage, and/or lifetime characteristics in an organic light emitting device.

FIG. 1 shows an example of an organic light-emitting device comprising 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 suppression 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 device comprising a cathode 4 is shown.

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

The present invention is a positive electrode; A cathode provided to face the anode; And an organic material layer provided between the anode and the cathode and including a compound represented by Formula 1 and a compound represented by Formula 2.

, 또는

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

, or

Means a bond connected to another substituent.

In the present specification, the term "substituted or unsubstituted" refers to 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; Alkyl sulfoxy group; Arylsulfoxy group; Silyl group; Boron group; Alkyl group; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; Aralkenyl group; Alkylaryl group; Alkylamine group; Aralkylamine group; Heteroarylamine group; Arylamine group; Arylphosphine group; Or it means a substituted or unsubstituted substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing one or more of N, O and S atoms, or linked with two or more substituents among the above-exemplified substituents. . For example, "a substituent to which two or more substituents are connected" 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 it 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 ester group may be substituted with an oxygen of the ester group 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 the present specification, the number of carbon atoms of the imide group is not particularly limited, but it 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 specifically includes a trimethyl boron group, a triethyl boron group, a t-butyldimethyl boron group, a triphenyl boron group, and a phenyl boron group, 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 a linear or branched chain, and the number of carbon atoms 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 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, cycloheptylmethyl, 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 are not limited thereto.

In the present specification, the alkenyl group may be a linear or branched chain, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to an exemplary 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, and the like, but are not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but is preferably 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 are 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 an exemplary embodiment, the aryl group has 6 to 30 carbon atoms. According to an exemplary embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a phenyl group, a biphenyl group, or a terphenyl group, but the monocyclic aryl group is not limited thereto. The polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, and the like, but is not limited thereto.

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.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 including at least one of O, N, Si and S as a heterogeneous element, and the number of carbons is not particularly limited, but it is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, acridyl group , Pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl 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, isoxazolyl group, thiiadia There may be a zolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but are not limited thereto.

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

The present invention, a negative electrode provided to face the positive electrode; And one or more organic material layers provided between the anode and the cathode, wherein the organic material layer includes a compound represented by Formula 1 and a compound represented by Formula 2. It provides an organic light-emitting device.

The organic light-emitting device may improve efficiency, low driving voltage, and/or lifetime characteristics in the organic light-emitting device by using the compound represented by Formula 1 and the compound represented by Formula 2 as host materials of the emission layer. .

Hereinafter, the present invention will be described in detail for each configuration.

Anode and cathode

As the anode material, a material having a large work function is preferable so that holes can be smoothly injected into the organic material 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); A combination of a metal and an oxide such as ZnO:Al or SNO ₂ :Sb; Poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), conductive polymers such as polypyrrole and polyaniline, and the like, but are not limited thereto.

It is preferable that the cathode material is 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 are multi-layered materials such as LiF/Al or LiO ₂ /Al, but are not limited thereto.

In addition, a hole injection layer may be additionally included on the anode. The hole injection layer is made of a hole injection material, and the hole injection material has the ability to transport holes, and thus has a hole injection effect at the anode, an excellent hole injection effect for the light emitting layer or the light emitting material. A compound that prevents migration to the electron injection layer or the electron injection material and has excellent thin film formation ability is preferable.

It is preferable that the HOMO (highest occupied molecular orbital) 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 material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, perylene There are a series of organic substances, anthraquinone, and polyaniline and a polythiophene series of conductive polymers, but are not limited thereto.

Emitting layer

As a light-emitting material included in the light-emitting layer, a material capable of emitting light in the visible light region by transporting and combining holes and electrons from the hole control layer and the electron transport layer, respectively, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable. .

The light-emitting layer may include a host material and a dopant material. In particular, in the present invention, as a host material, the compound represented by Formula 1 and the compound represented by Formula 2 are included.

Formula 1 may be any one selected from compounds represented by the following Formulas 1-A, 1-B, and 1-C.

In the above formulas 1-A, 1-B and 1-C,

Description of X ₁ , X ₂ , X ₃ , Ar ₁ , Ar ₂ , A and B is as defined above.

In Formula 1, all of X ₁ to X ₃ may be N.

Ar ₁ and Ar ₂ in Formula 1 are each independently It may be any one selected from the group consisting of the following.

Formula 1-1 may be selected from the group consisting of the following compounds.

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

The compound represented by Chemical Formula 1 can be prepared by a manufacturing method as shown in Scheme 1 or 2. The manufacturing method may be more specific in the manufacturing examples described later.

[Scheme 1]

[Scheme 2]

In Reaction Schemes 1 and 2, definitions other than Q are the same as defined above, and Q is halogen, more preferably bromo or chloro. The reaction is a Suzuki coupling reaction, and is preferably carried out in the presence of a palladium catalyst and a base, and the reactor for the Suzuki coupling reaction may be changed as known in the art. The manufacturing method may be more specific in the manufacturing examples to be described later.

In addition, as the host material, the compound represented by Formula 1 and the compound represented by Formula 2 may be used together.

The compound represented by Formula 2 may be a compound represented by Formula 2-1 below.

[Formula 2-1]

The description of Ar ₃ , Ar ₄ , L ₁ and L ₂ is as defined above.

In Formula 2, Ar ₃ and Ar ₄ may each independently be any one selected from the group consisting of the following.

In Formula 2, L ₁ and L ₂ may each independently be a single bond or any one selected from the group consisting of the following.

In Formula 2, R ₁₁ to R ₁₄ may be hydrogen.

The compound represented by Formula 2 may be selected from the group consisting of the following compounds.

The compound represented by Chemical Formula 2 can be prepared by the same method as in Scheme 3 below. The manufacturing method may be more specific in the manufacturing examples described later.

[Scheme 3]

In Reaction Scheme 3, definitions other than Q'are the same as defined above, and Q is halogen, more preferably bromo or chloro. The reaction is a Suzuki coupling reaction, and is preferably carried out in the presence of a palladium catalyst and a base, and the reactor for the Suzuki coupling reaction may be changed as known in the art. The manufacturing method may be more specific in the manufacturing examples to be described later.

The emission layer may further include a host material known in the art in addition to the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2. Specific examples of such a host material include condensed aromatic ring derivatives or heterocyclic-containing compounds. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Meanwhile, the emission layer may further include a dopant material. Dopant materials 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 pyrene, anthracene, chrysene, and periflanthene having an arylamino group, and the styrylamine compound is substituted or unsubstituted A compound in which at least one arylvinyl group is substituted on the arylamine, and one or two or more substituents selected from the group consisting of aryl group, silyl group, alkyl group, cycloalkyl group and arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but are not limited thereto. In addition, the metal complex includes an iridium complex, a platinum complex, and the like, but is not limited thereto.

For example, the dopant may be any one selected from compounds represented by the following Dp-1 to Dp-38.

Hole transport layer

The hole transport layer is a layer that receives holes from the anode or the hole injection layer formed on the anode and transports holes to the emission layer, and is a material capable of transporting holes from the anode or the hole injection layer as a hole transport material to the emission layer. Materials with high mobility are suitable.

Specific examples include an arylamine-based organic material, a conductive polymer, and a block copolymer including a conjugated portion and a non-conjugated portion, but are not limited thereto.

Hole control layer

The hole control layer refers to a layer that controls hole mobility according to the energy level of the emission layer in the organic light emitting device.

Electron transport layer

The electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the emission layer. As an electron transport material, a material capable of receiving electrons from the cathode and transferring them to the emission layer is suitable. Do. Specific examples include Al complex of 8-hydroxyquinoline; Complexes containing Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto. 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 conventional materials that have a low work function and are followed by an aluminum layer or a silver layer. Specifically, they are cesium, barium, calcium, ytterbium, and samarium, and in each case an aluminum layer or a silver layer follows.

Electron injection layer

The organic light-emitting device according to the present invention may include an electron injection layer between the electron transport layer and the cathode, if necessary. The electron injection layer is a layer that injects electrons from the electrode, has the ability to transport electrons, has an electron injection effect from the cathode, an excellent electron injection effect on the light emitting layer or the light emitting material, and hole injection of excitons generated in the light emitting layer A compound that prevents migration to the layer and has excellent thin film formation ability is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, and their derivatives, metals Complex compounds and nitrogen-containing 5-membered ring derivatives, but are not limited thereto.

Examples of the metal complex compound include lithium 8-hydroxyquinolinato, 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)( o-cresolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtholato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtholato)gallium, etc. It is not limited to this.

Organic light emitting element

The structure of the organic light emitting device according to the present invention is illustrated in FIGS. 1 and 2. FIG. 1 shows an example of an organic light-emitting device comprising a substrate 1, an anode 2, a light-emitting layer 3, and a cathode 4. In such a structure, the compounds represented by Formulas 1 and 2 may be included in the emission layer.

2 shows a substrate (1), an anode (2), a hole injection layer (5), a hole transport layer (6), an electron suppression 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 device comprising a cathode 4 is shown. In such a structure, the compounds represented by Formulas 1 and 2 may be included in one or more of the hole injection layer, hole transport layer, electron suppression layer, light emitting layer, hole blocking layer, and electron injection and transport layer. Specifically, the organic material layer may include an emission layer, and the emission layer may include two or more kinds of host materials. In this case, the two or more host materials may include compounds represented by Formulas 1 and 2.

The organic light emitting device according to the present invention can be manufactured by sequentially stacking the above-described configurations. At this time, using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, the anode is formed by depositing a metal or a conductive metal oxide or an alloy thereof on the substrate. And, after forming each of the above-described layers thereon, it can be prepared by depositing a material that can be used as a cathode thereon. 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 light emitting layer may be formed by a solution coating method as well as a vacuum deposition method of a host and a dopant. Here, the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, roll coating, and the like, but is not limited thereto.

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

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

The fabrication of the organic light emitting device described above will be described in detail in the following examples. However, the following examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

Preparation Example 1-1: Preparation of intermediate a

1) Preparation of intermediate a-1

Naphthalen-2-amine (300.0 g, 1.0 eq), 1-bromo-2-iodobenzene 592.7 g, 1.0 eq), sodium tert-butoxide ( NaOtBu, 302.0 g, 1.5 eq), palladium acetate (Pd(OAc) ₂ , 4.70 g, 0.01 eq), Xantphos (12.12 g, 0.01 eq) 1,4-dioxane (1,4-dioxane, 5L), refluxed and stirred. When the reaction was completed after 3 hours, the pressure was reduced to remove the solvent. Then, it was completely dissolved in ethyl acetate, washed with water, and reduced pressure to remove about 70% of the solvent. In the reflux state, hexane was added, the crystals were dropped, cooled, and filtered. This was subjected to column chromatography to obtain an intermediate a-1. (443.5 g, yield 71%, [M+H] ⁺ =299)

2) Preparation of intermediate a(5H-benzo[b]carbazole)

Intermediate a-1 (443.5 g, 1.0 eq) bis (tri-tert-butylphosphine) palladium (0) (Pd (t-Bu ₃ P) _2, 8.56 g, 0.01 eq), potassium carbonate (K ₂ CO ₃ , 463.2 g, 2.00 eq) was added to diethylacetamide (4L) and refluxed and stirred. After 3 hours, the reaction was poured into water to drop crystals and filtered. The filtered solid was completely dissolved in 1,2-dichlorobenzene, washed with water, and the solution in which the product was dissolved was concentrated under reduced pressure to drop crystals, cool, and then filtered. This was purified by column chromatography to obtain an intermediate a (5H-benzo[b]carbazole). (174.8 g, yield 48%, [M+H] ⁺ =218)

Preparation Example 1-2: Preparation of intermediate b

In the same manner as in Preparation Example 1-1, except that 1-bromo-2-iodonaphthalene was used instead of 1-bromo-2-iodobenzene. The following intermediate b(7H-dibenzo[b,g]carbazole) was obtained.

Preparation Example 1-3: Preparation of intermediate c

In the same manner as in Preparation Example 1-1, except that 2,3-dibromonaphthalene was used instead of 1-bromo-2-iodobenzene, the following intermediate c ( 6H-dibenzo[b,h]carbazole) was obtained.

Preparation Example 1-4: Preparation of intermediate d

The following intermediate in the same manner as in Preparation Example 1, except that 2-bromo-1-iodonaphthalene was used instead of 1-bromo-2-iodobenzene d(13H-dibenzo[a,h]carbazole) was prepared.

Manufacturing example 1-5: Preparation of intermediate e

1) Preparation of intermediate e-3

1-bromo-2-iodobenzene (1-bromo-2-iodobenzene, 200.0 g, 1.0 eq), (4-chloro-2-(methylthio)phenyl) boronic acid ((4-chloro-2-( methylthio)phenyl)boronic acid, 105.9 g, 1.0 eq), potassium carbonate (K ₂ CO ₃ , 173.9 g, 2.0 eq), tetrakis (triphenylphosphine) palladium(0) (Pd(PPh ₃ ) ₄ , 14.55 g, 0.02 eq) was dissolved in tetrahydrofuran (THF, 3 L), refluxed and stirred. When the reaction was completed after 2 hours, the pressure was reduced to remove the solvent. Then, it was completely dissolved in ethyl acetate, washed with water, and reduced pressure to remove about 80% of the solvent. In the reflux state, hexene was added, the crystals were dropped, cooled, and filtered. This was subjected to column chromatography to obtain an intermediate e-3. (138.36 g, yield 70%, [M+H] ⁺ =312)

2) Preparation of intermediate e-2

Intermediate e-3 (138.36 g, 1.0 eq) and hydrogen peroxide (H ₂ O ₂ , 22.5 g, 2.00 eq) were added to acetic acid (1 L) and refluxed and stirred. After 1 hour, the reaction was poured into water to drop crystals and filtered. The filtered solid was completely dissolved in ethyl acetate, washed with water, and reduced pressure to remove about 80% of the solvent. In the reflux state, hexene was added, the crystals were dropped, cooled, and filtered. This was subjected to column chromatography to obtain an intermediate e-2. (91.61 g, yield 63%, [M+H] ⁺ =328)

3) Preparation of intermediate e-1

Intermediate e-2 (91.61 g, 1.0 eq) was added to hydrogen peroxide (H ₂ O ₂ , 500 ml) and stirred while dissolving by refluxing. When the reaction was completed after 2 hours, the reaction product was poured into water to drop crystals and filtered. The filtered solid was completely dissolved in chloroform (CHCl ₃ ), washed with water, and the solution in which the product was dissolved was concentrated under reduced pressure to remove about 80% of the solvent. In the reflux state, hexene was added again, the crystals were dropped, cooled, and filtered to obtain an intermediate e-1. (50.45 g, 61% yield, [M+H] ⁺ = 296)

3) Preparation of intermediate e

Intermediate e-1 (50.45 g, 1.0 eq), bis (pinacolato) diboron, 55.96 g, 1.3 eq), 1,1-bis (diphenylphosphino) ferrocene-palladium (II ) Dichloride (Pd(dppf)Cl ₂ , 2.48 g, 0.02 eq) and potassium acetate (KOAc, 18.98 g, 2.00 eq) were added to dioxane (800 mL) and refluxed and stirred. When the reaction was completed after 3 hours, the pressure was reduced to remove the solvent. The filtered solid was completely dissolved in chloroform (CHCl ₃ ), washed with water, and the solution in which the product was dissolved was concentrated under reduced pressure to remove about 90% of the solvent. Ethanol was added to the mixture under reflux, the crystals were dropped, cooled, and filtered to obtain an intermediate e. (49.66 g, yield 84%, [M+H] ⁺ = 345)

Manufacturing example 1-6: Preparation of intermediate f

(5-chloro-2-(methylthio)phenyl)boronic acid ((5-chloro-2-(methylthio)phenyl)boronic acid) was used instead of (4-chloro-2-(methylthio)phenyl)boronic acid Except for the point, the following intermediate f was prepared in the same manner as in Preparation Example 1-5.

Manufacturing example 1-7: Preparation of intermediate g

In the same manner as in Preparation Example 1-5, except that 1-bromo-2-iodonaphthalene was used instead of 1-bromo-2-iodobenzene Intermediate g was prepared.

Manufacturing example 1-8: Preparation of intermediate h

In the same manner as in Preparation Example 1-7, except that (5-chloro-2-(methylthio)phenyl)boronic acid was used instead of (4-chloro-2-(methylthio)phenyl)boronic acid. The following intermediate h was prepared.

Manufacturing example 1-9: Preparation of intermediate i

In the same manner as in Preparation Example 1-5, except that 2-bromo-3-iodonaphthalene was used instead of 1-bromo-2-iodobenzene Intermediate i was prepared.

Manufacturing example 1-10: Preparation of intermediate j

In the same manner as in Preparation Example 1-9, except that (5-chloro-2-(methylthio)phenyl)boronic acid was used instead of (4-chloro-2-(methylthio)phenyl)boronic acid. The following intermediate j was prepared.

The intermediates e to j and the triazine-based intermediate were reflected through a Suzuki coupling reaction to prepare the following intermediates 1-1 to 21-1.

Preparation Example 2-1: Preparation of Compound 1

In a nitrogen atmosphere, Intermediate 1-1 (20.0 g, 44.5 mmol), Intermediate a (9.7 g, 44.5 mmol), sodium tert-butoxide (8.6 g, 89.1 mmol) were added to xylene (400 ml). ), and stirred and refluxed. Thereafter, bis (tri-tert-butylphosphine) palladium (0) (bis (tri-tert-butylphosphine) palladium (0), 0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 1. (14.9 g, yield 53%, MS: [M+H] ⁺ = 631)

Preparation Example 2-2: Preparation of Compound 2

In a nitrogen atmosphere, intermediate 2-1 (20.0 g, 40.1 mmol), intermediate a (8.7 g, 40.1 mmol), and shodium tert-butoxide (7.7 g, 80.1 mmol) were stirred and refluxed in xylene (400 ml). Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.9 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 2. (14.2 g, yield 52%, MS: [M+H] ⁺ = 681)

Preparation Example 2-3: Preparation of Compound 3

In a nitrogen atmosphere, intermediate 3-1 (20.0 g, 36.4 mmol), intermediate a (7.9 g, 36.4 mmol), and shodium tert-butoxide (7 g, 72.8 mmol) were added to xylene (400 ml) and stirred and refluxed. . After this, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 3. (13.3 g, yield 50%, MS: [M+H] ⁺ = 731)

Preparation Example 2-4: Preparation of compound 4

In a nitrogen atmosphere, intermediate 4-1 (20.0 g, 44.5 mmol), intermediate b (11.9 g, 44.5 mmol), and shodium tert-butoxide (8.6 g, 89.1 mmol) were added to xylene (400 ml) and stirred and refluxed. . After this, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 4. (17.6 g, yield 58%, MS: [M+H] ⁺ = 681)

Preparation Example 2-5: Preparation of compound 5

In a nitrogen atmosphere, intermediate 5-1 (20.0 g, 44.5 mmol), intermediate c (11.9 g, 44.5 mmol), and shodium tert-butoxide (8.6 g, 89.1 mmol) were added to xylene (400 ml) and stirred and refluxed. . After this, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 5. (15.4 g, yield 51%, MS: [M+H] ⁺ = 681)

Preparation Example 2-6: Preparation of Compound 6

In a nitrogen atmosphere, intermediate 6-1 (20.0 g, 40.1 mmol), intermediate c (10.7 g, 40.1 mmol), and shodium tert-butoxide (7.7 g, 80.1 mmol) were added to xylene (400 ml) and stirred and refluxed. . Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 6. (19.9 g, yield 68%, MS: [M+H] ⁺ = 731)

Manufacturing example 2-7: Preparation of compound 7

In a nitrogen atmosphere, intermediate 7-1 (20.0 g, 36.4 mmol), intermediate d (9.7g, 36.4 mmol), and shodium tert-butoxide (7 g, 72.8 mmol) were added to xylene (Xylene, 400 ml) and stirred. Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 7. (14.2 g, yield 50%, MS: [M+H] ⁺ = 781)

Manufacturing example 2-8: Preparation of compound 8

In a nitrogen atmosphere, intermediate 8-1 (20.0 g, 36.4 mmol), intermediate d (9.7g, 36.4 mmol), and shodium tert-butoxide (7 g, 72.8 mmol) were added to xylene, and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 8. (19.3 g, yield 68%, MS: [M+H] ⁺ = 781)

Preparation Example 2-9: Preparation of Compound 9

In a nitrogen atmosphere, intermediate 9-1 (20.0 g, 37.0 mmol), intermediate a (8 g, 37.0 mmol), and shodium tert-butoxide (7.1 g, 74.1 mmol) were added to xylene (Xylene, 400 ml) and stirred. Refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 9. (14.9 g, yield 56%, MS: [M+H] ⁺ = 722)

Preparation Example 2-10: Preparation of Compound 10

In a nitrogen atmosphere, intermediate 10-1 (20.0 g, 37.0 mmol), intermediate a (8 g, 37 mmol), shodium tert-butoxide (7.1 g, 74.1 mmol) was added to xylene, and stirred and Refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 10. (14.4 g, yield 54%, MS: [M+H] ⁺ = 722)

Preparation Example 2-11: Preparation of Compound 11

In a nitrogen atmosphere, intermediate 11-1 (20.0 g, 36.0 mmol), intermediate a (7.8 g, 36.0 mmol), and shodium tert-butoxide (6.9 g, 71.9 mmol) were added to xylene, and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 11. (15.6 g, yield 59%, MS: [M+H] ⁺ = 738)

Preparation Example 2-12: Preparation of Compound 12

In a nitrogen atmosphere, intermediate 12-1 (20.0 g, 38.0 mmol), intermediate a (8.3g, 38.0 mmol), and shodium tert-butoxide (7.3 g, 76.0 mmol) were added to xylene, and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 12. (18.0 g, yield 67%, MS: [M+H] ⁺ = 708)

Manufacturing example 2-13: Preparation of compound 13

In a nitrogen atmosphere, intermediate 13-1 (20.0 g, 29.3 mmol), intermediate a (6.4 g, 29.3 mmol), and shodium tert-butoxide (5.6 g, 58.6 mmol) were added to xylene, and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 13. (12.9 g, yield 51%, MS: [M+H] ⁺ = 864)

Manufacturing example 2-14: Preparation of compound 14

In a nitrogen atmosphere, intermediate 14-1 (20.0 g, 29.3 mmol), intermediate a (6.4 g, 29.3 mmol), shodium tert-butoxide (5.6 g, 58.6 mmol) was added to xylene, and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 14. (14.4 g, yield 57%, MS: [M+H] ⁺ = 864)

Manufacturing example 2-15: Preparation of compound 15

In a nitrogen atmosphere, intermediate 15-1 (20.0 g, 30.7 mmol), intermediate a (6.7 g, 30.7 mmol), shodium tert-butoxide (5.9 g, 61.3 mmol) was added to xylene, and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 15. (14.6 g, yield 57%, MS: [M+H] ⁺ = 834)

Manufacturing example 2-16: Preparation of compound 16

In a nitrogen atmosphere, intermediate 16-1 (20.0 g, 37.0 mmol), intermediate c (9.9 g, 37.0 mmol), and shodium tert-butoxide (7.1 g, 74.1 mmol) were added to xylene (Xylene, 400 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 16. (16.3 g, yield 57%, MS: [M+H] ⁺ = 772)

Preparation Example 2-17: Preparation of compound 17

In a nitrogen atmosphere, intermediate 17-1 (20.0 g, 37.0 mmol), intermediate c (9.9 g, 37 mmol), and shodium tert-butoxide (7.1 g, 74.1 mmol) were added to xylene, and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 17. (14.6 g, yield 51%, MS: [M+H] ⁺ = 772)

Manufacturing example 2-18: Preparation of compound 18

In a nitrogen atmosphere, intermediate 18-1 (20.0 g, 36.0 mmol), intermediate b (9.6 g, 36 mmol), and shodium tert-butoxide (6.9 g, 71.9 mmol) were added to xylene (Xylene, 400 ml) and stirred. Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 18. (14.2 g, yield 50%, MS: [M+H] ⁺ = 788)

Manufacturing example 2-19: Preparation of compound 19

In a nitrogen atmosphere, intermediate 19-1 (20.0 g, 33.3 mmol), intermediate d (8.9 g, 33.3 mmol), and shodium tert-butoxide (6.4 g, 66.7 mmol) were added to xylene (Xylene, 400 ml) and stirred. Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.7 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 19. (14.4 g, yield 52%, MS: [M+H] ⁺ = 832)

Preparation Example 2-20: Preparation of Compound 20

In a nitrogen atmosphere, intermediate 20-1 (20.0 g, 31.9 mmol), intermediate b (8.5 g, 31.9 mmol), and shodium tert-butoxide (6.1 g, 63.9 mmol) were added to xylene (Xylene, 400 ml) and stirred. Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 20. (14.5 g, yield 53%, MS: [M+H] ⁺ = 858)

Manufacturing example 2-21: Preparation of compound 21

In a nitrogen atmosphere, intermediate 21-1 (20.0 g, 31.9 mmol), intermediate a (6.9 g, 31.9 mmol), and shodium tert-butoxide (6.1 g, 63.9 mmol) were added to xylene (Xylene, 400 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 21. (16.3 g, yield 62%, MS: [M+H] ⁺ = 822)

Preparation Example 3-1: Preparation of compound 2-1

In a nitrogen atmosphere, intermediate 2-1-1 (10.0 g, 25.2 mmol) and intermediate 2-1-2 (8 g, 27.7 mmol) were added to tetrahydrofuran (THF, 200 ml) and stirred, and potassium carbonate (13.9 g , 100.7 mmol) was dissolved in water, and then sufficiently stirred and refluxed. Then, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.3 mmol) was added. After the reaction for 3 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 2-1. (9.0 g, yield 64%, MS: [M+H] ⁺ = 561)

Preparation Example 3-2: Preparation of Compound 2-2

In a nitrogen atmosphere, intermediate 2-2-1 (10.0 g, 25.2 mmol) and intermediate 2-2-2 (8 g, 27.7 mmol) were added to THF (200 ml) and stirred, and potassium carbonate (13.9 g, 100.7 mmol) Was dissolved in water, added, and sufficiently stirred and refluxed. Then, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.3 mmol) was added. After the reaction for 4 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 2-2. (10.6 g, yield 66%, MS: [M+H] ⁺ = 637)

Preparation Example 3-3: Preparation of Compound 2-3

In a nitrogen atmosphere, intermediate 2-3-1 (10.0 g, 25.2 mmol) and intermediate 2-3-2 (10.1 g, 27.7 mmol) were added to THF (200 ml) and stirred, and potassium carbonate (13.9 g, 100.7 mmol) Was dissolved in water, added, and sufficiently stirred and refluxed. Then, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.3 mmol) was added. After the reaction for 4 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 2-3. (9 g, yield 56%, MS: [M+H] ⁺ = 637)

Preparation Example 3-4: Preparation of compound 2-4

In a nitrogen atmosphere, intermediate 2-4-1 (10.0 g, 25.2 mmol) and intermediate 2-4-2 (9.3 g, 27.7 mmol) were added to THF (200 ml) and stirred, and potassium carbonate (13.9 g, 100.7 mmol) Was dissolved in water, added, and sufficiently stirred and refluxed. Then, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.3 mmol) was added. After the reaction for 2 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 2-4. (7.8 g, yield 51%, MS: [M+H] ⁺ = 611)

Preparation Example 3-5: Preparation of compound 2-5

In a nitrogen atmosphere, intermediate 2-5-1 (10.0 g, 25.2 mmol) and intermediate 2-5-2 (10.1 g, 27.7 mmol) were added to THF (200 ml) and stirred, and potassium carbonate (13.9 g, 100.7 mmol) Was dissolved in water, added, and sufficiently stirred and refluxed. Then, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.3 mmol) was added. After the reaction for 4 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 2-5. (10.4 g, yield 65%, MS: [M+H] ⁺ = 637)

Preparation Example 3-6: Preparation of compound 2-6

In a nitrogen atmosphere, intermediate 2-6-1 (10.0 g, 25.2 mmol) and intermediate 2-6-2 (11.4 g, 27.7 mmol) were added to THF (200 ml) and stirred, and potassium carbonate (13.9 g, 100.7 mmol) Was dissolved in water, added, and sufficiently stirred and refluxed. Then, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.3 mmol) was added. After the reaction for 2 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 2-6. (10.5 g, 61% yield, MS: [M+H] ⁺ = 687)

Preparation Example 3-7: Preparation of Compound 2-7

In a nitrogen atmosphere, intermediate 2-7-1 (10.0 g, 22.4 mmol) and intermediate 2-7-2 (10.2 g, 24.6 mmol) were added to THF (200 ml), stirred, and potassium carbonate (12.4 g, 89.5 mmol) was added. It was dissolved in water and added, and sufficiently stirred and refluxed. Thereafter, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After the reaction for 3 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 2-7. (11.0 g, yield 67%, MS: [M+H] ⁺ = 737)

Preparation Example 3-8: Preparation of compound 2-8

In a nitrogen atmosphere, intermediate 2-8-1 (10.0 g, 17.9 mmol) and intermediate 2-8-2 (5.6 g, 19.7 mmol) were added to THF (200 ml) and stirred, and potassium carbonate (9.9 g, 71.5 mmol) Was dissolved in water, added, and sufficiently stirred and refluxed. Thereafter, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After the reaction for 3 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 2-8. (7.8 g, yield 60%, MS: [M+H] ⁺ = 723)

Preparation Example 3-9: Preparation of Compound 2-9

In a nitrogen atmosphere, intermediate 2-9-1 (10.0 g, 21.1 mmol) and intermediate 2-9-2 (6.7 g, 23.3 mmol) were added to THF (200 ml) and stirred, and potassium carbonate (11.7 g, 84.6 mmol) Was dissolved in water, added, and sufficiently stirred and refluxed. Thereafter, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After the reaction for 3 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 2-9. (7.4 g, yield 55%, MS: [M+H] ⁺ = 637)

Preparation Example 3-10: Preparation of Compound 2-10

In a nitrogen atmosphere, intermediate 2-10-1 (10.0 g, 27 mmol) and intermediate 2-10-2 (10.0 g, 29.6 mmol) were added to THF (200 ml) and stirred, and potassium carbonate (14.9 g, 107.8 mmol) Was dissolved in water, added, and sufficiently stirred and refluxed. Then, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.3 mmol) was added. After the reaction for 2 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 2-10. (11 g, yield 70%, MS: [M+H] ⁺ = 585)

Preparation Example 3-11: Preparation of Compound 2-11

In a nitrogen atmosphere, intermediate 2-11-1 (10.0 g, 27 mmol) and intermediate 2-11-2 (11.5 g, 29.6 mmol) were added to THF (200 ml) and stirred, and potassium carbonate (14.9 g, 107.8 mmol) Was dissolved in water, added, and sufficiently stirred and refluxed. Then, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.3 mmol) was added. After the reaction for 2 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 2-11. (11.5 g, yield 67%, MS: [M+H] ⁺ = 635)

Preparation Example 3-12: Preparation of Compound 2-12

In a nitrogen atmosphere, intermediate 2-12-1 (10.0 g, 23.8 mmol) and intermediate 2-12-2 (8.8 g, 26.1 mmol) were added to THF (200 ml) and stirred, followed by potassium carbonate (13.1 g, 95 mmol). Was dissolved in water, added, and sufficiently stirred and refluxed. Thereafter, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After the reaction for 3 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 2-12. (10.4 g, yield 69%, MS: [M+H] ⁺ = 635)

Preparation Example 3-13: Preparation of Compound 2-13

In a nitrogen atmosphere, intermediate 2-13-1 (10.0 g, 24.3 mmol) and intermediate 2-13-2 (11.1 g, 26.8 mmol) were added to THF (200 ml) and stirred, and potassium carbonate (13.5 g, 97.3 mmol) Was dissolved in water, added, and sufficiently stirred and refluxed. Thereafter, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After the reaction for 2 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 2-13. (9 g, yield 53%, MS: [M+H] ⁺ = 701)

Preparation Example 3-14: Preparation of Compound 2-14

In a nitrogen atmosphere, intermediate 2-14-1 (10.0 g, 24.3 mmol) and intermediate 2-14-2 (7.7 g, 26.8 mmol) were added to THF (200 ml) and stirred, and potassium carbonate (13.5 g, 97.3 mmol) Was dissolved in water, added, and sufficiently stirred and refluxed. Thereafter, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After the reaction for 3 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 2-14. (8.9 g, yield 64%, MS: [M+H] ⁺ = 575)

Preparation Example 3-15: Preparation of Compound 2-15

In a nitrogen atmosphere, intermediate 2-15-1 (10.0 g, 24.3 mmol) and intermediate 2-15-2 (9 g, 26.8 mmol) were added to THF (200 ml) and stirred, and potassium carbonate (13.5 g, 97.3 mmol) Was dissolved in water, added, and sufficiently stirred and refluxed. Thereafter, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After the reaction for 4 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 2-15. (8.4 g, yield 55%, MS: [M+H] ⁺ = 625)

Preparation Example 3-16: Preparation of Compound 2-16

In a nitrogen atmosphere, intermediate 2-16-1 (10.0 g, 24.3 mmol) and intermediate 2-16-2 (11.1 g, 26.8 mmol) were added to THF (200 ml) and stirred, and potassium carbonate (13.5 g, 97.3 mmol) Was dissolved in water, added, and sufficiently stirred and refluxed. Thereafter, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After the reaction for 2 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 2-16. (11.2 g, yield 66%, MS: [M+H] ⁺ = 701)

Preparation Example 3-17: Preparation of Compound 2-17

In a nitrogen atmosphere, intermediate 2-17-1 (10.0 g, 24.3 mmol) and intermediate 2-17-2 (10.1 g, 26.8 mmol) were added to THF (200 ml) and stirred, and potassium carbonate (13.5 g, 97.3 mmol) Was dissolved in water, added, and sufficiently stirred and refluxed. Thereafter, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After the reaction for 3 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 2-17. (10.0 g, yield 62%, MS: [M+H] ⁺ = 665)

Preparation Example 3-18: Preparation of Compound 2-18

In a nitrogen atmosphere, intermediate 2-18-1 (10.0 g, 24.3 mmol) and intermediate 2-18-2 (10.5 g, 26.8 mmol) were added to THF (200 ml) and stirred, and potassium carbonate (13.5 g, 97.3 mmol) Was dissolved in water, added, and sufficiently stirred and refluxed. Thereafter, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After the reaction for 2 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 2-18. (9.8 g, yield 59%, MS: [M+H] ⁺ = 681)

Preparation Example 3-19: Preparation of Compound 2-19

In a nitrogen atmosphere, intermediate 2-19-1 (10.0 g, 24.3 mmol) and intermediate 2-19-2 (10.5 g, 26.8 mmol) were added to THF (200 ml) and stirred, and potassium carbonate (13.5 g, 97.3 mmol) Was dissolved in water, added, and sufficiently stirred and refluxed. Thereafter, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After the reaction for 3 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 2-19. (11.4 g, yield 69%, MS: [M+H] ⁺ = 681)

Preparation Example 3-20: Preparation of Compound 2-20

In a nitrogen atmosphere, intermediate 2-20-1 (10.0 g, 23.4 mmol) and intermediate 2-20-2 (9.4 g, 25.8 mmol) were added to THF (200 ml) and stirred, and potassium carbonate (12.9 g, 93.7 mmol) Was dissolved in water, added, and sufficiently stirred and refluxed. Thereafter, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After the reaction for 2 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 2-20. (9 g, yield 58%, MS: [M+H] ⁺ = 667)

Preparation Example 3-21: Preparation of Compound 2-21

In a nitrogen atmosphere, intermediate 2-21-1 (10.0 g, 23.4 mmol) and intermediate 2-21-2 (10.6 g, 25.8 mmol) were added to THF (200 ml) and stirred, and potassium carbonate (12.9 g, 93.7 mmol) Was dissolved in water, added, and sufficiently stirred and refluxed. Thereafter, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After the reaction for 4 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 2-21. (10.7 g, yield 64%, MS: [M+H] ⁺ = 717)

Preparation Example 3-22: Preparation of Compound 2-22

In a nitrogen atmosphere, intermediate 2-22-1 (10.0 g, 23.4 mmol) and intermediate 2-22-2 (11.3 g, 25.8 mmol) were added to THF (200 ml) and stirred, and potassium carbonate (12.9 g, 93.7 mmol) Was dissolved in water, added, and sufficiently stirred and refluxed. Thereafter, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After the reaction for 3 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 2-22. (9 g, yield 52%, MS: [M+H] ⁺ = 743)

Preparation Example 3-23: Preparation of Compound 2-23

In a nitrogen atmosphere, intermediate 2-23-1 (10.0 g, 23.4 mmol) and intermediate 2-23-2 (10.1 g, 25.8 mmol) were added to THF (200 ml) and stirred, and potassium carbonate (12.9 g, 93.7 mmol) Was dissolved in water, added, and sufficiently stirred and refluxed. Thereafter, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After the reaction for 4 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 2-23. (9.1 g, yield 56%, MS: [M+H] ⁺ = 697)

Example 1

A glass substrate coated with a thin film of ITO (indium tin oxide) having a thickness of 1,000Å was put in distilled water dissolved in a detergent and washed with ultrasonic waves. At this time, a product made by Fischer Co. was used as a detergent, and distilled water secondarily filtered with a filter manufactured by Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, it was repeated twice with distilled water to perform ultrasonic cleaning for 10 minutes. After washing with distilled water, ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator.

The following HI-1 compound was formed as a hole injection layer on the prepared ITO transparent electrode to a thickness of 1150Å, but the following compound A-1 was p-doped at a concentration of 1.5%. The following HT-1 compound was vacuum deposited on the hole injection layer to form a hole transport layer having a thickness of 800 Å. Subsequently, the following EB-1 compound was vacuum deposited on the hole transport layer with a film thickness of 150 Å to form an electron suppressing layer. Subsequently, compound 1 prepared in Preparation Example 2-1 and Compound 2-1 prepared in Preparation Example 3-1 were co-deposited at a weight ratio of 1:1 as a host material on the EB-1 deposition film, and a dopant Dp-7 The compound was vacuum-deposited at a weight ratio of 98:2 (host:dopant) to form a red light emitting layer having a thickness of 400 Å. A hole blocking layer was formed by vacuum vapor deposition of the following HB-1 compound having a thickness of 30 Å on the emission layer. 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. Lithium fluoride (LiF) at a thickness of 12 Å and aluminum at a thickness of 1,000 Å were sequentially deposited on the electron injection and transport layer to form a negative electrode.

In the above process, the deposition rate of organic materials was maintained at 0.4 to 0.7 Å/sec, lithium fluoride at the cathode was maintained at 0.3 Å/sec, and the deposition rate for aluminum was 2 Å/sec, and the vacuum degree during deposition was 2×10 ^-7 ~ An organic light-emitting device was fabricated by maintaining 5x10 ^-6 torr.

Examples 2 to 84 and Comparative Examples 1 to 64

In place of Compound 1 and Compound 2-1 used in the organic light-emitting device of Example 1, the above implementation was performed except that the first host and the second host described in Tables 1 to 5 were respectively co-deposited at 1:1. An organic light-emitting device was manufactured in the same manner as in Example 1.

At this time, the compounds C-1 to C-16 used in Comparative Examples 1 to 64 are as follows.

In the above Examples and Comparative Examples, voltage and efficiency were measured at a current density of 10 mA/cm ² of the organic light emitting device, and life was measured at a current density of 50 mA/cm ² , and the results are shown in Tables 1 to 5 below. Done. At this time, T ₉₅ means a time (hr) that becomes 95% of the initial luminance.

division Host 1 2nd host Driving voltage
(V) Efficiency (cd/A) Life T ₉₅ (hr) Luminous color Example 1 Compound 1 Compound 2-1 3.89 20.6 194 Red Example 2 Compound 2-2 3.91 20.4 190 Red Example 3 Compound 2-8 3.92 20.3 184 Red Example 4 Compound 2-19 3.88 20.5 178 Red Example 5 Compound 2 Compound 2-1 3.90 20.2 185 Red Example 6 Compound 2-2 3.87 20.3 187 Red Example 7 Compound 2-8 3.88 20.6 191 Red Example 8 Compound 2-19 3.87 20.1 195 Red Example 8 Compound 3 Compound 2-1 3.71 21.5 208 Red Example 10 Compound 2-2 3.72 22.0 211 Red Example 11 Compound 2-8 3.70 22.1 215 Red Example 12 Compound 2-19 3.73 21.4 204 Red Example 13 Compound 4 Compound 2-1 3.70 21.1 213 Red Example 14 Compound 2-2 3.68 21.3 209 Red Example 15 Compound 2-8 3.72 21.5 211 Red Example 16 Compound 2-19 3.69 22.7 220 Red Example 17 Compound 5 Compound 2-1 3.61 22.1 223 Red Example 18 Compound 2-2 3.62 21.3 217 Red Example 19 Compound 2-8 3.64 21.8 232 Red Example 20 Compound 2-19 3.60 21.7 213 Red Example 21 Compound 6 Compound 2-1 3.57 21.0 216 Red Example 22 Compound 2-2 3.60 21.4 223 Red Example 23 Compound 2-8 3.63 20.3 217 Red Example 24 Compound 2-19 3.62 20.5 211 Red Example 25 Compound 7 Compound 2-1 3.53 22.0 231 Red Example 26 Compound 2-2 3.51 22.2 233 Red Example 27 Compound 2-8 3.59 22.4 243 Red Example 28 Compound 2-19 3.53 22.3 224 Red

division Host 1 2nd host Driving voltage
(V) Efficiency (cd/A) Life T ₉₅ (hr) Luminous color Example 29 Compound 8 Compound 2-3 3.51 22.2 241 Red Example 30 Compound 2-5 3.50 23.0 236 Red Example 31 Compound 2-14 3.59 22.4 245 Red Example 32 Compound 2-21 3.55 23.1 240 Red Example 33 Compound 9 Compound 2-3 3.81 20.7 195 Red Example 34 Compound 2-5 3.79 20.5 187 Red Example 35 Compound 2-14 3.80 20.1 190 Red Example 36 Compound 2-21 3.77 20.4 199 Red Example 37 Compound 10 Compound 2-3 3.75 21.0 210 Red Example 38 Compound 2-5 3.80 20.6 204 Red Example 39 Compound 2-14 3.78 20.8 195 Red Example 40 Compound 2-21 3.81 21.0 201 Red Example 41 Compound 11 Compound 2-3 3.74 21.6 181 Red Example 42 Compound 2-5 3.78 21.2 174 Red Example 43 Compound 2-14 3.76 21.5 198 Red Example 44 Compound 2-21 3.80 21.1 196 Red Example 45 Compound 12 Compound 2-3 3.81 21.5 184 Red Example 46 Compound 2-5 3.77 22.0 181 Red Example 47 Compound 2-14 3.79 21.3 199 Red Example 48 Compound 2-21 3.83 21.4 191 Red Example 49 Compound 13 Compound 2-3 3.81 21.6 195 Red Example 50 Compound 2-5 3.82 20.9 190 Red Example 51 Compound 2-14 3.80 21.1 194 Red Example 52 Compound 2-21 3.85 21.0 191 Red Example 53 Compound 14 Compound 2-3 3.86 20.4 188 Red Example 54 Compound 2-5 3.87 21.0 176 Red Example 55 Compound 2-14 3.83 20.8 185 Red Example 56 Compound 2-21 3.86 20.6 191 Red

division Host 1 2nd host Driving voltage
(V) Efficiency (cd/A) Life T ₉₅ (hr) Luminous color Example 57 Compound 15 Compound 2-3 3.70 21.4 203 Red Example 58 Compound 2-5 3.72 21.8 204 Red Example 59 Compound 2-14 3.71 21.3 200 Red Example 60 Compound 2-21 3.70 21.9 197 Red Example 61 Compound 16 Compound 2-3 3.68 21.7 209 Red Example 62 Compound 2-5 3.69 21.8 197 Red Example 63 Compound 2-14 3.71 21.6 211 Red Example 64 Compound 2-21 3.73 22.2 203 Red Example 65 Compound 17 Compound 2-6 3.72 21.4 205 Red Example 66 Compound 2-7 3.73 20.0 207 Red Example 67 Compound 2-11 3.64 20.4 200 Red Example 68 Compound 2-18 3.75 20.5 215 Red Example 69 Compound 18 Compound 2-6 3.70 20.8 221 Red Example 70 Compound 2-7 3.72 21.5 217 Red Example 71 Compound 2-11 3.73 20.2 215 Red Example 72 Compound 2-18 3.75 21.1 216 Red Example 73 Compound 19 Compound 2-6 3.50 22.7 235 Red Example 74 Compound 2-7 3.52 22.1 233 Red Example 75 Compound 2-11 3.53 23.6 241 Red Example 76 Compound 2-18 3.52 22.8 239 Red Example 77 Compound 20 Compound 2-6 3.57 23.1 245 Red Example 78 Compound 2-7 3.60 22.6 251 Red Example 79 Compound 2-11 3.58 22.7 258 Red Example 80 Compound 2-18 3.62 22.9 254 Red Example 81 Compound 21 Compound 2-6 3.53 23.4 207 Red Example 82 Compound 2-7 3.55 23.0 192 Red Example 83 Compound 2-11 3.57 23.5 183 Red Example 84 Compound 2-18 3.58 23.7 204 Red

division Host 1 2nd host Driving voltage
(V) Efficiency (cd/A) Life T95(hr) Luminous color Comparative Example 1 Compound C-1 Compound 2-1 4.35 14.1 131 Red Comparative Example 2 Compound 2-2 4.34 14.3 133 Red Comparative Example 3 Compound 2-8 4.32 15.8 137 Red Comparative Example 4 Compound 2-19 4.33 15.5 132 Red Comparative Example 5 Compound C-2 Compound 2-1 4.20 15.0 164 Red Comparative Example 6 Compound 2-2 4.22 15.7 163 Red Comparative Example 7 Compound 2-8 4.25 15.2 174 Red Comparative Example 8 Compound 2-19 4.21 15.4 167 Red Comparative Example 9 Compound C-3 Compound 2-1 4.21 16.2 158 Red Comparative Example 10 Compound 2-2 4.23 15.8 167 Red Comparative Example 11 Compound 2-8 4.22 15.4 151 Red Comparative Example 12 Compound 2-19 4.08 15.0 154 Red Comparative Example 13 Compound C-4 Compound 2-1 4.05 15.8 105 Red Comparative Example 14 Compound 2-2 4.04 15.5 103 Red Comparative Example 15 Compound 2-8 4.17 15.2 111 Red Comparative Example 16 Compound 2-19 4.10 14.3 109 Red Comparative Example 17 Compound C-5 Compound 2-9 4.23 15.0 128 Red Comparative Example 18 Compound 2-10 4.10 13.8 123 Red Comparative Example 19 Compound 2-12 4.17 15.1 120 Red Comparative Example 20 Compound 2-16 4.12 14.5 111 Red Comparative Example 21 Compound C-6 Compound 2-3 4.22 15.0 117 Red Comparative Example 22 Compound 2-5 4.27 15.5 111 Red Comparative Example 23 Compound 2-14 4.23 15.1 115 Red Comparative Example 24 Compound 2-21 4.20 14.0 109 Red Comparative Example 25 Compound C-7 Compound 2-3 4.21 13.1 119 Red Comparative Example 26 Compound 2-5 4.27 14.0 121 Red Comparative Example 27 Compound 2-14 4.19 15.3 125 Red Comparative Example 28 Compound 2-21 4.20 13.2 128 Red Comparative Example 29 Compound C-8 Compound 2-3 4.10 13.8 130 Red Comparative Example 30 Compound 2-5 4.09 13.2 138 Red Comparative Example 31 Compound 2-14 4.07 13.3 131 Red Comparative Example 32 Compound 2-21 4.11 14.0 129 Red

division Host 1 2nd host Driving voltage
(V) Efficiency (cd/A) Life T95(hr) Luminous color Comparative Example 33 Compound C-9 Compound 2-3 4.15 13.4 116 Red Comparative Example 34 Compound 2-5 4.17 15.1 117 Red Comparative Example 35 Compound 2-14 4.19 15.5 119 Red Comparative Example 36 Compound 2-21 4.20 14.2 115 Red Comparative Example 37 Compound C-10 Compound 2-3 4.11 15.0 124 Red Comparative Example 38 Compound 2-5 4.13 15.4 136 Red Comparative Example 39 Compound 2-14 4.11 16.0 124 Red Comparative Example 40 Compound 2-21 4.10 15.7 129 Red Comparative Example 41 Compound C-11 Compound 2-3 4.13 16.1 124 Red Comparative Example 42 Compound 2-5 4.19 16.0 129 Red Comparative Example 43 Compound 2-14 4.23 17.2 133 Red Comparative Example 44 Compound 2-21 4.20 15.7 120 Red Comparative Example 45 Compound C-12 Compound 2-6 4.16 16.0 134 Red Comparative Example 46 Compound 2-7 4.17 15.2 128 Red Comparative Example 47 Compound 2-11 4.19 16.1 129 Red Comparative Example 48 Compound 2-18 4.18 15.4 131 Red Comparative Example 49 Compound C-13 Compound 2-6 4.28 15.6 103 Red Comparative Example 50 Compound 2-7 4.29 15.3 108 Red Comparative Example 51 Compound 2-11 4.28 15.4 104 Red Comparative Example 52 Compound 2-18 4.26 14.1 111 Red Comparative Example 53 Compound C-14 Compound 2-6 4.27 15.2 107 Red Comparative Example 54 Compound 2-7 4.24 13.7 105 Red Comparative Example 55 Compound 2-11 4.28 15.0 103 Red Comparative Example 56 Compound 2-18 4.25 14.4 108 Red Comparative Example 57 Compound C-15 Compound 2-6 4.14 16.0 138 Red Comparative Example 58 Compound 2-7 4.16 16.3 131 Red Comparative Example 59 Compound 2-11 4.18 16.5 127 Red Comparative Example 60 Compound 2-18 4.15 16.2 140 Red Comparative Example 61 Compound C-16 Compound 2-6 4.19 16.4 145 Red Comparative Example 62 Compound 2-7 4.18 16.7 133 Red Comparative Example 63 Compound 2-11 4.16 16.9 146 Red Comparative Example 64 Compound 2-18 4.18 16.8 138 Red

Referring to Tables 1 to 5, in Example 1, the EB-1 was used as the electron inhibiting layer, and the compound of Formula 1, the compound of Formula 2, and the dopant were Dp-7 as the red light emitting layer. Compared to the organic light emitting device of the example, it was confirmed that the driving voltage was low and the efficiency and lifespan were high. From this, when a combination of the compound of Formula 1 as the first host and the compound of Formula 2 as the second host is used, energy transfer to the red dopant in the red light emitting layer is well performed, and the efficiency and lifespan of the organic light emitting device are improved. It can be predicted that it will rise effectively. Further, it can be predicted that the Example has higher stability with respect to electrons and holes compared to the Comparative Example. Also, as the amount of holes increases as the second host is used, the electrons and holes in the red light emitting layer maintain a more stable balance. As a result, it can be predicted that the efficiency and lifespan will further increase. That is, it was confirmed that when the compound of Formula 1 and the compound of Formula 2 were co-deposited and used as a host of a red emission layer, the driving voltage, luminous efficiency, and lifetime characteristics of the organic light-emitting device could be improved.

1: substrate 2: anode
3: light emitting layer 4: cathode
5: hole injection layer 6: hole transport layer
7: electron suppression layer 8: hole block
9: electron injection and transport layer

Claims (14)

anode; A negative electrode provided to face the positive electrode; And as an organic light-emitting device comprising at least one organic material layer provided between the anode and the cathode,
The organic material layer comprises a compound represented by the following formula (1) and a compound represented by the following formula (2):
[Formula 1]

In Formula 1,
X ₁ to X ₃ are each independently N or CR ₅ , but at least any one is N,
Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted aryl having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl having 2 to 60 carbon atoms including at least one of O, N, Si and S,
R ₁ to R ₅ are each independently hydrogen; heavy hydrogen; halogen; Hydroxy; Nitrile; Nitro; Amino; Substituted or unsubstituted C2 to C60 alkyl; Substituted or unsubstituted 2 to 60 alkoxy; Substituted or unsubstituted 2 to 60 alkenyl; Substituted or unsubstituted 6 to 60 aryl; A substituted or unsubstituted heteroaryl having 2 to 60 carbon atoms including at least one of O, N, Si and S, or R ₁ to R ₃ are bonded to adjacent groups to form a condensed ring,
One of A and B is a substituent represented by the following formula 1-1, and the other is hydrogen or deuterium,
[Formula 1-1]

In Formula 1-1,
R ₆ to R ₁₀ are each independently hydrogen; heavy hydrogen; halogen; Hydroxy; Nitrile; Nitro; Amino; Substituted or unsubstituted C2 to C60 alkyl; Substituted or unsubstituted 2 to 60 alkoxy; Substituted or unsubstituted 2 to 60 alkenyl; Substituted or unsubstituted 6 to 60 aryl; A substituted or unsubstituted heteroaryl having 2 to 60 carbon atoms including one or more of O, N, Si and S, or R ₆ to R ₉ are bonded to adjacent groups to form a condensed ring,
a is an integer from 1 to 6,
[Formula 2]

In Chemical Formula 2,
Ar ₃ and Ar ₄ are each independently substituted or unsubstituted aryl having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl having 2 to 60 carbon atoms including at least one of O, N, Si and S,
L ₁ and L ₂ are each independently a single bond; Or a substituted or unsubstituted arylene having 6 to 60 carbon atoms,
R ₁₁ to R ₁₄ are each independently hydrogen; heavy hydrogen; halogen; Hydroxy; Nitrile; Nitro; Amino; Substituted or unsubstituted C2 to C60 alkyl; Substituted or unsubstituted 2 to 60 alkoxy; Substituted or unsubstituted 2 to 60 alkenyl; Substituted or unsubstituted 6 to 60 aryl; Or a substituted or unsubstituted heteroaryl having 2 to 60 carbon atoms including at least one of O, N, Si and S,
b and e are each independently an integer of 1 to 4
c and d are each independently an integer of 1 to 3.
The method of claim 1,
Formula 1 is any one selected from compounds represented by the following Formulas 1-A, 1-B, and 1-C, an organic light-emitting device:

In the above formulas 1-A, 1-B and 1-C,
Descriptions of X ₁ , X ₂ , X ₃ , Ar ₁ , Ar ₂ , A and B are as defined in claim 1.
The method of claim 1,
X ₁ to X ₃ are all N, the organic light-emitting device.
The method of claim 1,
Ar ₁ and Ar ₂ are each independently An organic light-emitting device which is any one selected from the group consisting of:

The method of claim 1,
Formula 1-1 is an organic light emitting device selected from the group consisting of the following compounds:

The method of claim 1,
The compound represented by Formula 1 is selected from the group consisting of the following compounds, an organic light-emitting device:

.
The method of claim 1,
The compound represented by Formula 2 is a compound represented by Formula 2-1 below:
[Formula 2-1]

In Formula 2-1,
Description of Ar ₃ , Ar ₄ , L ₁ and L ₂ is as defined in claim 1.
The method of claim 1,
Ar ₃ and Ar ₄ are each independently any one selected from the group consisting of the organic light emitting device:

The method of claim 1,
L ₁ and L ₂ are each independently a single bond or any one selected from the group consisting of the organic light emitting device:

The method of claim 1,
R ₁₁ to R ₁₄ are hydrogen, the organic light-emitting device.
The method of claim 1,
The compound represented by Formula 2 is selected from the group consisting of the following compounds, an organic light-emitting device:

The method of claim 1,
Organic light emission irradiation, wherein the compound represented by Formula 1 and the organic material layer including the compound represented by Formula 2 is an emission layer.
The method of claim 12,
The compound represented by Formula 1 and the compound represented by Formula 2 are host materials in the emission layer.
The method of claim 12
The light emitting layer further includes a dopant material.

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