KR20210158347A - Organic light emitting device - Google Patents

Abstract

The present invention provides an organic light emitting element. The organic light emitting element comprises an anode, a cathode, and a light emitting layer between the anode and the cathode. Therefore, the organic light emitting element increases a driving voltage, efficiency, and a lifespan.

Description

Organic light emitting device

The present invention relates to an organic light emitting device.

In general, the organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy using an organic material. The organic light emitting device using the organic light emitting phenomenon has a wide viewing angle, excellent contrast, fast response time, and 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 and a cathode and an organic material layer between the anode and the cathode. The organic layer is often formed 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, 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 the organic light emitting device, when a voltage is applied between the two electrodes, holes are injected into the organic material layer from the anode and electrons from the cathode are injected into the organic material layer. When the injected holes and electrons meet, excitons are formed, and the excitons When it falls back to the ground state, it lights up.

The 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 relates to an organic light emitting device having improved driving voltage, efficiency, and lifetime.

In order to solve the above problems, the present invention provides the following organic light emitting device:

anode; cathode; and a light emitting layer between the anode and the cathode,

The light emitting layer comprises a compound represented by the following formula (1) and a compound represented by the following formula (2),

Organic light emitting device:

[Formula 1]

In Formula 1,

Ar ₁ and Ar ₂ are each independently substituted or unsubstituted C _6-60 aryl; _{Or substituted or unsubstituted C 2-60} heteroaryl comprising any one or more selected from the group consisting of N, O and S,

L ₁ and L ₂ are each independently a single bond; Or a substituted or unsubstituted C _6-60 arylene,

L ₃ is a single bond; Or a substituted or unsubstituted C _6-60 arylene,

each R ₁ is independently hydrogen or deuterium; or two adjacent ones combine to form a benzene ring, and the remainder is hydrogen or deuterium;

each R ₂ is independently hydrogen or deuterium; or two adjacent ones combine to form a benzene ring, and the remainder is hydrogen or deuterium;

[Formula 2]

In Formula 2,

Ar ₃ and Ar ₄ are each independently substituted or unsubstituted C _6-60 aryl; _{Or C 2-60} heteroaryl comprising at least one selected from the group consisting of substituted or unsubstituted O and S,

L ₄ to L ₆ are each independently a single bond; or substituted or unsubstituted C _6-60 arylene.

The above-described organic light emitting device may improve efficiency, low driving voltage, and/or lifespan characteristics.

FIG. 1 shows an example of an organic light emitting device including a substrate 1 , an anode 2 , a light emitting layer 3 , and a cathode 4 .
2 is a substrate (1), an anode (2), a hole injection layer (5), a hole transport layer (6), a light emitting layer (3), an electron transport layer (7), an electron injection layer (8) and a cathode (4) It shows an example of the organic light emitting device made up.
3 is a substrate (1), anode (2), hole injection layer (5), hole transport layer (6), electron blocking layer (9), light emitting layer (3), hole blocking layer (10), electron transport layer (7) ), an example of an organic light emitting device comprising an electron injection layer 8 and a cathode 4 is shown.

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

또는

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

or

means a bond connected to another substituent.

As used herein, the term "substituted or unsubstituted" refers to deuterium; halogen group; nitrile group; nitro group; hydroxyl group; carbonyl group; ester group; imid; amino group; a phosphine oxide group; alkoxy group; aryloxy group; alkyl thiooxy group; arylthioxy group; an alkyl sulfoxy group; arylsulfoxy group; silyl group; boron group; an alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; aralkenyl group; an alkylaryl group; an alkylamine group; an aralkylamine group; heteroarylamine group; arylamine group; an arylphosphine group; Or N, O, and S atom means that it is substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group including one or more, or substituted or unsubstituted, two or more of the above-exemplified substituents are linked. . 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 in the carbonyl group is not particularly limited, but 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, in the ester group, oxygen of the ester group may be substituted with a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms. Specifically, 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 it is preferably from 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 specifically includes 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. However, the present invention is not limited thereto.

In the present specification, the boron group specifically includes, but is not limited to, a trimethylboron group, a triethylboron group, a t-butyldimethylboron group, a triphenylboron group, a phenylboron group, and the like.

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

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the number of carbon atoms in the alkyl group is 1 to 20. According to another exemplary embodiment, the number of carbon atoms in 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 and the like, but are not limited thereto.

In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to an exemplary embodiment, the carbon number of the alkenyl group is 2 to 20. According to another exemplary embodiment, the carbon number of the alkenyl group is 2 to 10. 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 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 carbon number of the cycloalkyl group is 3 to 20. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but is not limited thereto.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to an exemplary embodiment, the carbon number of the aryl group is 6 to 30. According to an exemplary embodiment, the carbon number of the aryl group is 6 to 20. The aryl group may be a monocyclic aryl group, such as a phenyl group, a biphenyl group, or a terphenyl group, but 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. can be However, the present invention 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 carbon atoms is not particularly limited, but it is preferably from 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, an 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, thiadia and a jolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but is not limited thereto.

In the present specification, the aryl group in the aralkyl group, the aralkenyl group, the alkylaryl group, and the arylamine group is 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 example of the above-described alkyl group. In the present specification, the description of the heterocyclic group described above for heteroaryl among heteroarylamines may be applied. In the present specification, the alkenyl group among the aralkenyl groups is the same as the above-described examples of the alkenyl group. In the present specification, the description of the above-described aryl group may be applied, except that arylene is a divalent group. In the present specification, the description of the above-described heterocyclic group may be applied, except that heteroarylene is a divalent group. In the present specification, the hydrocarbon ring is not a monovalent group, and the description of the above-described aryl group or cycloalkyl group may be applied, except that it 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.

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

positive and negative

The anode and cathode used in the present invention mean electrodes used in an organic light emitting device.

As the anode material, a material having a large work function is generally preferred so that holes can be smoothly injected into the organic material layer. Specific examples of the anode material include metals such as vanadium, chromium, copper, zinc, 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 to facilitate electron injection 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; and a multi-layered material such as LiF/Al or LiO ₂ /Al, but is not limited thereto.

hole injection layer

The organic light emitting diode according to the present invention may include a hole injection layer between the anode and a hole transport layer to be described later, if necessary.

The hole injection layer is a layer for injecting holes from the electrode, and as a hole injection material, it has the ability to transport holes, so it has a hole injection effect at the anode, an excellent hole injection effect on the light emitting layer or the light emitting material, and is produced in the light emitting layer A compound which prevents the movement of excitons to the electron injection layer or the electron injection material and is excellent in the ability to form a thin film is preferable. In addition, it is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer.

Specific examples of the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene-based organic material. of organic substances, anthraquinones, polyaniline and polythiophene-based conductive polymers, and the like, but are not limited thereto.

hole transport layer

The organic light emitting diode according to the present invention may include a hole transport layer between the anode and the light emitting layer to be described later or between the electron blocking layer and the hole injection layer to be described later.

The hole transport layer is a layer that receives holes from the hole injection layer and transports them to the light emitting layer. As a hole transport material, a material capable of transporting holes from the anode or hole injection layer to the light emitting layer and transferring them to the light emitting layer. This is suitable.

Specific examples of the hole transport material include, but are not limited to, an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together.

electron blocking layer

The electron blocking layer is a layer placed between the hole transport layer and the emission layer to prevent electrons injected from the cathode from passing to the hole transport layer without recombination in the emission layer, and is also called an electron blocking layer. For the electron blocking layer, a material having an electron affinity lower than that of the electron transport layer is preferable.

light emitting layer

The light emitting layer used in the present invention refers to a layer capable of emitting light in the visible ray region by combining holes and electrons transferred from the anode and the cathode. In general, the emission layer includes a host material and a dopant material, and in the present invention, the compound represented by Formula 1 and the compound represented by Formula 2 are included as hosts.

Preferably, the formula 1 is represented by any one selected from the group consisting of the following formulas 1-1 to 1-9:

In Formulas 1-1 to 1-9, Ar ₁ , Ar ₂ , L ₁ , L ₂ and L ₃ are as defined above.

Preferably, Ar ₁ and Ar ₂ are each independently substituted or unsubstituted C _6-20 aryl; Or it may be _{a C 2-20} heteroaryl comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S.

More preferably, Ar ₁ and Ar ₂ may each independently be phenyl, biphenylyl, naphthyl, phenanthrenyl, phenyl carbazolyl, dibenzofuranyl, dibenzothiophenyl, or benzonaphthofuranyl.

Preferably, L ₁ and L ₂ are each independently a single bond; Or it may be a substituted or unsubstituted C _{6-20 arylene.}

More preferably, L ₁ and L ₂ may each independently be a single bond, phenylene, or naphthylene.

Most preferably, L ₁ and L ₂ may each independently be a single bond or any one selected from the group consisting of:

.

.

Preferably, L ₃ is a single bond; Or it may be a substituted or unsubstituted C _{6-60 arylene.}

More preferably, L ₃ may be a single bond, phenylene, biphenylylene, or naphthylene.

Most preferably, L ₃ may be a single bond or any one selected from the group consisting of:

.

.

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

.

.

The compound represented by Formula 1 may be prepared by, for example, a preparation method as in Scheme 1 below, and other compounds may be prepared similarly.

[Scheme 1]

In Scheme 1, Ar ₁ , Ar ₂ , L ₁ to L ₃ , R ₁ and R ₂ are as defined in Formula 1 above, X ₁ is halogen, and preferably X ₁ is chloro or bromo.

Scheme 1 is an amine substitution reaction, preferably performed in the presence of a palladium catalyst and a base, and the reactor for the amine substitution reaction can be changed as known in the art. The manufacturing method may be more specific in Preparation Examples to be described later.

Preferably, Ar ₃ and Ar ₄ are each independently substituted or unsubstituted C _6-20 aryl; Or it may be _{C 2-20} heteroaryl including any one or more selected from the group consisting of substituted or unsubstituted O and S.

More preferably, Ar ₃ and Ar ₄ are each independently phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, dimethylfluorenyl, diphenylfluorenyl, dibenzofuranyl, dibenzo thiophenyl, or benzonaphthofuranyl.

Most preferably, Ar ₃ and Ar ₄ are each independently phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, 9,9-dimethyl-9H-fluorenyl, 9,9-diphenyl -9H-fluorenyl, dibenzofuranyl, dibenzothiophenyl, or benzo[b]naphtho[2,3-d]furanyl.

Preferably, L ₄ to L ₆ are each independently a single bond; Or it may be a substituted or unsubstituted C _{6-20 arylene.}

More preferably, L ₄ to L ₆ may each independently be a single bond, phenylene, or dimethylfluorenylene.

Most preferably, L ₄ to L ₆ may each independently be a single bond, phenylene, or 9,9-dimethyl-9H-fluorenylene.

Representative examples of the compound represented by Formula 2 are as follows:

.

.

The compound represented by Formula 2 may be prepared by, for example, a preparation method as shown in Scheme 2 below, and other compounds may be prepared similarly.

[Scheme 2]

In Scheme 2, Ar ₃ , Ar ₄ and L ₄ to L ₆ are as defined in Formula 2 above, X ₂ is halogen, and preferably X ₂ is chloro or bromo.

Scheme 2 is an amine substitution reaction, preferably performed in the presence of a palladium catalyst and a base, and the reactor for the amine substitution reaction can be changed as known in the art. The manufacturing method may be more specific in Preparation Examples to be described later.

In the light emitting layer, the weight ratio of the compound represented by Formula 1 to the compound represented by Formula 2 is 1:99 to 99:1, 5:95 to 95:5, or 10:90 to 90:10.

The dopant material is not particularly limited as long as it is a material used in an organic light emitting device. Examples include an aromatic amine derivative, a strylamine compound, a boron complex, a fluoranthene compound, and a metal complex. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, periflanthene, and the like, having an arylamino group. As the styrylamine compound, a substituted or unsubstituted It is a compound in which at least one arylvinyl group is substituted in the arylamine, and 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, and the like, but is not limited thereto. In addition, examples of the metal complex include, but are not limited to, an iridium complex and a platinum complex.

For example, one of the following compounds may be used as a dopant material, but is not limited thereto:

.

.

hole blocking layer

The hole blocking layer is a layer interposed between the electron transport layer and the emission layer to prevent the holes injected from the anode from passing to the electron transport layer without recombination in the emission layer, and is also called a hole blocking layer. A material having high ionization energy is preferable for the hole blocking layer.

electron transport layer

The organic light emitting device according to the present invention may include an electron transport layer between the light emitting layer and the cathode.

The electron transport layer is a layer that receives electrons from the electron injection layer formed on the cathode or the cathode, transports electrons to the light emitting layer, and suppresses the transfer of holes in the light emitting layer. As an electron transport material, electrons are well injected from the cathode As a material that can receive and transfer to the light emitting layer, a material with high electron mobility is suitable.

Specific examples of the electron transport material include an 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 may be used with any desired cathode material as used in accordance with the prior art. In particular, examples of suitable cathode materials are conventional materials having a low work function and followed by a layer of aluminum or silver. Specifically cesium, barium, calcium, ytterbium and samarium, followed in each case by an aluminum layer or a silver layer.

electron injection layer

The organic light emitting diode according to the present invention may further 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. It is preferable to use a compound which prevents movement to a layer and is excellent in the ability to form a thin film.

Specific examples of the material that can be used as the electron injection layer include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preole nylidene methane, anthrone and the like, derivatives thereof, metal complex compounds, nitrogen-containing 5-membered ring derivatives, and the like, but are not limited thereto.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h] Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) ( o-crezolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtolato)gallium, etc. However, the present invention is not limited thereto.

On the other hand, in the present invention, the "electron injection and transport layer" is a layer that performs both the role of the electron injection layer and the electron transport layer, and the materials serving the respective layers may be used alone or in combination, but limited thereto. doesn't happen

organic light emitting device

The structure of the organic light emitting diode according to the present invention is illustrated in FIGS. 1 to 3 . FIG. 1 shows an example of an organic light emitting device including a substrate 1 , an anode 2 , a light emitting layer 3 , and a cathode 4 . In addition, FIG. 2 shows the substrate 1, the anode 2, the hole injection layer 5, the hole transport layer 6, the light emitting layer 3, the electron transport layer 7, the electron injection layer 8 and the cathode 4 ) shows an example of an organic light emitting device made of 3 is a substrate (1), anode (2), hole injection layer (5), hole transport layer (6), electron blocking layer (9), light emitting layer (3), hole blocking layer (10), electron transport layer (7) ), an example of an organic light emitting device comprising an electron injection layer 8 and a cathode 4 is shown.

The organic light emitting device according to the present invention may be manufactured by sequentially stacking the above-described components. At this time, by using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, a metal or conductive metal oxide or an alloy thereof is deposited on a substrate to form an anode And, after forming each of the above-mentioned 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 the anode material on the substrate in the reverse order of the above-described configuration from the cathode material (WO 2003/012890). In addition, the light emitting layer may be formed by a solution coating method as well as a vacuum deposition method for the host and 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.

Meanwhile, the organic light emitting device according to the present invention may be a bottom emission device, a top emission device, or a double-sided light emitting device, and in particular, may be a bottom light emitting device requiring relatively high luminous efficiency.

Hereinafter, preferred examples are presented to help the understanding of the present invention. However, the following examples are only provided for easier understanding of the present invention, and thus the content of the present invention is not limited thereto.

[Production Example]

Preparation 1-1

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), compound sub1 (25.6 g, 62.8 mmol), and Potassium Phosphate (38.1 g, 179.4 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added. After 3 hours, the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 17.7 g of compound 1-1 (yield 55%, MS: [M+H] ⁺ = 539).

Preparation 1-2

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), compound sub2 (25.6 g, 62.8 mmol), and Potassium Phosphate (38.1 g, 179.4 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added. After 2 hours, the reaction was completed and the solvent was removed under reduced pressure after cooling to room temperature. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 19 g of compound 1-2 (yield 59%, MS: [M+H] ⁺ = 539).

Preparation 1-3

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), compound sub3 (27.2 g, 62.8 mmol), and Potassium Phosphate (38.1 g, 179.4 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added. After 3 hours, the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 18.5 g of compound 1-3 (yield 55%, MS: [M+H] ⁺ = 564).

Preparation Example 1-4

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), compound sub4 (30.4 g, 62.8 mmol), and Potassium Phosphate (38.1 g, 179.4 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added. After 3 hours, the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 20.9 g of compound 1-4 (yield 57%, MS: [M+H] ⁺ = 615).

Preparation 1-5

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), compound sub5 (29.5 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added. After 3 hours, the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 23.3 g of compound 1-5 (yield 65%, MS: [M+H] ⁺ = 601).

Preparation 1-6

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), compound sub6 (29.5 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added. After 3 hours, the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 20.5 g of compound 1-6 (yield 57%, MS: [M+H] ⁺ = 601).

Preparation 1-7

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), compound sub7 (27.2 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added. After 2 hours, the reaction was completed and the solvent was removed under reduced pressure after cooling to room temperature. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 19.2 g of compound 1-7 (yield 57%, MS: [M+H] ⁺ = 565).

Preparation 1-8

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), compound sub8 (32.7 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added. After 2 hours, the reaction was completed and the solvent was removed under reduced pressure after cooling to room temperature. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 26.4 g of compound 1-8 (yield 68%, MS: [M+H] ⁺ = 651).

Preparation 1-9

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), compound sub9 (30.4 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added. After 3 hours, the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 24.6 g of compound 1-9 (yield 67%, MS: [M+H] ⁺ = 615).

Preparation 1-10

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), compound sub10 (30.4 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added. After 3 hours, the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 23.5 g of compound 1-10 (yield 64%, MS: [M+H] ⁺ = 615).

Preparation Example 1-11

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), compound sub11 (27.2 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added. After 3 hours, the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 17.5 g of compound 1-11 (yield 52%, MS: [M+H] ⁺ = 565).

Preparation Example 1-12

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), compound sub12 (27.9 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added. After 2 hours, the reaction was completed and the solvent was removed under reduced pressure after cooling to room temperature. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 18.2 g of compound 1-12 (yield 53%, MS: [M+H] ⁺ = 575).

Preparation 1-13

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), compound sub13 (29.5 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added. After 3 hours, the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 19.4 g of compound 1-13 (yield 54%, MS: [M+H] ⁺ = 601).

Preparation 1-14

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), compound sub14 (35.1 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added. After 3 hours, the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 28.4 g of compound 1-14 (yield 69%, MS: [M+H] ⁺ = 690).

Preparation 1-15

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), compound sub15 (31 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added. After 3 hours, the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 26.1 g of compound 1-15 (yield 70%, MS: [M+H] ⁺ = 625).

Preparation 1-16

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), compound sub16 (31.4 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added. After 3 hours, the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 22.2 g of compound 1-16 (yield 59%, MS: [M+H] ⁺ = 631).

Preparation 1-17

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), compound sub17 (26.4 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added. After 3 hours, the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 18.1 g of compound 1-17 (yield 55%, MS: [M+H] ⁺ = 551).

Preparation Example 1-18

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), compound sub18 (32 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added. After 2 hours, the reaction was completed and the solvent was removed under reduced pressure after cooling to room temperature. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 24.5 g of compound 1-18 (yield 64%, MS: [M+H] ⁺ = 641).

Preparation 1-19

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), compound sub19 (31.1 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added. After 2 hours, the reaction was completed and the solvent was removed under reduced pressure after cooling to room temperature. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 25.1 g of compound 1-19 (yield 67%, MS: [M+H] ⁺ = 627).

Preparation 1-20

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), compound sub20 (33 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added. After 3 hours, the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 20 g of compound 1-20 (yield 51%, MS: [M+H] ⁺ = 657).

Preparation 1-21

In a nitrogen atmosphere, 7H-benzo[c]carbazole (10 g, 46 mmol), compound sub21 (18.1 g, 48.3 mmol), and Potassium Phosphate (29.3 g, 138.1 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 14.3 g of compound 1-21 (yield 56%, MS: [M+H] ⁺ = 555).

Preparation 1-22

In a nitrogen atmosphere, 7H-benzo[c]carbazole (10 g, 46 mmol), compound sub7 (21 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 14.7 g of compound 1-22 (yield 52%, MS: [M+H] ⁺ = 615).

Preparation 1-23

In a nitrogen atmosphere, 7H-benzo[c]carbazole (10 g, 46 mmol), compound sub22 (26.9 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 22 g of compound 1-23 (yield 65%, MS: [M+H] ⁺ = 737).

Preparation 1-24

In a nitrogen atmosphere, 7H-benzo[c]carbazole (10 g, 46 mmol), compound sub23 (16.6 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 12.1 g of compound 1-24 (yield 50%, MS: [M+H] ⁺ = 525).

Preparation 1-25

In a nitrogen atmosphere, 7H-benzo[c]carbazole (10 g, 46 mmol), compound sub24 (16.6 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 12.5 g of compound 1-25 (yield 52%, MS: [M+H] ⁺ = 525).

Preparation 1-26

In a nitrogen atmosphere, 7H-benzo[c]carbazole (10 g, 46 mmol), compound sub25 (25.1 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 20.3 g of compound 1-26 (yield 63%, MS: [M+H] ⁺ = 701).

Preparation 1-27

In a nitrogen atmosphere, 7H-benzo[c]carbazole (10 g, 46 mmol), compound sub26 (25.4 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.9 mmol) was added. After 2 hours, the reaction was completed and the solvent was removed under reduced pressure after cooling to room temperature. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 18.2 g of compound 1-27 (yield 56%, MS: [M+H] ⁺ = 707).

Preparation 1-28

5H-benzo[b]carbazole (10 g, 46 mmol), compound sub27 (17.8 g, 48.3 mmol), and Potassium Phosphate (29.3 g, 138.1 mmol) in Xylene 200 ml in a nitrogen atmosphere were stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.9 mmol) was added. After 2 hours, the reaction was completed and the solvent was removed under reduced pressure after cooling to room temperature. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 16.9 g of compound 1-28 (yield 67%, MS: [M+H] ⁺ = 549).

Preparation 1-29

In a nitrogen atmosphere, 5H-benzo[b]carbazole (10 g, 46 mmol), compound sub28 (20.3 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.9 mmol) was added. After 2 hours, the reaction was completed and the solvent was removed under reduced pressure after cooling to room temperature. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 19.3 g of compound 1-29 (yield 70%, MS: [M+H] ⁺ = 601).

Preparation 1-30

In a nitrogen atmosphere, 5H-benzo[b]carbazole (10 g, 46 mmol), compound sub29 (21.7 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.9 mmol) was added. After 2 hours, the reaction was completed and the solvent was removed under reduced pressure after cooling to room temperature. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 17.7 g of compound 1-30 (yield 61%, MS: [M+H] ⁺ = 631).

Preparation Example 1-31

In a nitrogen atmosphere, 5H-benzo[b]carbazole (10 g, 46 mmol), compound sub30 (24.6 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 20 g of compound 1-31 (yield 63%, MS: [M+H] ⁺ = 690).

Preparation Example 1-32

In a nitrogen atmosphere, 5H-benzo[b]carbazole (10 g, 46 mmol), compound sub31 (25.1 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 21.3 g of compound 1-32 (yield 66%, MS: [M+H] ⁺ = 701).

Preparation Example 1-33

In a nitrogen atmosphere, 5H-benzo[b]carbazole (10 g, 46 mmol), compound sub32 (19 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 14 g of compound 1-33 (yield 53%, MS: [M+H] ⁺ = 575).

Preparation Example 1-34

In a nitrogen atmosphere, 5H-benzo[b]carbazole (10 g, 46 mmol), compound sub33 (22.7 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 15.3 g of compound 1-34 (yield 51%, MS: [M+H] ⁺ = 651).

Preparation Example 1-35

In a nitrogen atmosphere, 5H-benzo[b]carbazole (10 g, 46 mmol), compound sub17 (20.3 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.9 mmol) was added. After 2 hours, the reaction was completed and the solvent was removed under reduced pressure after cooling to room temperature. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 18.2 g of compound 1-35 (yield 66%, MS: [M+H] ⁺ = 601).

Preparation Example 1-36

In a nitrogen atmosphere, 11H-benzo[a]carbazole (10 g, 46 mmol), compound sub34 (22.7 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.9 mmol) was added. After 2 hours, the reaction was completed and the solvent was removed under reduced pressure after cooling to room temperature. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 15 g of compound 1-36 (yield 50%, MS: [M+H] ⁺ = 651).

Preparation Example 1-37

In a nitrogen atmosphere, 11H-benzo[a]carbazole (10 g, 46 mmol), compound sub35 (21.7 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.9 mmol) was added. After 2 hours, the reaction was completed and the solvent was removed under reduced pressure after cooling to room temperature. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 20.3 g of compound 1-37 (yield 70%, MS: [M+H] ⁺ = 631).

Preparation Example 1-38

In a nitrogen atmosphere, 11H-benzo[a]carbazole (10 g, 46 mmol), compound sub36 (27.1 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 20.4 g of compound 1-38 (yield 60%, MS: [M+H] ⁺ = 741).

Preparation Example 1-39

In a nitrogen atmosphere, 11H-benzo[a]carbazole (10 g, 46 mmol), compound sub37 (25.4 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.9 mmol) was added. After 2 hours, the reaction was completed and the solvent was removed under reduced pressure after cooling to room temperature. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 17.9 g of compound 1-39 (yield 55%, MS: [M+H] ⁺ = 707).

Preparation 1-40

In a nitrogen atmosphere, 11H-benzo[a]carbazole (10 g, 46 mmol), compound sub38 (24.6 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0)(0.5 g, 0.9 mmol) was added. After 2 hours, the reaction was completed and the solvent was removed under reduced pressure after cooling to room temperature. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 15.9 g of compound 1-40 (yield 50%, MS: [M+H] ⁺ = 691).

Preparation Example 1-41

In a nitrogen atmosphere, 7H-dibenzo[b,g]carbazole (10 g, 37.4 mmol), compound sub39 (14.7 g, 39.3 mmol), and Potassium Phosphate (23.8 g, 112.2 mmol) were added to 200 ml of 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 completed and the solvent was removed under reduced pressure after cooling to room temperature. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 11.5 g of compound 1-41 (yield 51%, MS: [M+H] ⁺ = 605).

Preparation Example 1-42

In a nitrogen atmosphere, 7H-dibenzo[b,g]carbazole (10 g, 37.4 mmol), compound sub40 (19 g, 39.3 mmol), and sodium tert-butoxide (4.7 g, 48.6 mmol) were added to 200 ml of Xylene, stirred and refluxed. did. After this, bis(tri-tert-butylphosphine)palladium(0)(0.4 g, 0.7 mmol) was added. After 3 hours, the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 13.9 g of compound 1-42 (yield 52%, MS: [M+H] ⁺ = 715).

Preparation Example 1-43

In a nitrogen atmosphere, 6H-dibenzo[b,h]carbazole (10 g, 37.4 mmol), compound sub41 (14.1 g, 39.3 mmol), and Potassium Phosphate (23.8 g, 112.2 mmol) were added to 200 ml of 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 completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 13.6 g of compound 1-43 (yield 62%, MS: [M+H] ⁺ = 589).

Preparation Example 1-44

In a nitrogen atmosphere, 6H-dibenzo[b,h]carbazole (10 g, 37.4 mmol), compound sub42 (19.6 g, 39.3 mmol), and sodium tert-butoxide (4.7 g, 48.6 mmol) were added to 200 ml of Xylene, stirred and refluxed. did. After this, bis(tri-tert-butylphosphine)palladium(0)(0.4 g, 0.7 mmol) was added. After 2 hours, the reaction was completed and the solvent was removed under reduced pressure after cooling to room temperature. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 19.1 g of compound 1-44 (yield 70%, MS: [M+H] ⁺ = 731).

Preparation Example 1-45

In a nitrogen atmosphere, 13H-dibenzo[a,h]carbazole (10 g, 37.4 mmol), compound sub43 (16 g, 39.3 mmol), and Potassium Phosphate (23.8 g, 112.2 mmol) were added to 200 ml of 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 completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 14.1 g of compound 1-45 (yield 59%, MS: [M+H] ⁺ = 639).

Preparation Example 1-46

In a nitrogen atmosphere, 13H-dibenzo[a,h]carbazole (10 g, 37.4 mmol), compound sub44 (17.7 g, 39.3 mmol), and sodium tert-butoxide (4.7 g, 48.6 mmol) were added to 200 ml of Xylene, stirred and refluxed. did. After this, bis(tri-tert-butylphosphine)palladium(0)(0.4 g, 0.7 mmol) was added. After 3 hours, the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 13.7 g of compound 1-46 (yield 54%, MS: [M+H] ⁺ = 681).

Preparation Example 1-47

In a nitrogen atmosphere, 7H-dibenzo[c,g]carbazole (10 g, 37.4 mmol), compound sub45 (14.1 g, 39.3 mmol), and Potassium Phosphate (23.8 g, 112.2 mmol) were added to 200 ml of 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 completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 12.1 g of compound 1-47 (yield 55%, MS: [M+H] ⁺ = 589).

Preparation 2-1

In a nitrogen atmosphere, 2-bromotriphenylene (10 g, 32.6 mmol), compound amine 1 (11 g, 34.2 mmol), and sodium tert-butoxide (4.1 g, 42.3 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol) was added thereto. After 5 hours, the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 12.5 g of compound 2-1 (yield 70%, MS: [M+H] ⁺ = 548).

Preparation 2-2

In a nitrogen atmosphere, 2-bromotriphenylene (10 g, 32.6 mmol), the compound amine 2 (12.7 g, 34.2 mmol), and sodium tert-butoxide (4.1 g, 42.3 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol) was added thereto. After 5 hours, the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 13 g of compound 2-2 (yield 67%, MS: [M+H] ⁺ = 598).

Preparation 2-3

In a nitrogen atmosphere, 2-bromotriphenylene (10 g, 32.6 mmol), compound amine 3 (13.6 g, 34.2 mmol), and sodium tert-butoxide (4.1 g, 42.3 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol) was added thereto. After 5 hours, the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 13.4 g of compound 2-3 (yield 66%, MS: [M+H] ⁺ = 624).

Preparation 2-4

In a nitrogen atmosphere, 2-bromotriphenylene (10 g, 32.6 mmol), the compound amine 4 (12.7 g, 34.2 mmol), and sodium tert-butoxide (4.1 g, 42.3 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol) was added thereto. After 5 hours, the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 11.7 g of compound 2-4 (yield 60%, MS: [M+H] ⁺ = 598).

Preparation 2-5

In a nitrogen atmosphere, 2-bromotriphenylene (10 g, 32.6 mmol), the compound amine 5 (15.3 g, 34.2 mmol), and sodium tert-butoxide (4.1 g, 42.3 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol) was added thereto. After 5 hours, the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 13.2 g of compound 2-5 (yield 60%, MS: [M+H] ⁺ = 674)

Preparation Example 2-6

In a nitrogen atmosphere, 2-bromotriphenylene (10 g, 32.6 mmol), compound amine 6 (10.1 g, 34.2 mmol), and sodium tert-butoxide (4.1 g, 42.3 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol) was added thereto. After 5 hours, the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 10.9 g of compound 2-6 (yield 64%, MS: [M+H] ⁺ = 522).

Preparation 2-7

In a nitrogen atmosphere, 2-bromotriphenylene (10 g, 32.6 mmol), compound amine 7 (13.6 g, 34.2 mmol), and sodium tert-butoxide (4.1 g, 42.3 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol) was added thereto. After 5 hours, the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 12.6 g of compound 2-7 (yield 62%, MS: [M+H] ⁺ = 624).

Preparation 2-8

In a nitrogen atmosphere, 2-bromotriphenylene (10 g, 32.6 mmol), the compound amine 8 (13.6 g, 34.2 mmol), and sodium tert-butoxide (4.1 g, 42.3 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol) was added thereto. After 5 hours, the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 11.2 g of compound 2-8 (yield 55%, MS: [M+H] ⁺ = 624).

Preparation Example 2-9

In a nitrogen atmosphere, 2-bromotriphenylene (10 g, 32.6 mmol), the compound amine 9 (11.8 g, 34.2 mmol), and sodium tert-butoxide (4.1 g, 42.3 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol) was added thereto. After 5 hours, the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 10.6 g of compound 2-9 (yield 57%, MS: [M+H] ⁺ = 572).

Preparation Example 2-10

In a nitrogen atmosphere, 2-bromotriphenylene (10 g, 32.6 mmol), the compound amine 10 (10.9 g, 34.2 mmol), and sodium tert-butoxide (4.1 g, 42.3 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol) was added thereto. After 5 hours, the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 10.3 g of compound 2-10 (yield 58%, MS: [M+H] ⁺ = 546).

Preparation Example 2-11

In a nitrogen atmosphere, 2-bromotriphenylene (10 g, 32.6 mmol), the compound amine 11 (14.4 g, 34.2 mmol), and sodium tert-butoxide (4.1 g, 42.3 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol) was added thereto. After 5 hours, the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 10.7 g of compound 2-11 (yield 51%, MS: [M+H] ⁺ = 648).

Preparation Example 2-12

In a nitrogen atmosphere, 2-bromotriphenylene (15 g, 48.8 mmol) and (4-chlorophenyl)boronic acid (7.6 g, 48.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (13.5 g, 97.7 mmol) was dissolved in 40 ml of water, and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.5 mmol) was added. After 10 hours of reaction, 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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 sub1-1 (yield 75%, MS: [M+H] ⁺ = 339).

In a nitrogen atmosphere, sub1-1 (10 g, 29.5 mmol), compound amine 12 (7.6 g, 31 mmol), and sodium tert-butoxide (3.7 g, 38.4 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol) was added thereto. After 5 hours, the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 10 g of compound 2-12 (yield 62%, MS: [M+H] ⁺ = 548).

Preparation Example 2-13

In a nitrogen atmosphere, sub1-1 (10 g, 29.5 mmol), compound amine 13 (11.5 g, 31 mmol), and sodium tert-butoxide (3.7 g, 38.4 mmol) were added to 200 ml of Xylene, stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol) was added thereto. After 5 hours, the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 10.9 g of compound 2-13 (yield 55%, MS: [M+H] ⁺ = 674).

Preparation Example 2-14

In a nitrogen atmosphere, 2-bromotriphenylene (10 g, 32.6 mmol), the compound amine 15 (12 g, 34.2 mmol), and sodium tert-butoxide (4.1 g, 42.3 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol) was added thereto. After 5 hours, the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 12.6 g of compound 2-14 (yield 67%, MS: [M+H] ⁺ = 578).

Preparation 2-15

In a nitrogen atmosphere, 2-bromotriphenylene (10 g, 32.6 mmol), the compound amine 17 (13.2 g, 34.2 mmol), and sodium tert-butoxide (4.1 g, 42.3 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol) was added thereto. After 5 hours, the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 11.7 g of compound 2-15 (yield 59%, MS: [M+H] ⁺ = 612).

Preparation Example 2-16

In a nitrogen atmosphere, 2-bromotriphenylene (10 g, 32.6 mmol), the compound amine 18 (11.9 g, 34.2 mmol), and sodium tert-butoxide (4.1 g, 42.3 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol) was added thereto. After 5 hours, the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 10.5 g of compound 2-16 (yield 56%, MS: [M+H] ⁺ = 576).

Preparation Example 2-17

In a nitrogen atmosphere, 2-bromotriphenylene (10 g, 32.6 mmol), the compound amine 19 (12.5 g, 34.2 mmol), and sodium tert-butoxide (4.1 g, 42.3 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol) was added thereto. After 5 hours, the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 12.1 g of compound 2-17 (yield 63%, MS: [M+H] ⁺ = 592).

Preparation Example 2-18

In a nitrogen atmosphere, 2-bromotriphenylene (10 g, 32.6 mmol), the compound amine 20 (13 g, 34.2 mmol), and sodium tert-butoxide (4.1 g, 42.3 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol) was added thereto. After 5 hours, the reaction was completed, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, 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 11.1 g of compound 2-18 (yield 56%, MS: [M+H] ⁺ = 608).

[Example]

Example 1

A glass substrate coated with indium tin oxide (ITO) to a thickness of 1000 Å was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, a product manufactured by Fischer Co. was used as the detergent, and distilled water that was secondarily filtered with a filter manufactured by Millipore Co. was used as the distilled water. After washing ITO for 30 minutes, ultrasonic cleaning was performed for 10 minutes by repeating twice with distilled water. After washing with distilled water, ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, and after drying, it was 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 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 1.5 wt%. The following compound HT-1 was vacuum-deposited on the hole injection layer to form a hole transport layer having a thickness of 800 Å. Then, the following compound EB-1 was vacuum-deposited to a film thickness of 150 Å on the hole transport layer to form an electron blocking layer. Then, on the EB-1 deposited film, the compounds 1-1 and 2-1 prepared previously as a host and the Dp-7 compound as a dopant were vacuum-deposited in a weight ratio of 49:49:2 to form a 400 Å thick red light emitting layer. . A hole blocking layer was formed by vacuum-depositing the following compound HB-1 to a thickness of 30 Å on the light emitting layer. Then, on the hole blocking layer, the following compound ET-1 and the following compound LiQ were vacuum-deposited at a weight ratio of 2:1 to form an electron injection and transport layer to a thickness of 300 Å. A cathode was formed by sequentially depositing lithium fluoride (LiF) to a thickness of 12 Å and aluminum to a thickness of 1000 Å on the electron injection and transport layer.

In the above process, the deposition rate of organic material was maintained at 0.4 ~ 0.7 Å/sec, the deposition rate of lithium fluoride of the negative electrode was maintained at 0.3 Å/sec, and the deposition rate of aluminum was maintained at 2 Å/sec, and the vacuum degree during deposition was 2×10 ^-7 ~ 5×10 ^-6 torr was maintained to manufacture an organic light emitting device.

Examples 2 to 205

An organic light emitting device was manufactured in the same manner as in Example 1, except that in the organic light emitting device of Example 1, the first host and the second host compound described in Table 1 were used by co-deposition in a weight ratio of 1:1. did.

Comparative Examples 1 to 30

An organic light emitting device was manufactured in the same manner as in Example 1, except that in the organic light emitting device of Example 1, the first host and the second host compound described in Table 2 were used by co-deposition in a weight ratio of 1:1. did. Compounds B-1 to B-3 of Table 2 are as follows.

Comparative Examples 31 to 63

An organic light emitting device was manufactured in the same manner as in Example 1, except that in the organic light emitting device of Example 1, the first host and the second host compound described in Table 3 were used by co-deposition in a weight ratio of 1:1. did. Compounds C-1 to C-3 of Table 3 are as follows.

[Experimental example]

When a current was applied to the organic light emitting diodes prepared in Examples 1 to 205 and Comparative Examples 1 to 63, voltage and efficiency were measured (based on 15 mA/cm ² ), and the results are shown in Tables 1 to Table 3 shows. The lifetime T95 means the time it takes for the luminance to decrease to 95% from the initial luminance (6,000 nits).

division 1st host 2nd host drive voltage
(V) efficiency
(cd/A) Life T95
(hr) luminous color Example 1 compound 1-1 compound 2-1 3.53 19.98 173 Red Example 2 compound 1-1 compound 2-5 3.64 20.45 183 Red Example 3 compound 1-1 compound 2-11 3.55 21.39 180 Red Example 4 compound 1-1 compound 2-15 3.62 21.98 183 Red Example 5 compound 1-1 compound 2-17 3.60 21.67 182 Red Example 6 compound 1-2 compound 2-3 3.62 20.29 177 Red Example 7 compound 1-2 compound 2-6 3.65 20.25 182 Red Example 8 compound 1-2 compound 2-13 3.55 20.32 177 Red Example 9 compound 1-2 compound 2-14 3.63 21.05 171 Red Example 10 compound 1-2 compound 2-18 3.58 20.88 188 Red Example 11 compound 1-3 compound 2-2 3.53 21.05 189 Red Example 12 compound 1-3 compound 2-7 3.55 20.97 172 Red Example 13 compound 1-3 compound 2-10 3.59 21.28 181 Red Example 14 compound 1-3 compound 2-12 3.64 21.85 174 Red Example 15 compound 1-3 compound 2-17 3.64 22.56 171 Red Example 16 compound 1-4 compound 2-4 3.87 18.62 197 Red Example 17 compound 1-4 compound 2-8 3.75 18.93 195 Red Example 18 compound 1-4 compound 2-9 3.81 18.45 193 Red Example 19 compound 1-4 compound 2-16 3.88 19.31 203 Red Example 20 compound 1-4 compound 2-18 3.87 19.26 192 Red Example 21 compound 1-5 compound 2-1 3.84 18.31 192 Red Example 22 compound 1-5 compound 2-5 3.82 18.65 206 Red Example 23 compound 1-5 compound 2-11 3.84 18.74 207 Red Example 24 compound 1-5 compound 2-15 3.80 18.80 193 Red Example 25 compound 1-5 compound 2-17 3.78 18.39 194 Red Example 26 compound 1-6 compound 2-3 3.55 20.38 183 Red Example 27 compound 1-6 compound 2-6 3.61 21.36 190 Red Example 28 compound 1-6 compound 2-13 3.58 22.91 189 Red Example 29 compound 1-6 compound 2-14 3.64 22.60 183 Red Example 30 compound 1-6 compound 2-18 3.60 22.26 180 Red Example 31 compound 1-7 compound 2-2 3.50 22.06 190 Red Example 32 compound 1-7 compound 2-7 3.62 22.09 183 Red Example 33 compound 1-7 compound 2-10 3.63 22.78 173 Red Example 34 compound 1-7 compound 2-12 3.64 20.79 188 Red Example 35 compound 1-7 compound 2-17 3.58 21.11 176 Red Example 36 compound 1-8 compound 2-4 3.64 19.83 184 Red Example 37 compound 1-8 compound 2-8 3.63 20.36 189 Red Example 38 compound 1-8 compound 2-9 3.56 21.01 183 Red Example 39 compound 1-8 compound 2-16 3.61 21.35 171 Red Example 40 compound 1-8 compound 2-18 3.58 21.32 179 Red Example 41 compound 1-9 compound 2-1 3.60 22.91 170 Red Example 42 compound 1-9 compound 2-5 3.65 20.00 176 Red Example 43 compound 1-9 compound 2-11 3.56 20.12 190 Red Example 44 compound 1-9 compound 2-15 3.56 20.80 188 Red Example 45 compound 1-9 compound 2-17 3.61 22.77 180 Red Example 46 compound 1-10 compound 2-3 3.65 20.95 172 Red Example 47 compound 1-10 compound 2-6 3.61 21.30 189 Red Example 48 compound 1-10 compound 2-13 3.62 22.60 174 Red Example 49 compound 1-10 compound 2-14 3.65 20.82 190 Red Example 50 compound 1-10 compound 2-18 3.62 21.39 190 Red Example 51 compound 1-11 compound 2-2 3.77 20.01 188 Red Example 52 compound 1-11 compound 2-7 3.55 21.75 172 Red Example 53 compound 1-11 compound 2-10 3.64 19.53 189 Red Example 54 compound 1-11 compound 2-12 3.64 20.73 176 Red Example 55 compound 1-11 compound 2-17 3.57 19.78 178 Red Example 56 compound 1-12 compound 2-4 3.57 21.97 179 Red Example 57 compound 1-12 compound 2-8 3.64 21.59 189 Red Example 58 compound 1-12 compound 2-9 3.59 21.52 190 Red Example 59 compound 1-12 compound 2-16 3.64 20.66 185 Red Example 60 compound 1-12 compound 2-18 3.55 21.13 188 Red Example 61 compound 1-13 compound 2-1 3.87 19.53 219 Red Example 62 compound 1-13 compound 2-5 3.87 20.44 216 Red Example 63 compound 1-13 compound 2-11 3.80 19.92 218 Red Example 64 compound 1-13 compound 2-15 3.87 19.18 230 Red Example 65 compound 1-13 compound 2-17 3.81 20.04 214 Red Example 66 compound 1-14 compound 2-3 3.87 20.28 216 Red Example 67 compound 1-14 compound 2-6 3.89 19.55 230 Red Example 68 compound 1-14 compound 2-13 3.89 19.30 208 Red Example 69 compound 1-14 compound 2-14 3.80 19.99 230 Red Example 70 compound 1-14 compound 2-18 3.88 20.48 224 Red Example 71 compound 1-15 compound 2-2 3.59 22.26 173 Red Example 72 compound 1-15 compound 2-7 3.57 20.99 179 Red Example 73 compound 1-15 compound 2-10 3.61 21.28 180 Red Example 74 compound 1-15 compound 2-12 3.58 22.58 189 Red Example 75 compound 1-15 compound 2-17 3.60 22.94 177 Red Example 76 compound 1-16 compound 2-4 3.61 19.91 185 Red Example 77 compound 1-16 compound 2-8 3.63 20.71 180 Red Example 78 compound 1-16 compound 2-9 3.58 20.33 180 Red Example 79 compound 1-16 compound 2-16 3.56 22.79 175 Red Example 80 compound 1-16 compound 2-18 3.55 21.69 183 Red Example 81 compound 1-17 compound 2-1 3.52 20.66 175 Red Example 82 compound 1-17 compound 2-5 3.64 21.76 174 Red Example 83 compound 1-17 compound 2-11 3.59 22.69 171 Red Example 84 compound 1-17 compound 2-15 3.64 20.80 184 Red Example 85 compound 1-17 compound 2-17 3.65 21.59 188 Red Example 86 compound 1-18 compound 2-3 3.59 21.67 171 Red Example 87 compound 1-18 compound 2-6 3.58 21.88 175 Red Example 88 compound 1-18 compound 2-13 3.65 21.45 188 Red Example 89 compound 1-18 compound 2-14 3.63 22.66 189 Red Example 90 compound 1-18 compound 2-18 3.56 21.77 178 Red Example 91 compound 1-19 compound 2-2 3.52 22.83 178 Red Example 92 compound 1-19 compound 2-7 3.62 19.78 186 Red Example 93 compound 1-19 compound 2-10 3.57 21.17 174 Red Example 94 compound 1-19 compound 2-12 3.61 22.73 189 Red Example 95 compound 1-19 compound 2-17 3.57 22.23 189 Red Example 96 compound 1-20 compound 2-4 3.58 20.19 178 Red Example 97 compound 1-20 compound 2-8 3.60 22.27 184 Red Example 98 compound 1-20 compound 2-9 3.65 21.55 177 Red Example 99 compound 1-20 compound 2-16 3.63 19.81 185 Red Example 100 compound 1-20 compound 2-18 3.60 19.88 190 Red Example 101 compound 1-21 compound 2-1 3.89 20.13 206 Red Example 102 compound 1-21 compound 2-5 3.84 19.69 219 Red Example 103 compound 1-21 compound 2-11 3.83 20.16 213 Red Example 104 compound 1-21 compound 2-15 3.86 20.19 226 Red Example 105 compound 1-21 compound 2-17 3.81 19.02 214 Red Example 106 compound 1-23 compound 2-3 3.89 19.12 218 Red Example 107 compound 1-23 compound 2-6 3.84 19.84 216 Red Example 108 compound 1-23 compound 2-13 3.88 19.73 210 Red Example 109 compound 1-23 compound 2-14 3.89 19.99 216 Red Example 110 compound 1-23 compound 2-18 3.88 20.21 228 Red Example 111 compound 1-25 compound 2-2 3.87 19.93 207 Red Example 112 compound 1-25 compound 2-7 3.80 19.39 214 Red Example 113 compound 1-25 compound 2-10 3.81 19.35 223 Red Example 114 compound 1-25 compound 2-12 3.83 20.32 216 Red Example 115 compound 1-25 compound 2-17 3.88 19.01 226 Red Example 116 compound 1-26 compound 2-4 3.83 19.97 210 Red Example 117 compound 1-26 compound 2-8 3.84 20.04 207 Red Example 118 compound 1-26 compound 2-9 3.82 19.64 223 Red Example 119 compound 1-26 compound 2-16 3.84 19.86 222 Red Example 120 compound 1-26 compound 2-18 3.84 20.18 224 Red Example 121 compound 1-27 compound 2-1 3.67 17.07 304 Red Example 122 compound 1-27 compound 2-5 3.61 17.62 291 Red Example 123 compound 1-27 compound 2-11 3.60 17.43 310 Red Example 124 compound 1-27 compound 2-15 3.60 17.49 291 Red Example 125 compound 1-27 compound 2-17 3.64 18.25 282 Red Example 126 compound 1-28 compound 2-3 3.65 17.96 288 Red Example 127 compound 1-28 compound 2-6 3.69 17.84 305 Red Example 128 compound 1-28 compound 2-13 3.60 17.48 289 Red Example 129 compound 1-28 compound 2-14 3.66 18.20 281 Red Example 130 compound 1-28 compound 2-18 3.69 17.82 292 Red Example 131 compound 1-32 compound 2-2 3.62 17.59 283 Red Example 132 compound 1-32 compound 2-7 3.63 17.21 282 Red Example 133 compound 1-32 compound 2-10 3.68 18.41 303 Red Example 134 compound 1-32 compound 2-12 3.61 17.46 304 Red Example 135 compound 1-32 compound 2-17 3.66 18.33 287 Red Example 136 compound 1-33 compound 2-4 3.62 17.20 299 Red Example 137 compound 1-33 compound 2-8 3.63 18.44 291 Red Example 138 compound 1-33 compound 2-9 3.60 17.71 287 Red Example 139 compound 1-33 compound 2-16 3.63 18.09 296 Red Example 140 compound 1-33 compound 2-18 3.65 17.56 303 Red Example 141 compound 1-34 compound 2-1 3.58 20.87 186 Red Example 142 compound 1-34 compound 2-5 3.63 22.98 189 Red Example 143 compound 1-34 compound 2-11 3.64 20.39 176 Red Example 144 compound 1-34 compound 2-15 3.63 21.82 175 Red Example 145 compound 1-34 compound 2-17 3.56 22.36 170 Red Example 146 compound 1-35 compound 2-3 3.57 21.51 172 Red Example 147 compound 1-35 compound 2-6 3.62 21.51 175 Red Example 148 compound 1-35 compound 2-13 3.56 20.41 182 Red Example 149 compound 1-35 compound 2-14 3.62 21.26 170 Red Example 150 compound 1-35 compound 2-18 3.59 19.89 190 Red Example 151 compound 1-36 compound 2-2 3.98 17.87 166 Red Example 152 compound 1-36 compound 2-7 3.91 17.07 180 Red Example 153 compound 1-36 compound 2-10 3.95 18.47 170 Red Example 154 compound 1-36 compound 2-12 3.99 18.03 172 Red Example 155 compound 1-36 compound 2-17 3.99 17.43 165 Red Example 156 compound 1-37 compound 2-4 3.94 17.05 176 Red Example 157 compound 1-37 compound 2-8 3.94 18.25 176 Red Example 158 compound 1-37 compound 2-9 3.93 17.73 170 Red Example 159 compound 1-37 compound 2-16 3.98 17.24 169 Red Example 160 compound 1-37 compound 2-18 3.96 17.44 172 Red Example 161 compound 1-38 compound 2-1 3.98 17.97 175 Red Example 162 compound 1-38 compound 2-5 3.96 17.64 174 Red Example 163 compound 1-38 compound 2-11 3.94 17.54 170 Red Example 164 compound 1-38 compound 2-15 3.96 17.26 171 Red Example 165 compound 1-38 compound 2-17 3.98 17.77 170 Red Example 166 compound 1-39 compound 2-3 3.93 17.51 172 Red Example 167 compound 1-39 compound 2-6 3.95 17.88 171 Red Example 168 compound 1-39 compound 2-13 3.92 17.24 170 Red Example 169 compound 1-39 compound 2-14 3.91 17.44 174 Red Example 170 compound 1-39 compound 2-18 3.95 18.13 177 Red Example 171 compound 1-41 compound 2-2 3.57 17.97 174 Red Example 172 compound 1-41 compound 2-7 3.58 17.64 172 Red Example 173 compound 1-41 compound 2-10 3.64 17.54 179 Red Example 174 compound 1-41 compound 2-12 3.58 17.26 178 Red Example 175 compound 1-41 compound 2-17 3.65 17.77 185 Red Example 176 compound 1-42 compound 2-4 3.65 17.51 176 Red Example 177 compound 1-42 compound 2-8 3.55 17.88 187 Red Example 178 compound 1-42 compound 2-9 3.64 17.24 176 Red Example 179 compound 1-42 compound 2-16 3.64 17.44 177 Red Example 180 compound 1-42 compound 2-18 3.60 18.13 173 Red Example 181 compound 1-43 compound 2-1 3.75 19.37 236 Red Example 182 compound 1-43 compound 2-5 3.76 18.70 221 Red Example 183 compound 1-43 compound 2-11 3.81 18.16 232 Red Example 184 compound 1-43 compound 2-15 3.84 18.53 229 Red Example 185 compound 1-43 compound 2-17 3.86 19.40 216 Red Example 186 compound 1-44 compound 2-3 3.55 21.64 175 Red Example 187 compound 1-44 compound 2-6 3.65 21.33 183 Red Example 188 compound 1-44 compound 2-13 3.61 19.63 175 Red Example 189 compound 1-44 compound 2-14 3.56 20.85 185 Red Example 190 compound 1-44 compound 2-18 3.58 20.07 188 Red Example 191 compound 1-45 compound 2-2 3.55 21.45 173 Red Example 192 compound 1-45 compound 2-7 3.63 22.21 180 Red Example 193 compound 1-45 compound 2-10 3.60 21.45 187 Red Example 194 compound 1-45 compound 2-12 3.59 22.29 173 Red Example 195 compound 1-45 compound 2-17 3.56 20.66 171 Red Example 196 compound 1-46 compound 2-4 3.58 22.51 177 Red Example 197 compound 1-46 compound 2-8 3.64 21.86 187 Red Example 198 compound 1-46 compound 2-9 3.59 21.48 172 Red Example 199 compound 1-46 compound 2-16 3.63 20.57 182 Red Example 200 compound 1-46 compound 2-18 3.59 20.69 179 Red Example 201 compound 1-47 compound 2-1 3.62 21.73 175 Red Example 202 compound 1-47 compound 2-5 3.62 20.79 170 Red Example 203 compound 1-47 compound 2-11 3.58 22.45 184 Red Example 204 compound 1-47 compound 2-15 3.58 21.61 173 Red Example 205 compound 1-47 compound 2-17 3.61 22.53 183 Red

division 1st host 2nd host drive voltage
(V) efficiency
(cd/A) Life T95
(hr) luminous color Comparative Example 1 compound B-1 compound 2-1 4.29 16.01 109 Red Comparative Example 2 compound B-1 compound 2-5 4.32 16.47 109 Red Comparative Example 3 compound B-1 compound 2-11 4.26 15.75 111 Red Comparative Example 4 compound B-1 compound 2-15 4.25 15.86 113 Red Comparative Example 5 compound B-1 compound 2-17 4.35 16.34 117 Red Comparative Example 6 compound B-1 compound 2-3 4.35 15.68 135 Red Comparative Example 7 compound B-1 compound 2-6 4.22 16.38 116 Red Comparative Example 8 compound B-1 compound 2-13 4.30 15.93 129 Red Comparative Example 9 compound B-1 compound 2-14 4.23 16.09 124 Red Comparative Example 10 compound B-1 compound 2-18 4.27 16.80 113 Red Comparative Example 11 compound B-2 compound 2-2 4.30 14.93 92 Red Comparative Example 12 compound B-2 compound 2-7 4.44 14.66 95 Red Comparative Example 13 compound B-2 compound 2-10 4.38 15.35 108 Red Comparative Example 14 compound B-2 compound 2-12 4.35 15.41 99 Red Comparative Example 15 compound B-2 compound 2-17 4.48 14.95 97 Red Comparative Example 16 compound B-2 compound 2-4 4.37 14.71 95 Red Comparative Example 17 compound B-2 compound 2-8 4.47 15.07 103 Red Comparative Example 18 compound B-2 compound 2-9 4.36 15.28 91 Red Comparative Example 19 compound B-2 compound 2-16 4.39 14.95 88 Red Comparative Example 20 compound B-2 compound 2-18 4.47 14.71 99 Red Comparative Example 21 compound B-3 compound 2-1 4.28 16.50 109 Red Comparative Example 22 compound B-3 compound 2-5 4.25 16.32 112 Red Comparative Example 23 compound B-3 compound 2-11 4.29 16.26 119 Red Comparative Example 24 compound B-3 compound 2-15 4.29 16.86 121 Red Comparative Example 25 compound B-3 compound 2-17 4.24 16.36 121 Red Comparative Example 26 compound B-3 compound 2-3 4.33 15.74 125 Red Comparative Example 27 compound B-3 compound 2-6 4.23 16.50 118 Red Comparative Example 28 compound B-3 compound 2-13 4.21 15.96 130 Red Comparative Example 29 compound B-3 compound 2-14 4.21 15.77 126 Red Comparative Example 30 compound B-3 compound 2-18 4.30 16.65 108 Red

division 1st host 2nd host Driving voltage (V) efficiency
(cd/A) Life T95
(hr) luminous color Comparative Example 31 compound 1-1 compound C-1 4.39 15.04 107 Red Comparative Example 32 compound 1-4 compound C-1 4.37 15.34 98 Red Comparative Example 33 compound 1-7 compound C-1 4.39 14.62 101 Red Comparative Example 34 compound 1-13 compound C-1 4.31 15.08 96 Red Comparative Example 35 compound 1-19 compound C-1 4.30 15.44 109 Red Comparative Example 36 compound 1-23 compound C-1 4.35 14.90 93 Red Comparative Example 37 compound 1-28 compound C-1 4.41 14.65 91 Red Comparative Example 38 compound 1-32 compound C-1 4.49 15.50 100 Red Comparative Example 39 compound 1-38 compound C-1 4.48 14.73 106 Red Comparative Example 40 compound 1-41 compound C-1 4.40 14.93 113 Red Comparative Example 41 compound 1-44 compound C-1 4.30 15.16 91 Red Comparative Example 42 compound 1-2 compound C-2 4.27 15.88 116 Red Comparative Example 43 compound 1-5 compound C-2 4.33 15.89 127 Red Comparative Example 44 compound 1-8 compound C-2 4.26 16.70 122 Red Comparative Example 45 compound 1-15 compound C-2 4.27 16.56 125 Red Comparative Example 46 compound 1-20 compound C-2 4.35 16.66 111 Red Comparative Example 47 compound 1-25 compound C-2 4.30 15.77 117 Red Comparative Example 48 compound 1-30 compound C-2 4.32 16.34 130 Red Comparative Example 49 compound 1-35 compound C-2 4.32 16.21 115 Red Comparative Example 50 compound 1-39 compound C-2 4.23 15.64 117 Red Comparative Example 51 compound 1-42 compound C-2 4.26 16.44 128 Red Comparative Example 52 compound 1-45 compound C-2 4.26 15.81 114 Red Comparative Example 53 compound 1-3 compound C-3 4.24 15.74 119 Red Comparative Example 54 compound 1-6 compound C-3 4.35 16.75 112 Red Comparative Example 55 compound 1-9 compound C-3 4.30 17.00 110 Red Comparative Example 56 compound 1-17 compound C-3 4.21 15.76 108 Red Comparative Example 57 compound 1-22 compound C-3 4.25 16.06 124 Red Comparative Example 58 compound 1-26 compound C-3 4.33 16.75 125 Red Comparative Example 59 compound 1-31 compound C-3 4.31 16.95 129 Red Comparative Example 60 compound 1-36 compound C-3 4.29 15.59 119 Red Comparative Example 61 compound 1-40 compound C-3 4.25 15.73 109 Red Comparative Example 62 compound 1-43 compound C-3 4.27 16.87 110 Red Comparative Example 63 compound 1-47 compound C-3 4.26 15.80 122 Red

When a current was applied to the organic light emitting diodes fabricated in Examples 1 to 205 and Comparative Examples 1 to 63, the results shown in Tables 1 to 3 were obtained. The red organic light emitting diode of the above embodiment has a structure in which compound EB-1, a material widely used in the prior art, is used as an electron blocking layer material, and compound Dp-7 is used as a red dopant material. When the compound represented by Formula 1 and the compound represented by Formula 2 were co-deposited and used as a red light emitting layer as shown in Table 1, compared to Comparative Example, it can be seen that the driving voltage is decreased and the efficiency and lifespan are increased. In addition, as shown in Table 2, when the compounds of Comparative Examples B-1 to B-3 and the compound of Formula 2 of the present invention were co-deposited and used as a red light emitting layer, the driving voltage generally increased, and the efficiency and lifespan were higher than that of the combination of the present invention. As shown in Table 3, when the compounds of Comparative Examples C-1 to C-3 and the compound of Formula 1 of the present invention were co-deposited and used as a red light emitting layer, the driving voltage increased and the efficiency and lifespan decreased as shown in Table 3 showed

From these results, when the compound of Formula 1 as the first host and the compound of Formula 2 as the second host of the present invention are combined, energy transfer to the red dopant in the red light emitting layer is well made, so that the driving voltage is improved and the efficiency and lifespan are increased It can be inferred that That is, the combination of the compound represented by Formula 1 and the compound represented by Formula 2 of the present invention, rather than the combination with the compound of Comparative Example, combines electrons and holes through a more stable balance into the light emitting layer to form excitons, resulting in higher efficiency and lifetime. could be seen to rise. In conclusion, it was confirmed that the driving voltage, luminous efficiency, and lifespan characteristics of the organic light emitting device could be improved when the compound of Formula 1 and the compound of Formula 2 were combined and used as a host for the red light emitting layer by co-evaporation.

1: Substrate 2: Anode
3: light emitting layer 4: cathode
5: hole injection layer 6: hole transport layer
7: electron transport layer 8: electron injection layer
9: electron blocking layer 10: hole blocking layer

Claims (9)

anode; cathode; and a light emitting layer between the anode and the cathode,
The light emitting layer comprises a compound represented by the following formula (1) and a compound represented by the following formula (2),
Organic light emitting device:
[Formula 1]

In Formula 1,
Ar ₁ and Ar ₂ are each independently substituted or unsubstituted C _6-60 aryl; _{Or substituted or unsubstituted C 2-60} heteroaryl comprising any one or more selected from the group consisting of N, O and S,
L ₁ and L ₂ are each independently a single bond; Or a substituted or unsubstituted C _6-60 arylene,
L ₃ is a single bond; Or a substituted or unsubstituted C _6-60 arylene,
each R ₁ is independently hydrogen or deuterium; or two adjacent ones combine to form a benzene ring, and the remainder is hydrogen or deuterium;
each R ₂ is independently hydrogen or deuterium; or two adjacent ones combine to form a benzene ring, and the remainder is hydrogen or deuterium;
[Formula 2]

In Formula 2,
Ar ₃ and Ar ₄ are each independently substituted or unsubstituted C _6-60 aryl; _{Or C 2-60} heteroaryl comprising at least one selected from the group consisting of substituted or unsubstituted O and S,
L ₄ to L ₆ are each independently a single bond; or substituted or unsubstituted C _6-60 arylene.
According to claim 1,
Formula 1 is represented by any one selected from the group consisting of the following Formulas 1-1 to 1-9,
Organic light emitting device:

In Formulas 1-1 to 1-9,
Ar ₁ , Ar ₂ , L ₁ , L ₂ and L ₃ are as defined in claim 1.
According to claim 1,
Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, naphthyl, phenanthrenyl, phenyl carbazolyl, dibenzofuranyl, dibenzothiophenyl, or benzonaphthofuranyl;
organic light emitting device.
According to claim 1,
L ₁ and L ₂ are each independently a single bond, phenylene, or naphthylene,
organic light emitting device.
According to claim 1,
L ₃ is a single bond, phenylene, biphenylrylene, or naphthylene;
organic light emitting device.
According to claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of
Organic light emitting device:

.
According to claim 1,
Ar ₃ and Ar ₄ are each independently phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, dimethylfluorenyl, diphenylfluorenyl, dibenzofuranyl, dibenzothiophenyl, or benzo naphthofuranyl,
organic light emitting device.
According to claim 1,
L _{4 To} L ₆ are each independently a single bond, phenylene, or dimethyl fluorenylene,
organic light emitting device.
According to claim 1,
The compound represented by Formula 2 is any one selected from the group consisting of
Organic light emitting device:

.

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