KR102645016B1 - Organic light emitting device - Google Patents

Abstract

The present invention provides an organic light emitting device.

Description

Organic light emitting device

The present invention relates to organic light emitting devices.

In general, organic luminescence refers to a phenomenon that converts electrical energy into light energy using organic materials. Organic light-emitting devices using the organic light-emitting phenomenon have a wide viewing angle, excellent contrast, fast response time, and excellent luminance, driving voltage, and response speed characteristics, so much research is being conducted.

Organic light emitting devices generally have a structure including an anode, a cathode, and an organic layer between the anode and the cathode. The organic material layer is often composed of a multi-layer structure made of different materials to increase the efficiency and stability of the organic light-emitting device, and may be composed of, for example, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer. In the structure of this organic light-emitting device, when a voltage is applied between the two electrodes, holes are injected from the anode and electrons from the cathode into the organic material layer. When the injected holes and electrons meet, an exciton is formed, and this exciton is When it falls back to the ground state, it glows.

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 with improved driving voltage, efficiency, and lifespan.

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 includes a compound represented by Formula 1 below and a compound represented by Formula 2 below,

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 C _2-60 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O and S,

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

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

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

R ₂ is each 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,

A and B are each independently a benzene ring or a naphthalene ring fused to an adjacent ring,

L' ₁ is a single bond; Or substituted or unsubstituted C _6-60 arylene,

Ar' ₁ is a substituent represented by the following formula 3-1 or 3-2,

[Formula 3-1]

In Formula 3-1,

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

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

[Formula 3-2]

In Formula 3-2,

C and D are each independently a benzene ring fused to an adjacent ring, or a naphthalene ring,

Ar' ₂ is substituted or unsubstituted C _6-60 aryl; or C _2-60 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O, and S.

The organic light emitting device described above is excellent in driving voltage, efficiency, and lifespan.

Figure 1 shows an example of an organic light-emitting device consisting of a substrate 1, an anode 2, a light-emitting layer 3, and a cathode 4.
Figure 2 shows 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). An example of an organic light emitting device is shown.
3 shows a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 9, a light emitting layer 3, a hole blocking layer 10, and an electron transport layer 7. ), an electron injection layer (8), and a cathode (4).

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

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; imide group; amino group; Phosphine oxide group; Alkoxy group; Aryloxy group; Alkylthioxy group; Arylthioxy group; Alkyl sulphoxy group; Aryl sulfoxy group; silyl group; boron group; Alkyl group; Cycloalkyl group; alkenyl group; Aryl group; Aralkyl group; Aralkenyl group; Alkylaryl group; Alkylamine group; Aralkylamine group; heteroarylamine group; Arylamine group; Arylphosphine group; or substituted or unsubstituted with one or more substituents selected from the group consisting of heterocyclic groups containing one or more of N, O and S atoms, or substituted or unsubstituted with two or more of the above-exemplified substituents linked. . For example, “a substituent group in which two or more substituents are connected” may be a biphenyl group. That is, the biphenyl group may be an aryl group, or it may be interpreted as a substituent in which two phenyl groups are connected.

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

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

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

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

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

In this specification, examples of halogen groups include fluorine, chlorine, bromine, or iodine.

In the present specification, the alkyl group may be straight chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the carbon number of the alkyl group is 1 to 20. According to another embodiment, the carbon number of the alkyl group is 1 to 10. According to another embodiment, the carbon number of the alkyl group is 1 to 6. Specific examples of alkyl groups include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n. -pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, etc., but is not limited to these.

In the present specification, the alkenyl group may be straight chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-( Naphthyl-1-yl) vinyl-1-yl, 2,2-bis (diphenyl-1-yl) vinyl-1-yl, stilbenyl group, styrenyl group, etc., but are not limited to these.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another embodiment, the carbon number of the cycloalkyl group is 3 to 20. According to another embodiment, the carbon number of the cycloalkyl group is 3 to 6. Specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3, Examples include, but are not limited to, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, and cyclooctyl.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to one embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a monocyclic aryl group, such as a phenyl group, biphenyl group, or terphenyl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, etc., 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 combined with each other to form a spiro structure. When the fluorenyl group is substituted,

It can be etc. However, it is not limited to this.

In the present specification, the heterocyclic group is a heterocyclic group containing one or more of O, N, Si, and S as a heterogeneous element, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of heterocyclic groups include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, and 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, benzooxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, isoxazolyl group, thiadia These include, but are not limited to, a zolyl group, a phenothiazinyl group, and a dibenzofuranyl group.

In this specification, the aryl group among the aralkyl group, aralkenyl group, alkylaryl group, and arylamine group is the same as the example of the aryl group described above. In this specification, the aralkyl group, alkylaryl group, and alkylamine group are the same as the examples of the alkyl group described above. In the present specification, the description regarding the heterocyclic group described above may be applied to heteroaryl among heteroarylamines. In this specification, the alkenyl group among the aralkenyl groups is the same as the example of the alkenyl group described above. In the present specification, the description of the aryl group described above can be applied, except that arylene is a divalent group. In the present specification, the description of the heterocyclic group described above can be applied, except that heteroarylene is a divalent group. In the present specification, the description of the aryl group or cycloalkyl group described above can be applied, except that the hydrocarbon ring is not monovalent and is formed by combining two substituents. In the present specification, the description of the heterocyclic group described above can be applied, except that the heterocycle is not a monovalent group and is formed by combining two substituents.

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

anode and cathode

The anode and cathode used in the present invention refer to electrodes used in organic light-emitting devices.

The anode material is generally preferably a material with a large work function to facilitate hole injection into the organic layer. Specific examples of the anode material include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO:Al or SnO ₂ :Sb; Conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDOT), polypyrrole, and polyaniline are included, but are not limited to these.

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

Hole injection layer

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

The hole injection layer is a layer that injects holes from an electrode. The hole injection material has the ability to transport holes, has an excellent hole injection effect at the anode, a light-emitting layer or a light-emitting material, and has an excellent hole injection effect on the light-emitting layer or light-emitting material. A compound that prevents movement of excitons to the electron injection layer or electron injection material and has excellent thin film forming ability is preferred. Additionally, it is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic material layer.

Specific examples of hole injection materials include metal porphyrin, oligothiophene, arylamine-based organic substances, hexanitrilehexaazatriphenylene-based organic substances, quinacridone-based organic substances, and perylene-based organic substances. organic substances, anthraquinone, polyaniline, and polythiophene series conductive polymers, etc., but are not limited to these.

hole transport layer

The organic light emitting device 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 suppressing 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 holes to the light-emitting layer. It is a hole transport material that can receive holes from the anode or hole injection layer and transfer them to the light-emitting layer, and is a material with high mobility for holes. This is suitable.

Specific examples of the hole transport material include arylamine-based organic materials, conductive polymers, and block copolymers with both conjugated and non-conjugated portions, but are not limited to these.

Electronic blocking layer

The electron suppressing layer is a layer placed between the hole transport layer and the light emitting layer to prevent electrons injected from the cathode from being recombined in the light emitting layer and passing to the hole transport layer, and is also called an electron suppressing layer. A material with lower electron affinity than the electron transport layer is preferred for the electron blocking layer.

luminescent layer

The light-emitting layer used in the present invention refers to a layer that can emit light in the visible light range by combining holes and electrons received from the anode and cathode. Generally, the light emitting layer includes a host material and a dopant material, and in the present invention, it includes the compound represented by Formula 1 and the compound represented by Formula 2 as the host.

Preferably, 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 previously defined.

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 containing 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 substituted or unsubstituted C _6-20 arylene.

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

Preferably, L ₃ is a single bond; Or it may be substituted or unsubstituted C _6-60 arylene.

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

Representative examples of compounds represented by Formula 1 are as follows:

For example, the compound represented by Formula 1 can be prepared by a manufacturing method as shown in Scheme 1 below:

[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, which is preferably carried out in the presence of a palladium catalyst and a base, and the reactor for the amine substitution reaction can be changed according to what is known in the art. The manufacturing method may be further detailed in the manufacturing examples described later.

Preferably, Formula 2 is represented by any one selected from the group consisting of the following Formulas 2-1 to 2-6:

In Formulas 2-1 to 2-6, L' ₁ and Ar' ₁ are as defined in Formula 2.

Preferably, L' ₁ is a single bond; or any one selected from the group consisting of:

In the above, X' is NR', C(R') ₂ , O, or S, and R' is each independently hydrogen; Substituted or unsubstituted C _1-20 alkyl; Or substituted or unsubstituted C _6-20 aryl.

Preferably, X' is O or S.

Preferably, Ar' ₁ is any one selected from the group consisting of:

Representative examples of compounds represented by Formula 2 are as follows:

For example, the compound represented by Formula 2 can be prepared by a manufacturing method as shown in Scheme 2 below:

[Scheme 2]

In Scheme 2, A, B, L' ₁ , and Ar' ₁ 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, which is preferably carried out in the presence of a palladium catalyst and a base, and the reactor for the amine substitution reaction can be changed according to what is known in the art. The manufacturing method may be further detailed in the manufacturing examples described later.

In the light-emitting layer, the weight ratio of the compound represented by Formula 1 and 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 organic light-emitting devices. Examples include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, aromatic amine derivatives include condensed aromatic ring derivatives having a substituted or unsubstituted arylamino group, such as pyrene, anthracene, chrysene, and periplanthene, and styrylamine compounds include substituted or unsubstituted arylamino groups. It is a compound in which at least one arylvinyl group is substituted on the arylamine, and is substituted or unsubstituted with one or two or more substituents selected from the group consisting of aryl group, silyl group, alkyl group, cycloalkyl group, and arylamino group. Specifically, styrylamine, styryldiamine, styryltriamine, styryltetraamine, etc. are included, but are not limited thereto. Additionally, metal complexes include, but are not limited to, iridium complexes and platinum complexes.

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

.

.

hole blocking layer

The hole blocking layer is a layer placed between the electron transport layer and the light emitting layer to prevent holes injected from the anode from being recombined in the light emitting layer and passing to the electron transport layer, and is also called a hole blocking layer. A material with high ionization energy is preferred 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 cathode or the electron injection layer formed on the cathode and transports electrons to the light-emitting layer, and also suppresses the transfer of holes from the light-emitting layer. The electron transport material is used to effectively inject electrons 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 Al complex of 8-hydroxyquinoline; Complex containing Alq ₃ ; organic radical compounds; Hydroxyflavone-metal complexes, etc., but are not limited to these. The electron transport layer can be used with any desired cathode material as used according to the prior art. In particular, examples of suitable cathode materials are conventional materials with a low work function followed by an aluminum or silver layer. Specifically, cesium, barium, calcium, ytterbium and samarium, in each case followed by an aluminum layer or a silver layer.

electron injection layer

The organic light emitting device according to the present invention may additionally 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 excellent electron injection effect from the cathode, a light-emitting layer or a light-emitting material, and hole injection of excitons generated in the light-emitting layer. It is desirable to use a compound that prevents movement to the layer and has excellent thin film forming ability.

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

Examples of the metal complex compounds 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-cresolato) gallium, bis(2-methyl-8-quinolinato)(1-naphtolato) aluminum, bis(2-methyl-8-quinolinato)(2-naphtolato) gallium, etc. It is not limited to this.

Meanwhile, in the present invention, the “electron injection and transport layer” is a layer that performs the functions of both the electron injection layer and the electron transport layer. The materials that play the role of each layer can be used singly or in combination, but are limited thereto. It doesn't work.

organic light emitting device

The structure of the organic light emitting device according to the present invention is illustrated in Figures 1 to 3. Figure 1 shows an example of an organic light-emitting device consisting of a substrate 1, an anode 2, a light-emitting layer 3, and a cathode 4. In addition, Figure 2 shows 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. ) shows an example of an organic light-emitting device made of. 3 shows a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 9, a light emitting layer 3, a hole blocking layer 10, and an electron transport layer 7. ), an electron injection layer (8), and a cathode (4). In the above, the electron transport layer 7 and the electron injection layer 8 may be composed of a single layer (electron injection and transport layer).

The organic light emitting device according to the present invention can be manufactured by sequentially stacking the above-described structures. At this time, an anode is formed by depositing a metal or a conductive metal oxide or an alloy thereof on the substrate using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation. It can be manufactured by forming each layer described above and then depositing a material that can be used as a cathode on it.

In addition to this method, an organic light-emitting device can be made by sequentially depositing a cathode material on a substrate and then an anode material in the reverse order of the above-described configuration (WO 2003/012890). Additionally, the light-emitting layer can be formed by using a solution coating method as well as a vacuum deposition method for the host and dopant. Here, the solution application method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, etc., but is not limited to these.

Meanwhile, the organic light-emitting device according to the present invention may be a bottom-emitting device, a top-emitting device, or a double-sided light-emitting device. In particular, it may be a bottom-emitting device that requires relatively high luminous efficiency.

Below, preferred embodiments are presented to aid understanding of the present invention. However, the following examples are provided only to make the present invention easier to understand, and the content of the present invention is not limited thereto.

[Manufacturing example]

Manufacturing Example 1-1

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), sub1 (25.6 g, 62.8 mmol), and Potassium Phosphate (38.1 g, 179.4 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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)

Manufacturing Example 1-2

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), sub2 (25.6 g, 62.8 mmol), and Potassium Phosphate (38.1 g, 179.4 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added. After 2 hours, the reaction was completed, the reaction was cooled to room temperature, the pressure was reduced, and the solvent was removed. Afterwards, the compound was completely dissolved in chloroform, 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)

Manufacturing Example 1-3

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), sub3 (27.2 g, 62.8 mmol), and Potassium Phosphate (38.1 g, 179.4 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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)

Manufacturing Example 1-4

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), sub4 (30.4 g, 62.8 mmol), and Potassium Phosphate (38.1 g, 179.4 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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)

Manufacturing Example 1-5

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), sub5 (29.5 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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)

Manufacturing Example 1-6

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), sub6 (29.5 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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)

Manufacturing Example 1-7

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), sub7 (27.2 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added. After 2 hours, the reaction was completed, the reaction was cooled to room temperature, the pressure was reduced, and the solvent was removed. Afterwards, the compound was completely dissolved in chloroform, 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)

Manufacturing Example 1-8

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), sub8 (32.7 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added. After 2 hours, the reaction was completed, the reaction was cooled to room temperature, the pressure was reduced, and the solvent was removed. Afterwards, the compound was completely dissolved in chloroform, 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)

Manufacturing Example 1-9

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), sub9 (30.4 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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)

Manufacturing Example 1-10

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), sub10 (30.4 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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)

Manufacturing Example 1-11

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), sub11 (27.2 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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)

Manufacturing Example 1-12

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), sub12 (27.9 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added. After 2 hours, the reaction was completed, the reaction was cooled to room temperature, the pressure was reduced, and the solvent was removed. Afterwards, the compound was completely dissolved in chloroform, 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)

Manufacturing Example 1-13

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), sub13 (29.5 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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)

Manufacturing Example 1-14

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), sub14 (35.1 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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)

Manufacturing Example 1-15

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), sub15 (31 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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)

Manufacturing Example 1-16

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), sub16 (31.4 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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)

Manufacturing Example 1-17

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), sub17 (26.4 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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)

Manufacturing Example 1-18

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), sub18 (32 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added. After 2 hours, the reaction was completed, the reaction was cooled to room temperature, the pressure was reduced, and the solvent was removed. Afterwards, the compound was completely dissolved in chloroform, 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)

Manufacturing Example 1-19

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), sub19 (31.1 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added. After 2 hours, the reaction was completed, the reaction was cooled to room temperature, the pressure was reduced, and the solvent was removed. Afterwards, the compound was completely dissolved in chloroform, 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)

Manufacturing Example 1-20

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), sub20 (33 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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)

Manufacturing Example 1-21

In a nitrogen atmosphere, 7H-benzo[c]carbazole (10 g, 46 mmol), sub21 (18.1 g, 48.3 mmol), and Potassium Phosphate (29.3 g, 138.1 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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)

Manufacturing Example 1-22

In a nitrogen atmosphere, 7H-benzo[c]carbazole (10 g, 46 mmol), sub7 (21 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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)

Manufacturing Example 1-23

In a nitrogen atmosphere, 7H-benzo[c]carbazole (10 g, 46 mmol), sub22 (26.9 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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)

Manufacturing Example 1-24

In a nitrogen atmosphere, 7H-benzo[c]carbazole (10 g, 46 mmol), sub23 (16.6 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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)

Manufacturing Example 1-25

In a nitrogen atmosphere, 7H-benzo[c]carbazole (10 g, 46 mmol), sub24 (16.6 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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)

Manufacturing Example 1-26

In a nitrogen atmosphere, 7H-benzo[c]carbazole (10 g, 46 mmol), sub25 (25.1 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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)

Manufacturing Example 1-27

In a nitrogen atmosphere, 7H-benzo[c]carbazole (10 g, 46 mmol), sub26 (25.4 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 2 hours, the reaction was completed, the reaction was cooled to room temperature, the pressure was reduced, and the solvent was removed. Afterwards, the compound was completely dissolved in chloroform, 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)

Manufacturing Example 1-28

In a nitrogen atmosphere, 5H-benzo[b]carbazole (10 g, 46 mmol), sub27 (17.8 g, 48.3 mmol), and Potassium Phosphate (29.3 g, 138.1 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 2 hours, the reaction was completed, the reaction was cooled to room temperature, the pressure was reduced, and the solvent was removed. Afterwards, the compound was completely dissolved in chloroform, 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)

Manufacturing Example 1-29

In a nitrogen atmosphere, 5H-benzo[b]carbazole (10 g, 46 mmol), sub28 (20.3 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 2 hours, the reaction was completed, the reaction was cooled to room temperature, the pressure was reduced, and the solvent was removed. Afterwards, the compound was completely dissolved in chloroform, 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)

Manufacturing Example 1-30

In a nitrogen atmosphere, 5H-benzo[b]carbazole (10 g, 46 mmol), sub29 (21.7 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 2 hours, the reaction was completed, the reaction was cooled to room temperature, the pressure was reduced, and the solvent was removed. Afterwards, the compound was completely dissolved in chloroform, 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)

Manufacturing Example 1-31

In a nitrogen atmosphere, 5H-benzo[b]carbazole (10 g, 46 mmol), sub30 (24.6 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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)

Manufacturing Example 1-32

In a nitrogen atmosphere, 5H-benzo[b]carbazole (10 g, 46 mmol), sub31 (25.1 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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)

Manufacturing Example 1-33

In a nitrogen atmosphere, 5H-benzo[b]carbazole (10 g, 46 mmol), sub32 (19 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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)

Manufacturing Example 1-34

In a nitrogen atmosphere, 5H-benzo[b]carbazole (10 g, 46 mmol), sub33 (22.7 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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)

Manufacturing Example 1-35

In a nitrogen atmosphere, 5H-benzo[b]carbazole (10 g, 46 mmol), sub17 (20.3 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 2 hours, the reaction was completed, the reaction was cooled to room temperature, the pressure was reduced, and the solvent was removed. Afterwards, the compound was completely dissolved in chloroform, 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)

Manufacturing Example 1-36

In a nitrogen atmosphere, 11H-benzo[a]carbazole (10 g, 46 mmol), sub34 (22.7 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 2 hours, the reaction was completed, the reaction was cooled to room temperature, the pressure was reduced, and the solvent was removed. Afterwards, the compound was completely dissolved in chloroform, 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)

Manufacturing Example 1-37

In a nitrogen atmosphere, 11H-benzo[a]carbazole (10 g, 46 mmol), sub35 (21.7 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 2 hours, the reaction was completed, the reaction was cooled to room temperature, the pressure was reduced, and the solvent was removed. Afterwards, the compound was completely dissolved in chloroform, 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)

Manufacturing Example 1-38

In a nitrogen atmosphere, 11H-benzo[a]carbazole (10 g, 46 mmol), sub36 (27.1 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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)

Manufacturing Example 1-39

In a nitrogen atmosphere, 11H-benzo[a]carbazole (10 g, 46 mmol), sub37 (25.4 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 2 hours, the reaction was completed, the reaction was cooled to room temperature, the pressure was reduced, and the solvent was removed. Afterwards, the compound was completely dissolved in chloroform, 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)

Manufacturing Example 1-40

In a nitrogen atmosphere, 11H-benzo[a]carbazole (10 g, 46 mmol), sub38 (24.6 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 2 hours, the reaction was completed, the reaction was cooled to room temperature, the pressure was reduced, and the solvent was removed. Afterwards, the compound was completely dissolved in chloroform, 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)

Manufacturing Example 1-41

In a nitrogen atmosphere, 7H-dibenzo[b,g]carbazole (10 g, 37.4 mmol), sub39 (14.7 g, 39.3 mmol), and Potassium Phosphate (23.8 g, 112.2 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added. After 2 hours, the reaction was completed, the reaction was cooled to room temperature, the pressure was reduced, and the solvent was removed. Afterwards, the compound was completely dissolved in chloroform, 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)

Manufacturing Example 1-42

In a nitrogen atmosphere, 7H-dibenzo[b,g]carbazole (10 g, 37.4 mmol), 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. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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)

Manufacturing Example 1-43

In a nitrogen atmosphere, 6H-dibenzo[b,h]carbazole (10 g, 37.4 mmol), sub41 (14.1 g, 39.3 mmol), and Potassium Phosphate (23.8 g, 112.2 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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)

Manufacturing Example 1-44

In a nitrogen atmosphere, 6H-dibenzo[b,h]carbazole (10 g, 37.4 mmol), 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. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added. After 2 hours, the reaction was completed, the reaction was cooled to room temperature, the pressure was reduced, and the solvent was removed. Afterwards, the compound was completely dissolved in chloroform, 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)

Manufacturing Example 1-45

In a nitrogen atmosphere, 13H-dibenzo[a,h]carbazole (10 g, 37.4 mmol), sub43 (16 g, 39.3 mmol), and Potassium Phosphate (23.8 g, 112.2 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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)

Manufacturing Example 1-46

In a nitrogen atmosphere, 13H-dibenzo[a,h]carbazole (10 g, 37.4 mmol), 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. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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)

Manufacturing Example 1-47

In a nitrogen atmosphere, 7H-dibenzo[c,g]carbazole (10 g, 37.4 mmol), sub45 (14.1 g, 39.3 mmol), and Potassium Phosphate (23.8 g, 112.2 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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)

Manufacturing Example 2-1

In a nitrogen atmosphere, 2-bromo-9-phenyl-9H-carbazole (10g, 31mmol) and sub1 (5.3g, 34.1mmol) were added to 200ml of THF, stirred and refluxed. Afterwards, potassium carbonate (12.9g, 93.1mmol) was dissolved in 39ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.4g, 0.3mmol) was added. After reaction for 8 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.3 g of subA-1. (Yield 76%, MS: [M+H]+= 354)

In a nitrogen atmosphere, subA-1 (10 g, 28.3 mmol), compound A (6.9 g, 28.5 mmol), and sodium tert-butoxide (3.5 g, 36.7 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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 10.1 g of compound 2-1. (Yield 64%, MS: [M+H]+= 561)

Manufacturing Example 2-2

In a nitrogen atmosphere, 11H-benzo[a]carbazole (10 g, 46 mmol), sub2 (13.1 g, 46.5 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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 subA-2. (Yield 52%, MS: [M+H]+= 418)

In a nitrogen atmosphere, subA-2 (10 g, 23.9 mmol), compound A (5.9 g, 24.2 mmol), and sodium tert-butoxide (3 g, 31.1 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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 2-2. (Yield 70%, MS: [M+H]+= 625)

Manufacturing Example 2-3

In a nitrogen atmosphere, 7H-benzo[c]carbazole (10 g, 46 mmol), sub3 (12.4 g, 46.5 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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 9.8 g of subA-3. (Yield 53%, MS: [M+H]+= 404)

In a nitrogen atmosphere, subA-3 (10 g, 24.8 mmol), compound A (6.1 g, 25 mmol), and sodium tert-butoxide (3.1 g, 32.2 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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 2-3. (Yield 66%, MS: [M+H]+= 611)

Manufacturing Example 2-4

In a nitrogen atmosphere, 2-bromo-9-phenyl-9H-carbazole (10 g, 31 mmol), compound B (9.2 g, 31.3 mmol), and sodium tert-butoxide (3.9 g, 40.3 mmol) were added to 200 ml of Xylene, stirred and refluxed. did. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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 8.6 g of compound 2-4. (Yield 52%, MS: [M+H]+= 535)

Manufacturing Example 2-5

In a nitrogen atmosphere, 2-bromo-5H-benzo[b]carbazole (10 g, 33.8 mmol), sub4 (7 g, 34.1 mmol), and sodium tert-butoxide (4.2 g, 43.9 mmol) were added to 200 ml of Xylene, stirred, and refluxed. . Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.7 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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 7.3 g of subB-1. (Yield 58%, MS: [M+H]+= 373)

In a nitrogen atmosphere, subB-1 (10 g, 26.9 mmol), compound B (8 g, 27.1 mmol), and sodium tert-butoxide (3.4 g, 34.9 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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 9.1 g of compound 2-5. (Yield 58%, MS: [M+H]+= 585)

Manufacturing Example 2-6

In a nitrogen atmosphere, 3-bromo-11H-benzo[a]carbazole (10 g, 33.8 mmol), sub4 (7 g, 34.1 mmol), and sodium tert-butoxide (4.2 g, 43.9 mmol) were added to 200 ml of Xylene, stirred, and refluxed. . Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.7 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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 7 g of subB-2. (Yield 56%, MS: [M+H]+= 372)

In a nitrogen atmosphere, subB-2 (10g, 26.9mmol) and sub1 (4.6g, 29.5mmol) were added to 200ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (11.1g, 80.6mmol) was dissolved in 33ml of water and stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.3g, 0.3mmol) was added. After reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 7.9 g of subB-3. (Yield 73%, MS: [M+H]+= 404)

In a nitrogen atmosphere, subB-3 (10 g, 24.8 mmol), compound B (7.3 g, 25 mmol), and sodium tert-butoxide (3.1 g, 32.2 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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 8.8 g of compound 2-6. (Yield 54%, MS: [M+H]+= 661)

Manufacturing Example 2-7

In a nitrogen atmosphere, 9-bromo-7H-benzo[c]carbazole (10 g, 33.8 mmol), sub4 (7 g, 34.1 mmol), and sodium tert-butoxide (4.2 g, 43.9 mmol) were added to 200 ml of Xylene, stirred, and refluxed. . Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.7 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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 6.3 g of subC-1. (Yield 50%, MS: [M+H]+= 372)

In a nitrogen atmosphere, subC-1 (10 g, 26.9 mmol), compound C (8 g, 27.1 mmol), and sodium tert-butoxide (3.4 g, 34.9 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After 5 hours, the reaction was completed, it was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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 10.4 g of compound 2-7. (Yield 66%, MS: [M+H]+= 585)

Manufacturing Example 2-8

In a nitrogen atmosphere, 11H-benzo[a]carbazole (10 g, 46 mmol), sub5 (13.8 g, 46.5 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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 subC-2. (Yield 67%, MS: [M+H]+= 434)

In a nitrogen atmosphere, subC-2 (10 g, 23 mmol), compound C (6.8 g, 23.3 mmol), and sodium tert-butoxide (2.9 g, 30 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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 2-8. (Yield 65%, MS: [M+H]+= 691)

Manufacturing Example 2-9

In a nitrogen atmosphere, 2-bromo-7H-benzo[c]carbazole (10 g, 46 mmol), sub4 (9.5 g, 46.5 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of Xylene, stirred, and refluxed. . Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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 9.2 g of subC-3. (Yield 54%, MS: [M+H]+= 372)

In a nitrogen atmosphere, subC-3 (10 g, 26.9 mmol), compound C (8 g, 27.1 mmol), and sodium tert-butoxide (3.4 g, 34.9 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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 9.6 g of compound 2-9. (Yield 61%, MS: [M+H]+= 585)

Manufacturing Example 2-10

In a nitrogen atmosphere, 4-bromo-9-phenyl-9H-carbazole (10 g, 31 mmol), compound D (9.2 g, 31.3 mmol), and sodium tert-butoxide (3.9 g, 40.3 mmol) were added to 200 ml of Xylene, stirred and refluxed. did. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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 11.4 g of compound 2-10. (Yield 69%, MS: [M+H]+= 535)

Manufacturing Example 2-11

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), sub6 (17 g, 60.4 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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 subD-1. (Yield 57%, MS: [M+H]+= 368)

In a nitrogen atmosphere, subD-1 (10 g, 27.2 mmol), compound D (8.1 g, 27.5 mmol), and sodium tert-butoxide (3.4 g, 35.3 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After 5 hours, the reaction was completed, it was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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 9.2 g of compound 2-11. (Yield 54%, MS: [M+H]+= 625)

Manufacturing Example 2-12

In a nitrogen atmosphere, 9-bromo-11H-benzo[a]carbazole (10 g, 33.8 mmol), sub4 (7 g, 34.1 mmol), and sodium tert-butoxide (4.2 g, 43.9 mmol) were added to 200 ml of Xylene, stirred, and refluxed. . Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.7 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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 7.3 g of subD-2. (Yield 58%, MS: [M+H]+= 372)

In a nitrogen atmosphere, subD-2 (10g, 26.9mmol) and sub7 (6.1g, 29.5mmol) were added to 200ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (11.1g, 80.6mmol) was dissolved in 33ml of water and stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.3g, 0.3mmol) was added. After reacting for 10 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 7.9 g of subD-3. (Yield 65%, MS: [M+H]+= 454)

In a nitrogen atmosphere, subD-3 (10 g, 22 mmol), compound D (6.5 g, 22.2 mmol), and sodium tert-butoxide (2.8 g, 28.6 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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 10.2 g of compound 2-12. (Yield 65%, MS: [M+H]+= 711)

Manufacturing Example 2-13

In a nitrogen atmosphere, 5H-benzo[b]carbazole (10 g, 46 mmol), sub8 (13.1 g, 46.5 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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 12.9 g of subD-4. (Yield 67%, MS: [M+H]+= 418)

In a nitrogen atmosphere, subD-4 (10 g, 23.9 mmol), compound D (7.1 g, 24.2 mmol), and sodium tert-butoxide (3 g, 31.1 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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 2-13. (Yield 65%, MS: [M+H]+= 675)

Manufacturing Example 2-14

In a nitrogen atmosphere, 7H-benzo[c]carbazole (10 g, 46 mmol), sub9 (12.4 g, 46.5 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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 11.3 g of subD-5. (Yield 61%, MS: [M+H]+= 404)

In a nitrogen atmosphere, subD-5 (10 g, 24.8 mmol), compound D (7.3 g, 25 mmol), and sodium tert-butoxide (3.1 g, 32.2 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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 9.6 g of compound 2-14. (Yield 59%, MS: [M+H]+= 661)

Manufacturing Example 2-15

In a nitrogen atmosphere, 7-bromo-11H-benzo[a]carbazole (10 g, 33.8 mmol), sub4 (6.9 g, 34.1 mmol), and sodium tert-butoxide (4.2 g, 43.9 mmol) were added to 200 ml of Xylene, stirred and refluxed. did. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.7 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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 8.1 g of subE-1. (Yield 65%, MS: [M+H]+= 372)

In a nitrogen atmosphere, subE-1 (10 g, 26.9 mmol), compound E (8 g, 27.1 mmol), and sodium tert-butoxide (3.4 g, 34.9 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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 10.8 g of compound 2-15. (Yield 69%, MS: [M+H]+= 585)

Manufacturing Example 2-16

In a nitrogen atmosphere, 10-bromo-7H-benzo[c]carbazole (10 g, 33.8 mmol), sub4 (6.9 g, 34.1 mmol), and sodium tert-butoxide (4.2 g, 43.9 mmol) were added to 200 ml of Xylene, stirred and refluxed. did. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.7 mmol) was added. After 5 hours, the reaction was completed, it was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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 7.3 g of subE-2. (Yield 58%, MS: [M+H]+= 372)

In a nitrogen atmosphere, subE-2 (10 g, 26.9 mmol), compound E (8 g, 27.1 mmol), and sodium tert-butoxide (3.4 g, 34.9 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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 67%, MS: [M+H]+= 585)

Manufacturing Example 2-17

In a nitrogen atmosphere, 5H-benzo[b]carbazole (10 g, 46 mmol), sub10 (13.8 g, 46.5 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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 subE-3. (Yield 53%, MS: [M+H]+= 434)

In a nitrogen atmosphere, subE-3 (10 g, 23 mmol), compound E (6.8 g, 23.3 mmol), and sodium tert-butoxide (2.9 g, 30 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, 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 9.4 g of compound 2-17. (Yield 59%, MS: [M+H]+= 691)

[Example]

Example 1

A glass substrate coated with a thin film of ITO (indium tin oxide) with a thickness of 1,000 Å was placed in distilled water with a detergent dissolved in it and washed ultrasonically. At this time, a detergent from Fischer Co. was used, and distilled water filtered secondarily using a filter from Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, ultrasonic cleaning was repeated twice with distilled water for 10 minutes. After washing with distilled water, it was ultrasonic washed with solvents of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. Additionally, the substrate was cleaned for 5 minutes using oxygen plasma and then transported to a vacuum evaporator.

On the ITO transparent electrode prepared in this way, the following HI-1 compound was formed as a hole injection layer to a thickness of 1150 Å, and the following A-1 compound was p-doped at a concentration of 1.5% by weight. The following HT-1 compound was vacuum deposited on the hole injection layer to form a hole transport layer with a film thickness of 800 Å. Subsequently, the following EB-1 compound was vacuum deposited to a film thickness of 150 Å on the hole transport layer to form an electron blocking layer. Next, on the EB-1 deposition film, Compound 1-1 and Compound 2-1 as hosts and Dp-7 compound as a dopant were vacuum deposited at a weight ratio of 49:49:2 to form a red light-emitting layer with a thickness of 400 Å. The following HB-1 compound was vacuum deposited to a film thickness of 30 Å on the light emitting layer to form a hole blocking layer. Next, the following ET-1 compound and the following LiQ compound were vacuum deposited on the hole blocking layer at a weight ratio of 2:1 to form an electron injection and transport layer with 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 1,000 Å on the electron injection and transport layer.

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

Examples 2 to 205

Organic light emission was performed in the same manner as in Example 1, except that the compound of Formula 1 shown in Table 1 as the first host and the compound of Formula 2 shown in Table 1 as the second host were co-deposited in a 1:1 ratio. The device was manufactured.

Comparative Examples 1 to 30

Example 1 and An organic light emitting device was manufactured using the same method. Comparative compounds B-1 to B-3 are as follows.

Comparative Examples 31 to 63

Example 1 and An organic light emitting device was manufactured using the same method. Comparative compounds C-1 to C-3 are as follows.

[Experimental example]

When current was applied to the organic light-emitting devices manufactured in Examples 1 to 205 and Comparative Examples 1 to 63, the voltage, efficiency, and lifespan were measured (based on 15 mA/cm ² ), and the results are shown in Table 1 below. It is shown in Table 4. Lifespan T95 refers to the time it takes for luminance to decrease from the initial luminance (6,000 nits) to 95%.

division first host 2nd host Driving voltage (V) Efficiency (cd/A) Life T95(hr) Luminous color Example 1 Compound 1-1 Compound 2-1 3.69 17.54 172 Red Example 2 Compound 2-5 3.63 17.94 174 Red Example 3 Compound 2-9 3.61 17.56 166 Red Example 4 Compound 2-13 3.68 17.43 151 Red Example 5 Compound 2-17 3.68 17.98 177 Red Example 6 Compound 1-2 Compound 2-2 3.63 17.81 179 Red Example 7 Compound 2-6 3.63 17.72 155 Red Example 8 Compound 2-10 3.60 17.00 157 Red Example 9 Compound 2-14 3.64 17.34 162 Red Example 10 Compound 2-17 3.67 17.87 166 Red Example 11 Compound 1-3 Compound 2-3 3.71 19.48 185 Red Example 12 Compound 2-7 3.79 18.24 229 Red Example 13 Compound 2-11 3.77 18.65 188 Red Example 14 Compound 2-15 3.72 19.41 189 Red Example 15 Compound 2-17 3.72 18.85 230 Red Example 16 Compound 1-4 Compound 2-4 3.70 18.63 204 Red Example 17 Compound 2-8 3.77 19.13 224 Red Example 18 Compound 2-12 3.72 18.08 207 Red Example 19 Compound 2-16 3.71 19.24 227 Red Example 20 Compound 2-17 3.78 18.04 213 Red Example 21 Compound 1-5 Compound 2-1 3.57 17.54 196 Red Example 22 Compound 2-5 3.61 17.94 207 Red Example 23 Compound 2-9 3.59 17.56 203 Red Example 24 Compound 2-13 3.64 17.43 206 Red Example 25 Compound 2-17 3.61 17.98 198 Red Example 26 Compound 1-6 Compound 2-2 3.60 17.81 206 Red Example 27 Compound 2-6 3.56 17.72 176 Red Example 28 Compound 2-10 3.59 17.00 175 Red Example 29 Compound 2-14 3.63 17.34 181 Red Example 30 Compound 2-17 3.65 17.87 204 Red Example 31 Compound 1-7 Compound 2-3 3.60 19.80 172 Red Example 32 Compound 2-7 3.61 21.43 174 Red Example 33 Compound 2-11 3.59 21.75 166 Red Example 34 Compound 2-15 3.64 22.61 151 Red Example 35 Compound 2-17 3.61 22.81 177 Red Example 36 Compound 1-8 Compound 2-4 3.60 22.09 179 Red Example 37 Compound 2-8 3.56 19.67 155 Red Example 38 Compound 2-12 3.59 19.61 157 Red Example 39 Compound 2-16 3.63 22.13 162 Red Example 40 Compound 2-17 3.65 21.66 166 Red Example 41 Compound 1-9 Compound 2-1 3.83 19.01 190 Red Example 42 Compound 2-5 3.87 19.14 191 Red Example 43 Compound 2-9 3.89 20.11 200 Red Example 44 Compound 2-13 3.81 20.39 189 Red Example 45 Compound 2-17 3.85 19.65 181 Red Example 46 Compound 1-10 Compound 2-2 3.80 19.81 191 Red Example 47 Compound 2-6 3.84 19.43 185 Red Example 48 Compound 2-10 3.80 19.90 180 Red Example 49 Compound 2-14 3.88 19.01 187 Red Example 50 Compound 2-17 3.86 19.49 185 Red Example 51 Compound 1-11 Compound 2-3 3.60 17.61 159 Red Example 52 Compound 2-7 3.65 17.33 174 Red Example 53 Compound 2-11 3.62 17.81 171 Red Example 54 Compound 2-15 3.60 17.20 152 Red Example 55 Compound 2-17 3.63 18.09 166 Red Example 56 Compound 1-12 Compound 2-4 3.66 18.08 155 Red Example 57 Compound 2-8 3.60 18.23 174 Red Example 58 Compound 2-12 3.61 17.20 165 Red Example 59 Compound 2-16 3.65 17.83 151 Red Example 60 Compound 2-17 3.66 17.04 171 Red Example 61 Compound 1-13 Compound 2-1 3.76 18.19 207 Red Example 62 Compound 2-5 3.70 18.00 203 Red Example 63 Compound 2-9 3.75 18.91 188 Red Example 64 Compound 2-13 3.71 19.08 198 Red Example 65 Compound 2-17 3.73 18.85 208 Red Example 66 Compound 1-14 Compound 2-2 3.76 18.02 206 Red Example 67 Compound 2-6 3.71 18.84 192 Red Example 68 Compound 2-10 3.75 18.51 210 Red Example 69 Compound 2-14 3.78 18.55 199 Red Example 70 Compound 2-17 3.71 19.29 190 Red Example 71 Compound 1-15 Compound 2-3 3.63 17.61 204 Red Example 72 Compound 2-7 3.59 17.33 202 Red Example 73 Compound 2-11 3.65 17.81 198 Red Example 74 Compound 2-15 3.58 17.20 182 Red Example 75 Compound 2-17 3.64 18.09 208 Red Example 76 Compound 1-16 Compound 2-4 3.58 18.08 184 Red Example 77 Compound 2-8 3.64 18.23 175 Red Example 78 Compound 2-12 3.61 17.20 194 Red Example 79 Compound 2-16 3.60 17.83 208 Red Example 80 Compound 2-17 3.57 17.04 177 Red Example 81 Compound 1-17 Compound 2-1 3.63 20.25 187 Red Example 82 Compound 2-5 3.59 22.94 188 Red Example 83 Compound 2-9 3.65 21.45 192 Red Example 84 Compound 2-13 3.58 21.02 194 Red Example 85 Compound 2-17 3.64 20.02 207 Red Example 86 Compound 1-18 Compound 2-2 3.58 20.93 229 Red Example 87 Compound 2-6 3.64 21.65 213 Red Example 88 Compound 2-10 3.61 19.64 201 Red Example 89 Compound 2-14 3.60 22.85 214 Red Example 90 Compound 2-17 3.57 22.40 224 Red Example 91 Compound 1-19 Compound 2-3 3.68 18.20 162 Red Example 92 Compound 2-7 3.61 18.17 161 Red Example 93 Compound 2-11 3.62 17.50 180 Red Example 94 Compound 2-15 3.61 17.53 168 Red Example 95 Compound 2-17 3.68 18.16 175 Red Example 96 Compound 1-20 Compound 2-4 3.60 17.88 174 Red Example 97 Compound 2-8 3.63 18.11 162 Red Example 98 Compound 2-12 3.60 17.00 179 Red Example 99 Compound 2-16 3.65 17.50 158 Red Example 100 Compound 2-17 3.67 17.63 152 Red Example 101 Compound 1-21 Compound 2-1 3.73 19.08 207 Red Example 102 Compound 2-5 3.74 18.67 198 Red Example 103 Compound 2-9 3.79 18.91 194 Red Example 104 Compound 2-13 3.75 18.41 195 Red Example 105 Compound 2-17 3.71 18.84 208 Red Example 106 Compound 1-23 Compound 2-2 3.75 18.66 195 Red Example 107 Compound 2-6 3.78 18.33 199 Red Example 108 Compound 2-10 3.77 19.23 230 Red Example 109 Compound 2-14 3.73 19.45 200 Red Example 110 Compound 2-17 3.75 18.76 226 Red Example 111 Compound 1-25 Compound 2-3 3.59 18.20 187 Red Example 112 Compound 2-7 3.62 18.17 172 Red Example 113 Compound 2-11 3.63 17.50 194 Red Example 114 Compound 2-15 3.65 17.53 181 Red Example 115 Compound 2-17 3.57 18.16 194 Red Example 116 Compound 1-26 Compound 2-4 3.61 17.88 172 Red Example 117 Compound 2-8 3.59 18.11 175 Red Example 118 Compound 2-12 3.62 17.00 200 Red Example 119 Compound 2-16 3.63 17.50 183 Red Example 120 Compound 2-17 3.55 17.63 172 Red Example 121 Compound 1-27 Compound 2-1 3.81 19.32 183 Red Example 122 Compound 2-5 3.86 19.20 180 Red Example 123 Compound 2-9 3.85 19.34 192 Red Example 124 Compound 2-13 3.81 19.92 194 Red Example 125 Compound 2-17 3.88 19.46 183 Red Example 126 Compound 1-28 Compound 2-2 3.88 19.31 183 Red Example 127 Compound 2-6 3.86 20.48 198 Red Example 128 Compound 2-10 3.85 19.74 194 Red Example 129 Compound 2-14 3.89 19.81 189 Red Example 130 Compound 2-17 3.89 19.01 199 Red Example 131 Compound 1-32 Compound 2-3 3.84 20.48 198 Red Example 132 Compound 2-7 3.82 19.40 196 Red Example 133 Compound 2-11 3.81 20.27 197 Red Example 134 Compound 2-15 3.87 20.40 193 Red Example 135 Compound 2-17 3.85 19.98 191 Red Example 136 Compound 1-33 Compound 2-4 3.86 20.02 190 Red Example 137 Compound 2-8 3.80 20.16 191 Red Example 138 Compound 2-12 3.82 20.14 182 Red Example 139 Compound 2-16 3.86 19.69 190 Red Example 140 Compound 2-17 3.87 19.72 183 Red Example 141 Compound 1-34 Compound 2-1 3.54 20.37 152 Red Example 142 Compound 2-5 3.65 21.48 175 Red Example 143 Compound 2-9 3.56 22.03 173 Red Example 144 Compound 2-13 3.58 21.65 177 Red Example 145 Compound 2-17 3.59 20.95 176 Red Example 146 Compound 1-35 Compound 2-2 3.57 19.56 166 Red Example 147 Compound 2-6 3.63 21.77 150 Red Example 148 Compound 2-10 3.62 20.67 151 Red Example 149 Compound 2-14 3.65 22.96 177 Red Example 150 Compound 2-17 3.63 22.78 160 Red Example 151 Compound 1-36 Compound 2-3 3.79 17.66 152 Red Example 152 Compound 2-7 3.67 18.25 175 Red Example 153 Compound 2-11 3.67 18.45 173 Red Example 154 Compound 2-15 3.67 17.97 177 Red Example 155 Compound 2-17 3.61 18.08 176 Red Example 156 Compound 1-37 Compound 2-4 3.67 18.13 166 Red Example 157 Compound 2-8 3.67 18.01 150 Red Example 158 Compound 2-12 3.66 17.11 151 Red Example 159 Compound 2-16 3.63 17.88 177 Red Example 160 Compound 2-17 3.61 17.35 160 Red Example 161 Compound 1-38 Compound 2-1 3.79 18.39 216 Red Example 162 Compound 2-5 3.77 18.59 197 Red Example 163 Compound 2-9 3.73 18.67 220 Red Example 164 Compound 2-13 3.71 18.81 217 Red Example 165 Compound 2-17 3.74 18.42 188 Red Example 166 Compound 1-39 Compound 2-2 3.74 18.51 212 Red Example 167 Compound 2-6 3.71 18.92 215 Red Example 168 Compound 2-10 3.71 18.54 201 Red Example 169 Compound 2-14 3.72 19.41 215 Red Example 170 Compound 2-17 3.71 18.31 195 Red Example 171 Compound 1-41 Compound 2-3 3.89 19.71 210 Red Example 172 Compound 2-7 3.84 19.82 200 Red Example 173 Compound 2-11 3.87 19.58 204 Red Example 174 Compound 2-15 3.86 20.41 198 Red Example 175 Compound 2-17 3.89 19.77 186 Red Example 176 Compound 1-42 Compound 2-4 3.73 18.22 205 Red Example 177 Compound 2-8 3.73 18.35 209 Red Example 178 Compound 2-12 3.70 18.02 213 Red Example 179 Compound 2-16 3.71 18.46 188 Red Example 180 Compound 2-17 3.73 19.18 215 Red Example 181 Compound 1-43 Compound 2-1 3.70 19.33 224 Red Example 182 Compound 2-5 3.76 18.25 204 Red Example 183 Compound 2-9 3.70 18.83 224 Red Example 184 Compound 2-13 3.78 18.89 187 Red Example 185 Compound 2-17 3.71 19.08 215 Red Example 186 Compound 1-44 Compound 2-2 3.61 17.29 176 Red Example 187 Compound 2-6 3.69 17.37 162 Red Example 188 Compound 2-10 3.60 17.68 172 Red Example 189 Compound 2-14 3.60 17.42 174 Red Example 190 Compound 2-17 3.63 17.69 156 Red Example 191 Compound 1-45 Compound 2-3 3.65 17.62 171 Red Example 192 Compound 2-7 3.67 17.10 162 Red Example 193 Compound 2-11 3.66 18.19 154 Red Example 194 Compound 2-15 3.65 17.32 151 Red Example 195 Compound 2-17 3.61 17.45 177 Red Example 196 Compound 1-46 Compound 2-4 3.55 18.12 183 Red Example 197 Compound 2-8 3.61 18.10 186 Red Example 198 Compound 2-12 3.64 18.29 180 Red Example 199 Compound 2-16 3.57 18.22 170 Red Example 200 Compound 2-17 3.58 17.56 196 Red Example 201 Compound 1-47 Compound 2-1 3.64 18.15 206 Red Example 202 Compound 2-5 3.55 17.98 210 Red Example 203 Compound 2-9 3.63 17.61 187 Red Example 204 Compound 2-13 3.65 17.25 192 Red Example 205 Compound 2-17 3.56 17.97 190 Red

division first host 2nd host Driving voltage (V) Efficiency (cd/A) Life T95(hr) Luminous color Comparative Example 1 Compound B-1 Compound 2-1 4.08 15.43 132 Red Comparative Example 2 Compound 2-5 4.02 16.67 138 Red Comparative Example 3 Compound 2-9 4.11 15.22 139 Red Comparative Example 4 Compound 2-13 4.07 16.43 133 Red Comparative Example 5 Compound 2-15 4.07 15.38 129 Red Comparative Example 6 Compound 2-2 4.05 16.01 141 Red Comparative Example 7 Compound 2-6 4.05 15.24 133 Red Comparative Example 8 Compound 2-10 4.06 16.18 144 Red Comparative Example 9 Compound 2-14 4.10 16.77 141 Red Comparative Example 10 Compound 2-17 4.14 15.35 128 Red Comparative Example 11 Compound B-2 Compound 2-3 4.25 14.29 101 Red Comparative Example 12 Compound 2-7 4.05 14.66 130 Red Comparative Example 13 Compound 2-11 4.06 14.93 123 Red Comparative Example 14 Compound 2-14 4.12 14.70 116 Red Comparative Example 15 Compound 2-15 4.06 14.13 126 Red Comparative Example 16 Compound 2-4 4.15 14.19 109 Red Comparative Example 17 Compound 2-8 4.03 14.95 127 Red Comparative Example 18 Compound 2-12 4.09 14.26 114 Red Comparative Example 19 Compound 2-16 4.03 14.72 124 Red Comparative Example 20 Compound 2-17 4.05 14.22 108 Red Comparative Example 21 Compound B-3 Compound 2-1 4.08 15.43 132 Red Comparative Example 22 Compound 2-5 4.02 16.67 138 Red Comparative Example 23 Compound 2-9 4.11 15.22 139 Red Comparative Example 24 Compound 2-13 4.07 16.43 133 Red Comparative Example 25 Compound 2-15 4.07 15.38 129 Red Comparative Example 26 Compound 2-2 4.05 16.01 141 Red Comparative Example 27 Compound 2-6 4.05 15.24 133 Red Comparative Example 28 Compound 2-10 4.06 16.18 144 Red Comparative Example 29 Compound 2-14 4.10 16.77 141 Red Comparative Example 30 Compound 2-17 4.14 15.35 128 Red

division first host 2nd host Driving voltage (V) Efficiency (cd/A) Life T95(hr) Luminous color Comparative Example 31 Compound 1 -1 Compound C-1 4.28 14.25 114 Red Comparative Example 32 Compound 1-4 4.28 14.21 135 Red Comparative Example 33 Compound 1-7 4.23 14.70 124 Red Comparative Example 34 Compound 1-13 4.28 14.71 110 Red Comparative Example 35 Compound 1-19 4.32 14.76 120 Red Comparative Example 36 Compound 1-23 4.34 14.24 110 Red Comparative Example 37 Compound 1-28 4.32 14.62 125 Red Comparative Example 38 Compound 1-32 4.29 14.05 116 Red Comparative Example 39 Compound 1-38 4.24 14.02 119 Red Comparative Example 40 Compound 1-41 4.26 14.29 127 Red Comparative Example 41 Compound 1-44 4.30 15.16 91 Red Comparative Example 42 Compound 1 -2 Compound C-2 4.20 14.42 122 Red Comparative Example 43 Compound 1-5 4.20 14.45 132 Red Comparative Example 44 Compound 1-8 4.29 14.80 128 Red Comparative Example 45 Compound 1-15 4.35 14.32 115 Red Comparative Example 46 Compound 1-20 4.32 14.77 115 Red Comparative Example 47 Compound 1-25 4.23 14.64 134 Red Comparative Example 48 Compound 1-30 4.20 14.14 127 Red Comparative Example 49 Compound 1-35 4.25 14.83 134 Red Comparative Example 50 Compound 1-39 4.22 14.98 116 Red Comparative Example 51 Compound 1-42 4.26 14.40 128 Red Comparative Example 52 Compound 1-45 4.26 15.81 114 Red Comparative Example 53 Compound 1-3 Compound C-3 4.45 11.14 68 Red Comparative Example 54 Compound 1-6 4.46 10.89 78 Red Comparative Example 55 Compound 1-9 4.43 10.01 94 Red Comparative Example 56 Compound 1-17 4.36 10.51 71 Red Comparative Example 57 Compound 1-22 4.43 12.14 85 Red Comparative Example 58 Compound 1-26 4.43 10.36 107 Red Comparative Example 59 Compound 1-31 4.50 11.92 60 Red Comparative Example 60 Compound 1-36 4.34 13.00 76 Red Comparative Example 61 Compound 1-40 4.50 10.63 72 Red Comparative Example 62 Compound 1-43 4.48 10.90 62 Red Comparative Example 63 Compound 1-47 4.26 15.80 122 Red

When current was applied to the organic light-emitting devices manufactured 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 device of the above example has a structure in which compound EB-1, a widely used material, is used as an electron blocking layer material, and compound Dp-7 is used as a red dopant material. When the compound of Formula 1 and the compound of Formula 2 of the present invention are co-deposited and used as a red light-emitting layer, it can be seen that the driving voltage decreases and the efficiency and lifespan increase compared to the comparative example, as shown in Table 1.

However, as shown in Table 2, when co-deposited with Comparative Example Compounds B-1 to B-3 and the compound of Formula 2 of the present invention and used as a red light-emitting layer, the driving voltage generally increases and the efficiency and efficiency decrease compared to the combination of the present invention. As shown in Table 3, even when co-deposited with Comparative Example Compounds C-1 to C-3 and the compound of Formula 1 of the present invention and used as a red light-emitting layer, the driving voltage increased and efficiency and lifespan decreased. The results were shown.

From these results, when combining the compound of formula 1, which is the first host of the present invention, with the compound of formula 2, which is the second host, energy is transferred well to the red dopant in the red light-emitting layer, improving the driving voltage and increasing efficiency and lifespan. 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 is more stable than the combination with the comparative example compound, and electrons and holes combine to form excitons through a more stable balance in the light-emitting layer, thereby greatly increasing efficiency and lifespan. A rise could be seen. In conclusion, it was confirmed that the driving voltage, luminous efficiency, and lifespan characteristics of an organic light-emitting device can be improved when the compound of Formula 1 and the compound of Formula 2 of the present invention are combined and co-deposited and used as a host for a red light-emitting layer.

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 (11)

anode; cathode; And a light emitting layer between the anode and the cathode,
The light-emitting layer includes a compound represented by Formula 1 below and a compound represented by Formula 2 below,
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 C _2-60 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O and S,
L ₁ and L ₂ are each independently a single bond; Or substituted or unsubstituted C _6-60 arylene,
L ₃ is a single bond; Or substituted or unsubstituted C _6-60 arylene,
R ₁ is each independently hydrogen or deuterium; Or, two adjacent ones combine to form a benzene ring, and the remainder is each independently hydrogen or deuterium,
R ₂ is each independently hydrogen or deuterium; Or, two adjacent ones combine to form a benzene ring, and the remainder is each independently hydrogen or deuterium,
[Formula 2]

In Formula 2,
A and B are each independently a benzene ring or a naphthalene ring fused to an adjacent ring,
L' ₁ is a single bond; Or substituted or unsubstituted C _6-60 arylene,
Ar' ₁ is a substituent represented by Formula 3-1 or Formula 3-2,
[Formula 3-1]

[Formula 3-2]

In Formula 3-1 and Formula 3-2,
C and D are each independently a benzene ring fused to an adjacent ring, or a naphthalene ring,
Ar' ₂ is substituted or unsubstituted C _6-60 aryl; or C _2-60 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O, and S.
According to paragraph 1,
The 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 clause 1.
According to paragraph 1,
Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, naphthyl, phenanthrenyl, phenylcarbazolyl, dibenzofuranyl, dibenzothiophenyl, or benzonaphthofuranyl,
Organic light emitting device.
According to paragraph 1,
L ₁ and L ₂ are each independently a single bond, phenylene, or naphthylene,
Organic light emitting device.
According to paragraph 1,
L ₃ is a single bond, phenylene, biphenylylene, or naphthylene,
Organic light emitting device.
According to paragraph 1,
The compound represented by Formula 1 is any one selected from the group consisting of:
Organic light emitting device:

According to paragraph 1,
The formula 2 is represented by any one selected from the group consisting of the following formulas 2-1 to 2-6,
Organic light emitting device:

In Formulas 2-1 to 2-6,
L' ₁ and Ar' ₁ are as defined in clause 1.
According to paragraph 1,
L' ₁ is a single bond; Or any one selected from the group consisting of:
Organic light emitting device:

In the above, X' is NR', C(R') ₂ , O, or S,
R' is each independently hydrogen; Substituted or unsubstituted C _1-20 alkyl; Or substituted or unsubstituted C _6-20 aryl.
According to clause 8,
X' is O or S,
Organic light emitting device.
According to paragraph 1,
Ar' ₁ is any one selected from the group consisting of:
Organic light emitting device:

According to paragraph 1,
The compound represented by Formula 2 is any one selected from the group consisting of:
Organic light emitting device:

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