KR20220000844A - Organic light emitting device - Google Patents

Abstract

The present invention provides an organic light emitting device. The organic light emitting device may include: an anode; a cathode; and a light emitting layer between the anode and the cathode. The light emitting layer includes a host comprising a compound represented by the following chemical formula 1 and a compound represented by the following chemical formula 2. An object of the present invention is to provide an organic light emitting device having improved driving voltage, efficiency, and lifetime.

Description

Organic light emitting device

The present invention relates to an organic light emitting device.

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

An organic light emitting device generally has a structure including an anode and a cathode and an organic material layer between the anode and the cathode. The organic layer is often formed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light-emitting device, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. In the structure of the organic light emitting device, when a voltage is applied between the two electrodes, holes are injected into the organic material layer from the anode and electrons from the cathode are injected into the organic material layer. When the injected holes and electrons meet, excitons are formed, and the excitons It lights up when it falls back to the ground state.

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

Korean Patent Publication No. 10-2000-0051826

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

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

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

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

Organic light emitting device:

[Formula 1]

In Formula 1,

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

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

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

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

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

[Formula 2]

In Formula 2,

L ₄ and L ₅ are each independently a single bond, substituted or unsubstituted C _{6-60 arylene, or substituted or unsubstituted C 2} including any one or more selected from the group consisting of N, O and S _-60 heteroarylene;

Ar _{3 To} Ar ₆ are each independently substituted or unsubstituted C _{6-60 aryl, or substituted or unsubstituted C 2-60} heteroaryl including at least one selected from the group consisting of N, O and S to be.

The above-described organic light emitting device has excellent driving voltage, efficiency, and lifetime.

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

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

또는

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

or

means a bond connected to another substituent.

As used herein, the term "substituted or unsubstituted" refers to deuterium; halogen group; nitrile group; nitro group; hydroxyl group; carbonyl group; ester group; imid; amino group; a phosphine oxide group; alkoxy group; aryloxy group; alkyl thiooxy group; arylthioxy group; an alkyl sulfoxy group; arylsulfoxy group; silyl group; boron group; an alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; aralkenyl group; an alkylaryl group; an alkylamine group; an aralkylamine group; heteroarylamine group; arylamine group; an arylphosphine group; Or N, O, and S atom means that it is substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing one or more, or substituted or unsubstituted, two or more of the above-exemplified substituents are linked. . For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.

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

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

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

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

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

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

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

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

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

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

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.In the present specification, the fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure. When the fluorenyl group is substituted,

etc. can be However, the present invention is not limited thereto.

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

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

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

positive and negative

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

As the anode material, a material having a large work function is generally preferred so that holes can be smoothly injected into the organic material layer. Specific examples of the anode material include metals such as vanadium, chromium, copper, zinc, gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SnO _{2 :Sb;} conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDOT), polypyrrole, and polyaniline, but are not limited thereto.

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

light emitting layer

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

Specifically, when the host consisting of two types of the compound represented by Formula 1 and the compound represented by Formula 2 is applied as either one of the two compounds (one type of host), any one of the two compounds is used as the other. When changing to a compound of the structure (two types of hosts), when both compounds are changed to a compound of a different structure (two types of hosts), at the same time changing one of the two compounds to a compound of a different structure Compared to the case where compounds of different structures are added (three kinds of hosts), etc., it has a remarkable synergistic effect, and can improve the driving voltage, efficiency, and lifespan of the organic light-emitting device.

Hereinafter, the two compounds will be described in detail.

First, Chemical Formula 1 may be represented by any one selected from the group consisting of Chemical Formulas 1-1 to 1-9:

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

In Formula 1, Ar ₁ and Ar ₂ are each independently substituted or unsubstituted C _6-30 aryl; Or it may be _{C 2-30} heteroaryl including any one or more selected from the group consisting of substituted or unsubstituted N, O and S.

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

L ₁ and L ₂ are each independently a single bond; Or it may be a substituted or unsubstituted C _{6-30 arylene.}

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

L ₃ is a single bond; Or it may be a substituted or unsubstituted C _{6-30 arylene.}

For example, L ₃ may be a single bond, phenylene, biphenylrylene, or naphthylene.

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

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

[Scheme 1]

In Scheme 1, definitions other than X are as previously defined, wherein X is halogen, more preferably bromo or chloro.

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

Meanwhile, in Chemical Formula 2, Chemical Formula 2 may be represented by the following Chemical Formula 2-1 or 2-2.

[Formula 2-1]

[Formula 2-2]

In Formulas 2-1 to 2-2, L ₄ , L ₅ , and Ar ₃ to Ar ₆ are each as defined above.

For example, Chemical Formula 2-1 may be represented by any one selected from the group consisting of the following 2-1-1 to 2-1-6, and Chemical Formula 2-2 may be represented by the following 2-2-1 to 2-2 It may be represented by any one selected from the group consisting of -4:

In each of the above formulas, L ₄ , L ₅ , and Ar ₃ to Ar ₆ are each as defined above.

In Formula 1, any one or more selected from the group consisting of a single bond, substituted or unsubstituted C _6-30 arylene, or substituted or unsubstituted N, O, and S, _{each independently of L 4} and L ₅ It may be a C _{2-30 heteroarylene comprising a.}

Specifically, L ₄ and L ₅ may each independently be a single bond or phenylene. For example, _{any one of L 4} and L ₅ may be a single bond, and the other may be a single bond or phenylene, but is not limited thereto.

Ar _{3 To} Ar ₆ are each independently substituted or unsubstituted C _{6-30 aryl, or substituted or unsubstituted C 2-30} heteroaryl including at least one selected from the group consisting of N, O and S can be

For example, Ar ₃ to Ar ₆ are each independently phenyl, (naphthyl)phenylyl, (phenanthrenyl)phenylyl, biphenylyl, (phenyl)biphenylyl, naphthyl, (phenyl)naphthyl, phenanthre nyl, dibenzofuranyl, dibenzothiophenyl, or benzonaphthofuranyl.

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

On the other hand, the present invention provides a method for preparing a compound represented by Formula 2, as shown in Scheme 2 below.

[Scheme 2]

In Scheme 2, _{the definitions of L 4} , L ₅ , and Ar ₃ to Ar ₆ are as defined above.

Steps 2-1 and 2-2 are amine substitution reactions, preferably performed in the presence of a palladium catalyst and a base, and the reactor for the amine substitution reaction can be changed as known in the art. The manufacturing method may be more specific in Preparation Examples to be described later.

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

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

hole transport layer

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

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

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

hole injection layer

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

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

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

electron transport layer

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

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

Specific examples of the electron transport material include an Al complex of 8-hydroxyquinoline; complexes containing Alq _{3 ;} organic radical compounds; hydroxyflavone-metal complexes, and the like, but are not limited thereto. The electron transport layer may be used with any desired cathode material as used in accordance with the prior art. In particular, examples of suitable cathode materials are conventional materials having a low work function and followed by a layer of aluminum or silver. Specifically cesium, barium, calcium, ytterbium and samarium, followed in each case by an aluminum layer or a silver layer.

electron injection layer

The organic light emitting diode according to the present invention may further include an electron injection layer between the electron transport layer and the cathode, if necessary.

The electron injection layer is a layer that injects electrons from the electrode, has the ability to transport electrons, has an electron injection effect from the cathode, an excellent electron injection effect on the light emitting layer or the light emitting material, and hole injection of excitons generated in the light emitting layer. It is preferable to use a compound which prevents movement to a layer and is excellent in the ability to form a thin film.

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

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

organic light emitting device

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

The organic light emitting device according to the present invention may be manufactured by sequentially stacking the above-described components. At this time, by using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, a metal or conductive metal oxide or an alloy thereof is deposited on a substrate to form an anode And, after forming each of the above-mentioned layers thereon, it can be prepared by depositing a material that can be used as a cathode thereon.

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

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

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

[Production Example]

Preparation 1-1

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), compound sub1 (25.6 g, 62.8 mmol), and potassium phosphate (38.1 g, 179.4 mmol) were added to xylene (200 ml) and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added thereto. After 3 hours, when the reaction was completed, the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 17.7 g of Compound 1-1. (Yield 55%, MS: [M+H] ⁺ = 539)

Preparation 1-2

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), compound sub2 (25.6 g, 62.8 mmol), and potassium phosphate (38.1 g, 179.4 mmol) were added to xylene (200 ml) and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added thereto. After 2 hours, when the reaction was completed, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 19 g of compound 1-2. (yield 59%, MS: [M+H] ⁺ = 539)

Preparation 1-3

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), compound sub3 (27.2 g, 62.8 mmol), and potassium phosphate (38.1 g, 179.4 mmol) were added to xylene (200 ml) and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added thereto. After 3 hours, when the reaction was completed, the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 18.5 g of compound 1-3. (Yield 55%, MS: [M+H] ⁺ = 564)

Preparation Example 1-4

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), compound sub4 (30.4 g, 62.8 mmol), and potassium phosphate (38.1 g, 179.4 mmol) were added to xylene (200 ml) and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added thereto. After 3 hours, when the reaction was completed, the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 20.9 g of Compound 1-4. (Yield 57%, MS: [M+H] ⁺ = 615)

Preparation 1-5

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), compound sub5 (29.5 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to xylene (200 ml) and stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added thereto. After 3 hours, when the reaction was completed, the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 23.3 g of Compound 1-5. (Yield 65%, MS: [M+H] ⁺ = 601)

Preparation 1-6

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), compound sub6 (29.5 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to xylene (200 ml) and stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added thereto. After 3 hours, when the reaction was completed, the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 20.5 g of Compound 1-6. (Yield 57%, MS: [M+H] ⁺ = 601)

Preparation 1-7

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), compound sub7 (27.2 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to xylene (200 ml) and stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added thereto. After 2 hours, when the reaction was completed, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 19.2 g of Compound 1-7. (Yield 57%, MS: [M+H] ⁺ = 565)

Preparation 1-8

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), compound sub8 (32.7 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to xylene (200 ml) and stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added thereto. After 2 hours, when the reaction was completed, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 26.4 g of Compound 1-8. (Yield 68%, MS: [M+H] ⁺ = 651)

Preparation 1-9

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), compound sub9 (30.4 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to xylene (200 ml) and stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added thereto. After 3 hours, when the reaction was completed, the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 24.6 g of compound 1-9. (Yield 67%, MS: [M+H] ⁺ = 615)

Preparation 1-10

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), compound sub10 (30.4 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to xylene (200 ml) and stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added thereto. After 3 hours, when the reaction was completed, the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 23.5 g of Compound 1-10. (Yield 64%, MS: [M+H] ⁺ = 615)

Preparation Example 1-11

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), compound sub11 (27.2 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to xylene (200 ml) and stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added thereto. After 3 hours, when the reaction was completed, the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 17.5 g of Compound 1-11. (Yield 52%, MS: [M+H] ⁺ = 565)

Preparation Example 1-12

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), compound sub12 (27.9 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to xylene (200 ml) and stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added thereto. After 2 hours, when the reaction was completed, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 18.2 g of Compound 1-12. (Yield 53%, MS: [M+H] ⁺ = 575)

Preparation 1-13

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), compound sub13 (29.5 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to xylene (200 ml) and stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added thereto. After 3 hours, when the reaction was completed, the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 19.4 g of Compound 1-13. (Yield 54%, MS: [M+H] ⁺ = 601)

Preparation 1-14

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), compound sub14 (35.1 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to xylene (200 ml) and stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added thereto. After 3 hours, when the reaction was completed, the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 28.4 g of Compound 1-14. (yield 69%, MS: [M+H] ⁺ = 690)

Preparation 1-15

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), compound sub15 (31 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to xylene (200 ml) and stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added thereto. After 3 hours, when the reaction was completed, the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 26.1 g of Compound 1-15. (Yield 70%, MS: [M+H] ⁺ = 625)

Preparation 1-16

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), compound sub16 (31.4 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to xylene (200 ml) and stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added thereto. After 3 hours, when the reaction was completed, the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 22.2 g of Compound 1-16. (yield 59%, MS: [M+H] ⁺ = 631)

Preparation 1-17

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), compound sub17 (26.4 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to xylene (200 ml) and stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added thereto. After 3 hours, when the reaction was completed, the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 18.1 g of Compound 1-17. (Yield 55%, MS: [M+H] ⁺ = 551)

Preparation Example 1-18

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), compound sub18 (32 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to xylene (200 ml), stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added thereto. After 2 hours, when the reaction was completed, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 24.5 g of compound 1-18. (Yield 64%, MS: [M+H] ⁺ = 641)

Preparation 1-19

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), compound sub19 (31.1 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to xylene (200 ml) and stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added thereto. After 2 hours, when the reaction was completed, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 25.1 g of Compound 1-19. (Yield 67%, MS: [M+H] ⁺ = 627)

Preparation 1-20

In a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), compound sub20 (33 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to xylene (200 ml) and stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added thereto. After 3 hours, when the reaction was completed, the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 20 g of compound 1-20. (Yield 51%, MS: [M+H] ⁺ = 657)

Preparation 1-21

7H-benzo [c] carbazole (10 g, 46 mmol), compound sub21 (18.1 g, 48.3 mmol), potassium phosphate (29.3 g, 138.1 mmol) in xylene (200 ml) in a nitrogen atmosphere, stirred and refluxed did After that, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, when the reaction was completed, the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.3 g of compound 1-21. (Yield 56%, MS: [M+H] ⁺ = 555)

Preparation 1-22

In a nitrogen atmosphere, 7H-benzo [c] carbazole (10 g, 46 mmol), compound sub7 (21 g, 48.3 mmol), sodium tert-butoxide (5.7 g, 59.8 mmol) was added to xylene (200 ml) Stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, when the reaction was completed, the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.7 g of compound 1-22. (Yield 52%, MS: [M+H] ⁺ = 615)

Preparation 1-23

7H-benzo [c] carbazole (10 g, 46 mmol), compound sub22 (26.9 g, 48.3 mmol), sodium tert-butoxide (5.7 g, 59.8 mmol) in xylene (200 ml) in a nitrogen atmosphere Stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, when the reaction was completed, the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 22 g of compound 1-23. (Yield 65%, MS: [M+H] ⁺ = 737)

Preparation 1-24

In a nitrogen atmosphere, 7H-benzo [c] carbazole (10 g, 46 mmol), compound sub23 (16.6 g, 48.3 mmol), sodium tert-butoxide (5.7 g, 59.8 mmol) was added to xylene (200 ml) Stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, when the reaction was completed, the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.1 g of compound 1-24. (Yield 50%, MS: [M+H] ⁺ = 525)

Preparation 1-25

In a nitrogen atmosphere, 7H-benzo [c] carbazole (10 g, 46 mmol), compound sub24 (16.6 g, 48.3 mmol), sodium tert-butoxide (5.7 g, 59.8 mmol) was added to xylene (200 ml) Stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, when the reaction was completed, the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.5 g of compound 1-25. (Yield 52%, MS: [M+H] ⁺ = 525)

Preparation 1-26

In a nitrogen atmosphere, 7H-benzo [c] carbazole (10 g, 46 mmol), compound sub25 (25.1 g, 48.3 mmol), sodium tert-butoxide (5.7 g, 59.8 mmol) was added to xylene (200 ml) Stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, when the reaction was completed, the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 20.3 g of compound 1-26. (Yield 63%, MS: [M+H] ⁺ = 701)

Preparation 1-27

In a nitrogen atmosphere, 7H-benzo [c] carbazole (10 g, 46 mmol), compound sub26 (25.4 g, 48.3 mmol), sodium tert-butoxide (5.7 g, 59.8 mmol) was added to xylene (200 ml) Stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 2 hours, when the reaction was completed, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 18.2 g of compound 1-27. (Yield 56%, MS: [M+H] ⁺ = 707)

Preparation 1-28

5H-benzo [b] carbazole (10 g, 46 mmol), compound sub27 (17.8 g, 48.3 mmol), potassium phosphate (29.3 g, 138.1 mmol) in xylene (200 ml) in a nitrogen atmosphere, stirred and refluxed did After that, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 2 hours, when the reaction was completed, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 16.9 g of compound 1-28. (Yield 67%, MS: [M+H] ⁺ = 549)

Preparation 1-29

5H-benzo [b] carbazole (10 g, 46 mmol), compound sub28 (20.3 g, 48.3 mmol), sodium tert-butoxide (5.7 g, 59.8 mmol) in xylene (200 ml) in a nitrogen atmosphere Stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 2 hours, when the reaction was completed, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 19.3 g of compound 1-29. (Yield 70%, MS: [M+H] ⁺ = 601)

Preparation 1-30

In a nitrogen atmosphere, 5H-benzo [b] carbazole (10 g, 46 mmol), compound sub29 (21.7 g, 48.3 mmol), sodium tert-butoxide (5.7 g, 59.8 mmol) was added to xylene (200 ml) Stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 2 hours, when the reaction was completed, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 17.7 g of Compound 1-30. (Yield 61%, MS: [M+H] ⁺ = 631)

Preparation Example 1-31

5H-benzo [b] carbazole (10 g, 46 mmol), compound sub30 (24.6 g, 48.3 mmol), sodium tert-butoxide (5.7 g, 59.8 mmol) in xylene (200 ml) in a nitrogen atmosphere Stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, when the reaction was completed, the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 20 g of compound 1-31. (Yield 63%, MS: [M+H] ⁺ = 690)

Preparation Example 1-32

5H-benzo [b] carbazole (10 g, 46 mmol), compound sub31 (25.1 g, 48.3 mmol), sodium tert-butoxide (5.7 g, 59.8 mmol) in xylene (200 ml) in a nitrogen atmosphere Stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, when the reaction was completed, the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 21.3 g of compound 1-32. (Yield 66%, MS: [M+H] ⁺ = 701)

Preparation Example 1-33

5H-benzo[b]carbazole (10 g, 46 mmol), compound sub32 (19 g, 48.3 mmol), sodium tert-butoxide (5.7 g, 59.8 mmol) in xylene (200 ml) in a nitrogen atmosphere Stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, when the reaction was completed, the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14 g of compound 1-33. (Yield 53%, MS: [M+H] ⁺ = 575)

Preparation Example 1-34

5H-benzo[b]carbazole (10 g, 46 mmol), compound sub33 (22.7 g, 48.3 mmol), sodium tert-butoxide (5.7 g, 59.8 mmol) in xylene (200 ml) in a nitrogen atmosphere Stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, when the reaction was completed, the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.3 g of compound 1-34. (Yield 51%, MS: [M+H] ⁺ = 651)

Preparation Example 1-35

In a nitrogen atmosphere, 5H-benzo [b] carbazole (10 g, 46 mmol), compound sub17 (20.3 g, 48.3 mmol), sodium tert-butoxide (5.7 g, 59.8 mmol) was added to xylene (200 ml) Stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 2 hours, when the reaction was completed, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 18.2 g of compound 1-35. (Yield 66%, MS: [M+H] ⁺ = 601)

Preparation Example 1-36

11H-benzo [a] carbazole (10 g, 46 mmol), compound sub34 (22.7 g, 48.3 mmol), sodium tert-butoxide (5.7 g, 59.8 mmol) in xylene (200 ml) in a nitrogen atmosphere Stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 2 hours, when the reaction was completed, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15 g of compound 1-36. (Yield 50%, MS: [M+H] ⁺ = 651)

Preparation Example 1-37

11H-benzo [a] carbazole (10 g, 46 mmol), compound sub35 (21.7 g, 48.3 mmol), sodium tert-butoxide (5.7 g, 59.8 mmol) in xylene (200 ml) in a nitrogen atmosphere Stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 2 hours, when the reaction was completed, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 20.3 g of compound 1-37. (Yield 70%, MS: [M+H] ⁺ = 631)

Preparation Example 1-38

11H-benzo [a] carbazole (10 g, 46 mmol), compound sub36 (27.1 g, 48.3 mmol), sodium tert-butoxide (5.7 g, 59.8 mmol) in xylene (200 ml) in a nitrogen atmosphere Stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, when the reaction was completed, the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 20.4 g of compound 1-38. (yield 60%, MS: [M+H] ⁺ = 741)

Preparation Example 1-39

11H-benzo [a] carbazole (10 g, 46 mmol), compound sub37 (25.4 g, 48.3 mmol), sodium tert-butoxide (5.7 g, 59.8 mmol) in xylene (200 ml) in a nitrogen atmosphere Stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 2 hours, when the reaction was completed, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 17.9 g of compound 1-39. (Yield 55%, MS: [M+H] ⁺ = 707)

Preparation 1-40

11H-benzo [a] carbazole (10 g, 46 mmol), compound sub38 (24.6 g, 48.3 mmol), sodium tert-butoxide (5.7 g, 59.8 mmol) in xylene (200 ml) in a nitrogen atmosphere Stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 2 hours, when the reaction was completed, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.9 g of Compound 1-40. (Yield 50%, MS: [M+H] ⁺ = 691)

Preparation Example 1-41

In a nitrogen atmosphere, 7H-dibenzo[b,g]carbazole (10 g, 37.4 mmol), compound sub39 (14.7 g, 39.3 mmol), potassium phosphate (23.8 g, 112.2 mmol) were added to xylene (200 ml) Stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added thereto. After 2 hours, when the reaction was completed, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.5 g of compound 1-41. (Yield 51%, MS: [M+H] ⁺ = 605)

Preparation Example 1-42

7H-dibenzo[b,g]carbazole (10 g, 37.4 mmol), compound sub40 (19 g, 39.3 mmol), sodium tert-butoxide (4.7 g, 48.6 mmol) in xylene (200 ml) in a nitrogen atmosphere ), stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added thereto. After 3 hours, when the reaction was completed, the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.9 g of compound 1-42. (Yield 52%, MS: [M+H] ⁺ = 715)

Preparation Example 1-43

In a nitrogen atmosphere, 6H-dibenzo[b,h]carbazole (10 g, 37.4 mmol), compound sub41 (14.1 g, 39.3 mmol), potassium phosphate (23.8 g, 112.2 mmol) were added to xylene (200 ml) Stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added thereto. After 3 hours, when the reaction was completed, the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.6 g of compound 1-43. (Yield 62%, MS: [M+H] ⁺ = 589)

Preparation Example 1-44

6H-dibenzo[b,h]carbazole (10 g, 37.4 mmol), compound sub42 (19.6 g, 39.3 mmol), sodium tert-butoxide (4.7 g, 48.6 mmol) in xylene (200 ml) in a nitrogen atmosphere ), stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added thereto. After 2 hours, when the reaction was completed, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 19.1 g of compound 1-44. (Yield 70%, MS: [M+H] ⁺ = 731)

Preparation Example 1-45

In a nitrogen atmosphere, 13H-dibenzo[a,h]carbazole (10 g, 37.4 mmol), compound sub43 (16 g, 39.3 mmol), potassium phosphate (23.8 g, 112.2 mmol) were added to xylene (200 ml) Stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added thereto. After 3 hours, when the reaction was completed, the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.1 g of compound 1-45. (yield 59%, MS: [M+H] ⁺ = 639)

Preparation Example 1-46

13H-dibenzo[a,h]carbazole (10 g, 37.4 mmol), compound sub44 (17.7 g, 39.3 mmol), sodium tert-butoxide (4.7 g, 48.6 mmol) in xylene (200 ml) in a nitrogen atmosphere ), stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added thereto. After 3 hours, when the reaction was completed, the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.7 g of compound 1-46. (Yield 54%, MS: [M+H] ⁺ = 681)

Preparation Example 1-47

In a nitrogen atmosphere, 7H-dibenzo[c,g]carbazole (10 g, 37.4 mmol), compound sub45 (14.1 g, 39.3 mmol), potassium phosphate (23.8 g, 112.2 mmol) were added to xylene (200 ml) Stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added thereto. After 3 hours, when the reaction was completed, the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.1 g of compound 1-47. (Yield 55%, MS: [M+H] ⁺ = 589)

Preparation 2-1

In a nitrogen atmosphere, 2-bromo7-chloronaphthalene (15 g, 62.1 mmol) and the compound amine1 (19.8 g, 68.3 mmol) were added to THF (300 ml), and the mixture was stirred and refluxed. Thereafter, potassium carbonate (17.2 g, 124.2 mmol) was dissolved in water (52 ml), and after stirring sufficiently, tetrakis (triphenylphosphine) palladium (0) (0.7 g, 0.6 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.4 g of compound sub1. (Yield 77%, MS: [M+H] ⁺ = 406)

Compound sub1 (10 g, 24.6 mmol), compound amine2 (4.4 g, 25.9 mmol), and sodium tert-butoxide (3.1 g, 32 mmol) were added to xylene (200 ml) in a nitrogen atmosphere, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added thereto. When the reaction was completed after 3 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.6 g of Compound 2-1. (Yield 57%, MS: [M+H] ⁺ = 539)

Preparation 2-2

Compound sub1 (10 g, 24.6 mmol), compound amine3 (6.3 g, 25.9 mmol), and sodium tert-butoxide (3.1 g, 32 mmol) were added to xylene (200 ml) in a nitrogen atmosphere, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added thereto. When the reaction was completed after 2 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9.1 g of Compound 2-2. (yield 60%, MS: [M+H] ⁺ = 615)

Preparation 2-3

In a nitrogen atmosphere, 2-bromo7-chloronaphthalene (15 g, 62.1 mmol) and the compound amine4 (25 g, 68.3 mmol) were added to THF (300 ml), and the mixture was stirred and refluxed. Thereafter, potassium carbonate (17.2 g, 124.2 mmol) was dissolved in water (52 ml), and after stirring sufficiently, tetrakis (triphenylphosphine) palladium (0) (0.7 g, 0.6 mmol) was added. After the 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, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.9 g of compound sub2. (Yield 60%, MS: [M+H] ⁺ = 482)

Compound sub2 (10 g, 20.7 mmol), compound amine5 (5.6 g, 21.8 mmol), and sodium tert-butoxide (2.6 g, 27 mmol) were added to xylene (200 ml) in a nitrogen atmosphere, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. When the reaction was completed after 2 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.5 g of compound 2-3. (Yield 51%, MS: [M+H] ⁺ = 705)

Preparation 2-4

In a nitrogen atmosphere, 2-bromo7-chloronaphthalene (10 g, 41.4 mmol), compound amine3 (10.4 g, 42.2 mmol), sodium tert-butoxide (4.8 g, 49.7 mmol) was added to xylene (200 ml) Stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added thereto. When the reaction was completed after 3 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.7 g of compound sub3. (Yield 64%, MS: [M+H] ⁺ = 406)

In a nitrogen atmosphere, compound sub3 (10 g, 24.6 mmol), compound amine6 (8.9 g, 25.9 mmol), and sodium tert-butoxide (3.1 g, 32 mmol) were added to xylene (200 ml), stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the solvent was removed under reduced pressure after cooling to room temperature. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.2 g of Compound 2-4. (Yield 58%, MS: [M+H] ⁺ = 715)

Preparation 2-5

Compound sub3 (10 g, 24.6 mmol), compound amine7 (8 g, 25.9 mmol), and sodium tert-butoxide (3.1 g, 32 mmol) were added to xylene (200 ml) in a nitrogen atmosphere, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added thereto. When the reaction was completed after 3 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.2 g of Compound 2-5. (Yield 67%, MS: [M+H] ⁺ = 679)

Preparation Example 2-6

In a nitrogen atmosphere, 2-bromo7-chloronaphthalene (10 g, 41.4 mmol), compound amine2 (7.1 g, 42.2 mmol), sodium tert-butoxide (4.8 g, 49.7 mmol) was added to xylene (200 ml) Stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added thereto. When the reaction was completed after 3 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.6 g of compound sub4. (Yield 56%, MS: [M+H] ⁺ = 330)

In a nitrogen atmosphere, compound sub4 (10 g, 30.3 mmol), compound amine8 (10.2 g, 31.8 mmol), sodium tert-butoxide (3.8 g, 39.4 mmol) were added to xylene (200 ml), and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added thereto. When the reaction was completed after 2 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.7 g of Compound 2-6. (Yield 68%, MS: [M+H] ⁺ = 615)

Preparation 2-7

In a nitrogen atmosphere, compound sub4 (10 g, 30.3 mmol), compound amine9 (11.1 g, 31.8 mmol), sodium tert-butoxide (3.8 g, 39.4 mmol) were added to xylene (200 ml), and the mixture was stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added thereto. When the reaction was completed after 3 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.5 g of Compound 2-7. (Yield 54%, MS: [M+H] ⁺ = 643)

Preparation 2-8

In a nitrogen atmosphere, 2-bromo-6-chloronaphthalene (15 g, 62.1 mmol) and the compound amine1 (19.8 g, 68.3 mmol) were added to THF (300 ml), and the mixture was stirred and refluxed. Thereafter, potassium carbonate (17.2 g, 124.2 mmol) was dissolved in water (52 ml), and after stirring sufficiently, tetrakis (triphenylphosphine) palladium (0) (0.7 g, 0.6 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.6 g of compound sub5. (Yield 66%, MS: [M+H] ⁺ = 406)

Compound sub5 (10 g, 24.6 mmol), compound amine2 (6.3 g, 25.9 mmol), and sodium tert-butoxide (3.1 g, 32 mmol) were added to xylene (200 ml) in a nitrogen atmosphere, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added thereto. When the reaction was completed after 2 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 8.8 g of compound 2-8. (Yield 58%, MS: [M+H] ⁺ = 615)

Preparation Example 2-9

In a nitrogen atmosphere, compound sub5 (10 g, 24.6 mmol), compound amine5 (6.7 g, 25.9 mmol), sodium tert-butoxide (3.1 g, 32 mmol) were added to xylene (200 ml), and the mixture was stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added thereto. When the reaction was completed after 2 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.7 g of compound 2-9. (yield 69%, MS: [M+H] ⁺ = 629)

Preparation Example 2-10

In a nitrogen atmosphere, compound sub5 (10 g, 24.6 mmol), compound amine10 (7.6 g, 25.9 mmol), and sodium tert-butoxide (3.1 g, 32 mmol) were added to xylene (200 ml), stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added thereto. When the reaction was completed after 3 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.1 g of Compound 2-10. (Yield 62%, MS: [M+H] ⁺ = 665)

Preparation Example 2-11

2-bromo-6-chloronaphthalene (10 g, 41.4 mmol), compound amine11 (25.7 g, 87 mmol), sodium tert-butoxide (9.9 g, 103.5 mmol) in xylene (300 ml) in a nitrogen atmosphere added, stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (1.1 g, 2.1 mmol) was added thereto. When the reaction was completed after 3 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 16.3 g of Compound 2-11. (Yield 55%, MS: [M+H] ⁺ = 715)

Preparation Example 2-12

2-Bromo-6-chloronaphthalene (10 g, 41.4 mmol), compound amine12 (22.5 g, 87 mmol), sodium tert-butoxide (9.9 g, 103.5 mmol) in xylene (300 ml) in a nitrogen atmosphere added, stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (1.1 g, 2.1 mmol) was added thereto. When the reaction was completed after 2 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 17 g of compound 2-12. (Yield 64%, MS: [M+H] ⁺ = 643)

Preparation Example 2-13

2-bromo-6-chloronaphthalene (10 g, 41.4 mmol), compound amine2 (7.1 g, 42.2 mmol), sodium tert-butoxide (4.8 g, 49.7 mmol) in xylene (200 ml) in a nitrogen atmosphere added, stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added thereto. When the reaction was completed after 2 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9.4 g of compound sub6. (yield 69%, MS: [M+H] ⁺ = 330)

In a nitrogen atmosphere, compound sub6 (10 g, 30.3 mmol), compound amine13 (12.1 g, 31.8 mmol), sodium tert-butoxide (3.8 g, 39.4 mmol) were added to xylene (200 ml), and the mixture was stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added thereto. When the reaction was completed after 2 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.9 g of compound 2-13. (Yield 63%, MS: [M+H] ⁺ = 675)

Preparation Example 2-14

In a nitrogen atmosphere, 1-bromo-6-chloronaphthalene (15 g, 62.1 mmol) and the compound amine1 (41.3 g, 142.9 mmol) were added to THF (450 ml), stirred and refluxed. After that, potassium carbonate (42.9 g, 310.5 mmol) was dissolved in water (129 ml), and after stirring sufficiently, bis (tri-tert-butylphosphine) palladium (0) (0.6 g, 1.2 mmol) was added. After the 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, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 25.6 g of compound 2-14. (Yield 67%, MS: [M+H] ⁺ = 615)

Preparation 2-15

In a nitrogen atmosphere, 1-bromo-6-chloronaphthalene (15 g, 62.1 mmol) and the compound amine14 (27 g, 68.3 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (17.2 g, 124.2 mmol) was dissolved in water (52 ml), and after stirring sufficiently, tetrakis (triphenylphosphine) palladium (0) (0.7 g, 0.6 mmol) was added. After the reaction for 12 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 25.1 g of compound sub7. (yield 79%, MS: [M+H] ⁺ = 512)

Compound sub7 (15 g, 29.3 mmol) and compound amine1 (9.3 g, 32.2 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (12.1 g, 87.9 mmol) was dissolved in water (36 ml), and after stirring sufficiently, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.3 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16 g of compound 2-15. (yield 76%, MS: [M+H] ⁺ = 721)

Preparation Example 2-16

1-Bromo-6-chloronaphthalene (10 g, 41.4 mmol), compound amine15 (10.4 g, 42.2 mmol), sodium tert-butoxide (4.8 g, 49.7 mmol) in xylene (200 ml) in a nitrogen atmosphere added, stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added thereto. When the reaction was completed after 2 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9.6 g of compound sub8. (Yield 57%, MS: [M+H] ⁺ = 406)

In a nitrogen atmosphere, compound sub8 (10 g, 24.6 mmol), compound amine 16 (7.6 g, 25.9 mmol), and sodium tert-butoxide (3.1 g, 32 mmol) were added to xylene (200 ml), stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added thereto. When the reaction was completed after 2 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 8.7 g of compound 2-16. (Yield 53%, MS: [M+H] ⁺ = 665)

Preparation Example 2-17

Compound sub8 (10 g, 24.6 mmol), compound amine6 (8.9 g, 25.9 mmol), and sodium tert-butoxide (3.1 g, 32 mmol) were added to xylene (200 ml) in a nitrogen atmosphere, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added thereto. When the reaction was completed after 2 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.1 g of Compound 2-17. (yield 69%, MS: [M+H] ⁺ = 715)

Preparation Example 2-18

In a nitrogen atmosphere, 1-bromo-7-chloronaphthalene (15 g, 62.1 mmol) and the compound amine4 (25 g, 68.3 mmol) were added to THF (300 ml), and the mixture was stirred and refluxed. Thereafter, potassium carbonate (17.2 g, 124.2 mmol) was dissolved in water (52 ml), and after stirring sufficiently, tetrakis (triphenylphosphine) palladium (0) (0.7 g, 0.6 mmol) was added. After the 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, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.5 g of compound sub9. (Yield 62%, MS: [M+H] ⁺ = 482)

Compound sub9 (15 g, 31.1 mmol) and compound amine17 (11.6 g, 34.2 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (12.9 g, 93.4 mmol) was dissolved in water (39 ml), and after stirring sufficiently, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.3 mmol) was added. After the 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, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.7 g of compound 2-18. (Yield 77%, MS: [M+H] ⁺ = 741)

Preparation Example 2-19

1-bromo-7-chloronaphthalene (10 g, 41.4 mmol), compound amine18 (11.4 g, 42.2 mmol), sodium tert-butoxide (4.8 g, 49.7 mmol) in xylene (200 ml) in a nitrogen atmosphere added, stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added thereto. When the reaction was completed after 3 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.1 g of compound sub10. (Yield 68%, MS: [M+H] ⁺ = 430)

Compound sub10 (10 g, 23.3 mmol), compound amine3 (6 g, 24.4 mmol), sodium tert-butoxide (2.9 g, 30.2 mmol) in xylene (200 ml) in a nitrogen atmosphere was stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 2 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9.4 g of Compound 2-19. (Yield 63%, MS: [M+H] ⁺ = 639)

Preparation 2-20

In a nitrogen atmosphere, 1-bromo-3-chloronaphthalene (15 g, 62.1 mmol) and the compound amine19 (25 g, 68.3 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (17.2 g, 124.2 mmol) was dissolved in water (52 ml), and after stirring sufficiently, tetrakis (triphenylphosphine) palladium (0) (0.7 g, 0.6 mmol) was added. After the reaction for 12 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.8 g of compound sub11. (Yield 73%, MS: [M+H] ⁺ = 482)

In a nitrogen atmosphere, compound sub11 (10 g, 20.7 mmol), compound amine15 (5.3 g, 21.8 mmol), and sodium tert-butoxide (2.6 g, 27 mmol) were added to xylene (200 ml), stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. When the reaction was completed after 2 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 8.9 g of Compound 2-20. (Yield 62%, MS: [M+H] ⁺ = 691)

Preparation 2-21

1-Bromo-3-chloronaphthalene (10 g, 41.4 mmol), compound amine20 (11.6 g, 42.2 mmol), sodium tert-butoxide (4.8 g, 49.7 mmol) in xylene (200 ml) in a nitrogen atmosphere added, stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added thereto. When the reaction was completed after 2 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.2 g of compound sub12. (Yield 62%, MS: [M+H] ⁺ = 436)

Compound sub12 (15 g, 34.4 mmol) and compound amine4 (13.8 g, 37.8 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (14.3 g, 103.2 mmol) was dissolved in water (43 ml), and after stirring sufficiently, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.3 mmol) was added. After the 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, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.1 g of compound 2-21. (Yield 61%, MS: [M+H] ⁺ = 721)

Preparation 2-22

1-bromo-3-chloronaphthalene (10 g, 41.4 mmol), compound amine5 (11 g, 42.2 mmol), sodium tert-butoxide (4.8 g, 49.7 mmol) in xylene (200 ml) in a nitrogen atmosphere added, stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added thereto. When the reaction was completed after 2 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.1 g of compound sub13. (Yield 58%, MS: [M+H] ⁺ = 420)

In a nitrogen atmosphere, compound sub13 (10 g, 23.8 mmol), compound amine12 (6.5 g, 25 mmol), and sodium tert-butoxide (3 g, 31 mmol) were added to xylene (200 ml), and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 3 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.4 g of compound 2-22. (Yield 68%, MS: [M+H] ⁺ = 643)

Preparation 2-23

1-bromo-3-chloronaphthalene (10 g, 41.4 mmol), compound amine10 (25.7 g, 87 mmol), sodium tert-butoxide (9.9 g, 103.5 mmol) in xylene (300 ml) in a nitrogen atmosphere added, stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (1.1 g, 2.1 mmol) was added thereto. When the reaction was completed after 2 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 19.5 g of compound 2-23. (Yield 66%, MS: [M+H] ⁺ = 715)

Preparation 2-24

In a nitrogen atmosphere, 2-bromo-3-chloronaphthalene (15 g, 62.1 mmol) and the compound amine17 (48.5 g, 142.9 mmol) were added to THF (450 ml), stirred and refluxed. After that, potassium carbonate (42.9 g, 310.5 mmol) was dissolved in water (129 ml), and after stirring sufficiently, bis (tri-tert-butylphosphine) palladium (0) (0.6 g, 1.2 mmol) was added. After the reaction for 12 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 34.6 g of compound 2-24. (Yield 78%, MS: [M+H] ⁺ = 715)

Preparation 2-25

In a nitrogen atmosphere, 2-bromo-3-chloronaphthalene (15 g, 62.1 mmol) and the compound amine21 (28.4 g, 68.3 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (17.2 g, 124.2 mmol) was dissolved in water (52 ml), and after stirring sufficiently, tetrakis (triphenylphosphine) palladium (0) (0.7 g, 0.6 mmol) was added. After the reaction for 12 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 25.4 g of compound sub14. (Yield 77%, MS: [M+H] ⁺ = 532)

Compound sub14 (10 g, 18.8 mmol), compound amine3 (4.8 g, 19.7 mmol), sodium tert-butoxide (2.3 g, 24.4 mmol) in xylene (200 ml) in a nitrogen atmosphere was stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. When the reaction was completed after 3 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 8.2 g of Compound 2-25. (yield 59%, MS: [M+H] ⁺ = 741)

Preparation 2-26

2-bromo-3-chloronaphthalene (10 g, 41.4 mmol), compound amine 16 (25.7 g, 87 mmol), sodium tert-butoxide (9.9 g, 103.5 mmol) in xylene (300 ml) in a nitrogen atmosphere added, stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (1.1 g, 2.1 mmol) was added thereto. When the reaction was completed after 2 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 19.2 g of compound 2-26. (Yield 65%, MS: [M+H] ⁺ = 715)

Preparation 2-27

In a nitrogen atmosphere, 1-bromo-8-chloronaphthalene (15 g, 62.1 mmol) and the compound amine22 (29.3 g, 68.3 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (17.2 g, 124.2 mmol) was dissolved in water (52 ml), and after stirring sufficiently, tetrakis (triphenylphosphine) palladium (0) (0.7 g, 0.6 mmol) was added. After the reaction for 9 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, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.7 g of compound sub15. (Yield 67%, MS: [M+H] ⁺ = 546)

In a nitrogen atmosphere, compound sub15 (10 g, 18.3 mmol), compound amine3 (4.7 g, 19.2 mmol), sodium tert-butoxide (2.3 g, 23.8 mmol) were added to xylene (200 ml), and the mixture was stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. When the reaction was completed after 2 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.6 g of compound 2-27. (Yield 55%, MS: [M+H] ⁺ = 755)

Preparation 2-28

In a nitrogen atmosphere, 1-bromo-4-chloronaphthalene (15 g, 62.1 mmol) and the compound amine4 (25 g, 68.3 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (17.2 g, 124.2 mmol) was dissolved in water (52 ml), and after stirring sufficiently, tetrakis (triphenylphosphine) palladium (0) (0.7 g, 0.6 mmol) was added. After the 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, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.2 g of compound sub16. (Yield 61%, MS: [M+H] ⁺ = 482)

Compound sub16 (10 g, 20.7 mmol), compound amine23 (6.7 g, 21.8 mmol), sodium tert-butoxide (2.6 g, 27 mmol) in xylene (200 ml) in a nitrogen atmosphere were stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. When the reaction was completed after 3 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 8.9 g of compound 2-28. (Yield 57%, MS: [M+H] ⁺ = 755)

Preparation 2-29

1-bromo-4-chloronaphthalene (10 g, 41.4 mmol), compound amine3 (10.4 g, 42.2 mmol), sodium tert-butoxide (4.8 g, 49.7 mmol) in xylene (200 ml) in a nitrogen atmosphere added, stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added thereto. When the reaction was completed after 2 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9.7 g of compound sub17. (Yield 58%, MS: [M+H] ⁺ = 406)

In a nitrogen atmosphere, compound sub17 (10 g, 24.6 mmol), compound amine24 (7.6 g, 25.9 mmol), and sodium tert-butoxide (3.1 g, 32 mmol) were added to xylene (200 ml), stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added thereto. When the reaction was completed after 3 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11 g of compound 2-29. (Yield 67%, MS: [M+H] ⁺ = 665)

Preparation 2-30

1-bromo-4-chloronaphthalene (10 g, 41.4 mmol), compound amine3 (21.3 g, 87 mmol), sodium tert-butoxide (9.9 g, 103.5 mmol) in xylene (300 ml) in a nitrogen atmosphere added, stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (1.1 g, 2.1 mmol) was added thereto. When the reaction was completed after 2 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.7 g of Compound 2-30. (Yield 50%, MS: [M+H] ⁺ = 615)

Preparation 2-31

In a nitrogen atmosphere, compound sub17 (10 g, 24.6 mmol), compound amine25 (8.4 g, 25.9 mmol), and sodium tert-butoxide (3.1 g, 32 mmol) were added to xylene (200 ml), stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added thereto. When the reaction was completed after 2 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9.7 g of compound 2-31. (Yield 57%, MS: [M+H] ⁺ = 695)

Preparation 2-32

1-Bromo-5-chloronaphthalene (10 g, 41.4 mmol), compound amine2 (7.1 g, 42.2 mmol), sodium tert-butoxide (4.8 g, 49.7 mmol) in xylene (200 ml) in a nitrogen atmosphere added, stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added thereto. When the reaction was completed after 3 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 8 g of compound sub18. (yield 59%, MS: [M+H] ⁺ = 330)

Compound sub18 (15 g, 45.5 mmol) and compound amine26 (20.8 g, 50 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (18.9 g, 136.4 mmol) was dissolved in water (57 ml), and after stirring sufficiently, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.5 mmol) was added. After the reaction for 12 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.8 g of compound 2-32. (Yield 72%, MS: [M+H] ⁺ = 665)

Preparation 2-33

Compound sub18 (10 g, 30.3 mmol), compound amine27 (11.6 g, 31.8 mmol), sodium tert-butoxide (3.8 g, 39.4 mmol) in xylene (200 ml) in a nitrogen atmosphere were stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added thereto. When the reaction was completed after 3 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.2 g of compound 2-33. (Yield 56%, MS: [M+H] ⁺ = 659)

Preparation 2-34

Compound sub18 (10 g, 30.3 mmol), compound amine28 (10.2 g, 31.8 mmol), sodium tert-butoxide (3.8 g, 39.4 mmol) in xylene (200 ml) in a nitrogen atmosphere were stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added thereto. When the reaction was completed after 2 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.9 g of compound 2-34. (yield 69%, MS: [M+H] ⁺ = 615)

Preparation 2-35

In a nitrogen atmosphere, compound sub18 (10 g, 30.3 mmol), compound amine29 (11.1 g, 31.8 mmol), sodium tert-butoxide (3.8 g, 39.4 mmol) were added to xylene (200 ml), and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added thereto. When the reaction was completed after 3 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.9 g of compound 2-35. (Yield 56%, MS: [M+H] ⁺ = 643)

Preparation 2-36

In a nitrogen atmosphere, 2-bromo-1-chloronaphthalene (15 g, 62.1 mmol) and the compound amine30 (27 g, 68.3 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (17.2 g, 124.2 mmol) was dissolved in water (52 ml), and after stirring sufficiently, tetrakis (triphenylphosphine) palladium (0) (0.7 g, 0.6 mmol) was added. After the reaction for 12 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.1 g of compound sub19. (Yield 76%, MS: [M+H] ⁺ = 512)

Compound sub19 (10 g, 19.5 mmol), compound amine2 (3.5 g, 20.5 mmol), sodium tert-butoxide (2.4 g, 25.4 mmol) in xylene (200 ml) in a nitrogen atmosphere were stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. When the reaction was completed after 3 hours, the mixture was cooled to room temperature and reduced pressure to remove the solvent. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.7 g of compound 2-36. (Yield 53%, MS: [M+H] ⁺ = 645)

[Example]

Example 1

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

The following compound HI-1 was formed to a thickness of 1150 Å as a hole injection layer on the prepared ITO transparent electrode, but the following compound A-1 was p-doped at a concentration of 1.5%. On the hole injection layer, the following compound HT-1 was vacuum-deposited to form a hole transport layer having a thickness of 800 Å. Then, on the hole transport layer, the following compound EB-1 was vacuum-deposited to a film thickness of 150 Å to form an electron blocking layer. Then, on the electron blocking layer, the compound 1-1 prepared previously as a host, compound 2-1, and the following compound Dp-7 as a dopant were vacuum-deposited in a weight ratio of 49:49:2 to form a 400 Å-thick light emitting layer did On the light emitting layer, the following compound HB-1 was vacuum-deposited to a thickness of 30 Å to form a hole blocking layer. Then, on the hole blocking layer, the following compound ET-1 and the following compound LiQ were vacuum-deposited at a weight ratio of 2:1 to form an electron injection and transport layer to a thickness of 300 Å. A cathode was formed by sequentially depositing lithium fluoride (LiF) to a thickness of 12 Å and aluminum to a thickness of 1,000 Å on the electron injection and transport layer.

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

Examples 2 to 205

An organic light emitting device was manufactured in the same manner as in Example 1, except that the host material was changed as shown in Tables 1 to 7 when the light emitting layer was manufactured.

Comparative Examples 1 to 63

An organic light emitting diode was manufactured in the same manner as in Example 1, except that the host material was changed as shown in Tables 8 and 9 when preparing the emission layer. Compounds B-1, B-2, and B-3 used in Table 8, and compounds C-1, C-2, and C-3 used in Table 9 are as follows.

When a current was applied to the organic light emitting devices prepared in Examples and Comparative Examples, voltage, efficiency, and lifetime were measured (based on 15 mA/cm ² ), and the results are shown in Tables 1 to 9 below. In this case, the lifetime T95 means the time required for the luminance to decrease from the initial luminance (6,000 nits) to 95%.

first host second host drive voltage
(V) efficiency
(cd/A) life span
T95(hr) luminous color Example 1 compound 1-1 compound 2-1 3.66 18.09 179 Red Example 2 compound 2-8 3.65 17.20 164 Red Example 3 compound 2-14 3.64 17.39 166 Red Example 4 compound 2-26 3.64 17.65 173 Red Example 5 compound 2-31 3.60 17.19 175 Red Example 6 compound 1-2 compound 2-4 3.62 17.83 162 Red Example 7 compound 2-10 3.66 18.14 178 Red Example 8 compound 2-17 3.66 17.64 160 Red Example 9 compound 2-27 3.64 17.67 180 Red Example 10 compound 2-32 3.68 17.01 167 Red Example 11 compound 1-3 compound 2-6 3.74 18.07 187 Red Example 12 compound 2-11 3.76 18.50 205 Red Example 13 compound 2-18 3.79 18.93 223 Red Example 14 compound 2-28 3.78 19.25 189 Red Example 15 compound 2-34 3.72 18.18 196 Red Example 16 compound 1-4 compound 2-7 3.76 18.07 190 Red Example 17 compound 2-12 3.79 18.63 207 Red Example 18 compound 2-22 3.79 19.26 219 Red Example 19 compound 2-29 3.75 18.43 218 Red Example 20 compound 2-36 3.79 18.68 201 Red Example 21 compound 1-5 compound 2-1 3.62 21.63 226 Red Example 22 compound 2-8 3.55 20.70 206 Red Example 23 compound 2-14 3.65 22.26 194 Red Example 24 compound 2-26 3.63 21.89 208 Red Example 25 compound 2-31 3.62 20.99 196 Red Example 26 compound 1-6 compound 2-4 3.63 22.49 217 Red Example 27 compound 2-10 3.60 20.13 220 Red Example 28 compound 2-17 3.64 22.13 210 Red Example 29 compound 2-27 3.60 20.16 204 Red Example 30 compound 2-32 3.64 21.77 203 Red

first host second host drive voltage
(V) efficiency
(cd/A) life span
T95(hr) luminous color Example 31 compound 1-7 compound 2-6 3.89 19.98 185 Red Example 32 compound 2-11 3.84 19.62 195 Red Example 33 compound 2-18 3.81 20.43 182 Red Example 34 compound 2-28 3.85 20.18 185 Red Example 35 compound 2-34 3.84 19.64 186 Red Example 36 compound 1-8 compound 2-7 3.83 19.13 196 Red Example 37 compound 2-12 3.89 19.59 199 Red Example 38 compound 2-22 3.81 20.07 188 Red Example 39 compound 2-29 3.83 19.12 183 Red Example 40 compound 2-36 3.86 19.11 185 Red Example 41 compound 1-9 compound 2-1 3.77 19.32 195 Red Example 42 compound 2-8 3.79 18.06 211 Red Example 43 compound 2-14 3.70 19.17 189 Red Example 44 compound 2-26 3.79 18.73 188 Red Example 45 compound 2-31 3.75 19.27 199 Red Example 46 compound 1-10 compound 2-4 3.77 18.43 194 Red Example 47 compound 2-10 3.75 18.28 215 Red Example 48 compound 2-17 3.72 19.42 185 Red Example 49 compound 2-27 3.73 18.93 221 Red Example 50 compound 2-32 3.70 18.38 192 Red Example 51 compound 1-11 compound 2-6 3.61 18.16 161 Red Example 52 compound 2-11 3.66 17.70 166 Red Example 53 compound 2-18 3.60 17.87 161 Red Example 54 compound 2-28 3.66 17.31 173 Red Example 55 compound 2-34 3.68 18.48 167 Red Example 56 compound 1-12 compound 2-7 3.63 17.63 152 Red Example 57 compound 2-12 3.60 18.34 154 Red Example 58 compound 2-22 3.60 18.39 160 Red Example 59 compound 2-29 3.60 18.10 167 Red Example 60 compound 2-36 3.63 18.15 157 Red

first host second host drive voltage
(V) efficiency
(cd/A) life span
T95(hr) luminous color Example 61 compound 1-13 compound 2-1 3.87 19.37 192 Red Example 62 compound 2-8 3.84 19.74 197 Red Example 63 compound 2-14 3.81 20.37 185 Red Example 64 compound 2-26 3.86 20.15 194 Red Example 65 compound 2-31 3.89 20.07 195 Red Example 66 compound 1-14 compound 2-4 3.83 19.18 190 Red Example 67 compound 2-10 3.89 19.01 182 Red Example 68 compound 2-17 3.87 19.70 186 Red Example 69 compound 2-27 3.87 19.24 195 Red Example 70 compound 2-32 3.80 20.42 196 Red Example 71 compound 1-15 compound 2-6 3.63 18.27 158 Red Example 72 compound 2-11 3.63 17.39 170 Red Example 73 compound 2-18 3.66 17.85 171 Red Example 74 compound 2-28 3.66 17.48 155 Red Example 75 compound 2-34 3.69 17.95 152 Red Example 76 compound 1-16 compound 2-7 3.61 17.20 167 Red Example 77 compound 2-12 3.62 17.85 151 Red Example 78 compound 2-22 3.61 17.56 173 Red Example 79 compound 2-29 3.64 18.22 165 Red Example 80 compound 2-36 3.68 18.06 153 Red Example 81 compound 1-17 compound 2-1 3.87 19.37 192 Red Example 82 compound 2-8 3.84 19.74 197 Red Example 83 compound 2-14 3.81 20.37 185 Red Example 84 compound 2-26 3.86 20.15 194 Red Example 85 compound 2-31 3.89 20.07 195 Red Example 86 compound 1-18 compound 2-4 3.83 19.18 190 Red Example 87 compound 2-10 3.89 19.01 182 Red Example 88 compound 2-17 3.87 19.70 186 Red Example 89 compound 2-27 3.87 19.24 195 Red Example 90 compound 2-32 3.80 20.42 196 Red

first host second host drive voltage
(V) efficiency
(cd/A) life span
T95(hr) luminous color Example 91 compound 1-19 compound 2-6 3.79 18.80 205 Red Example 92 compound 2-11 3.73 18.12 187 Red Example 93 compound 2-18 3.70 18.72 194 Red Example 94 compound 2-28 3.72 18.64 211 Red Example 95 compound 2-34 3.73 18.53 214 Red Example 96 compound 1-20 compound 2-7 3.71 18.73 199 Red Example 97 compound 2-12 3.74 19.36 227 Red Example 98 compound 2-22 3.73 18.31 221 Red Example 99 compound 2-29 3.70 18.78 192 Red Example 100 compound 2-36 3.71 18.06 230 Red Example 101 compound 1-21 compound 2-1 3.61 20.98 223 Red Example 102 compound 2-8 3.61 22.18 185 Red Example 103 compound 2-14 3.59 21.51 199 Red Example 104 compound 2-26 3.58 20.01 211 Red Example 105 compound 2-31 3.65 19.52 210 Red Example 106 compound 1-23 compound 2-4 3.65 19.64 193 Red Example 107 compound 2-10 3.57 21.43 220 Red Example 108 compound 2-17 3.62 21.19 224 Red Example 109 compound 2-27 3.55 20.78 211 Red Example 110 compound 2-32 3.61 20.96 229 Red Example 111 compound 1-25 compound 2-6 3.54 20.98 164 Red Example 112 compound 2-11 3.61 22.18 157 Red Example 113 compound 2-18 3.59 21.51 157 Red Example 114 compound 2-28 3.58 20.01 154 Red Example 115 compound 2-34 3.65 19.52 175 Red Example 116 compound 1-26 compound 2-7 3.65 19.64 155 Red Example 117 compound 2-12 3.57 21.43 170 Red Example 118 compound 2-22 3.62 21.19 180 Red Example 119 compound 2-29 3.55 20.78 163 Red Example 120 compound 2-36 3.61 20.96 166 Red

first host second host drive voltage
(V) efficiency
(cd/A) life span
T95(hr) luminous color Example 121 compound 1-27 compound 2-1 3.61 18.35 177 Red Example 122 compound 2-8 3.61 18.49 199 Red Example 123 compound 2-14 3.59 18.26 192 Red Example 124 compound 2-26 3.58 17.34 179 Red Example 125 compound 2-31 3.65 17.46 203 Red Example 126 compound 1-28 compound 2-4 3.65 17.10 191 Red Example 127 compound 2-10 3.57 17.59 209 Red Example 128 compound 2-17 3.62 18.39 171 Red Example 129 compound 2-27 3.55 18.28 204 Red Example 130 compound 2-32 3.61 17.88 189 Red Example 131 compound 1-32 compound 2-6 3.77 18.48 225 Red Example 132 compound 2-11 3.73 19.29 229 Red Example 133 compound 2-18 3.77 18.06 213 Red Example 134 compound 2-28 3.76 18.89 193 Red Example 135 compound 2-34 3.76 19.42 209 Red Example 136 compound 1-33 compound 2-7 3.76 18.90 202 Red Example 137 compound 2-12 3.77 19.39 226 Red Example 138 compound 2-22 3.70 18.57 225 Red Example 139 compound 2-29 3.70 18.26 192 Red Example 140 compound 2-36 3.70 18.68 199 Red Example 141 compound 1-34 compound 2-1 3.60 18.05 167 Red Example 142 compound 2-8 3.65 18.45 167 Red Example 143 compound 2-14 3.62 18.35 177 Red Example 144 compound 2-26 3.69 17.48 174 Red Example 145 compound 2-31 3.66 17.61 150 Red Example 146 compound 1-35 compound 2-4 3.63 17.15 176 Red Example 147 compound 2-10 3.60 17.81 155 Red Example 148 compound 2-17 3.69 17.22 163 Red Example 149 compound 2-27 3.61 18.45 175 Red Example 150 compound 2-32 3.67 18.09 156 Red

first host second host drive voltage
(V) efficiency
(cd/A) life span
T95(hr) luminous color Example 151 compound 1-36 compound 2-6 3.88 20.33 181 Red Example 152 compound 2-11 3.80 20.47 187 Red Example 153 compound 2-18 3.81 19.83 200 Red Example 154 compound 2-28 3.82 20.14 180 Red Example 155 compound 2-34 3.85 19.15 193 Red Example 156 compound 1-37 compound 2-7 3.80 19.00 186 Red Example 157 compound 2-12 3.81 19.13 190 Red Example 158 compound 2-22 3.89 19.38 180 Red Example 159 compound 2-29 3.83 19.51 194 Red Example 160 compound 2-36 3.83 19.26 199 Red Example 161 compound 1-38 compound 2-1 3.59 22.58 220 Red Example 162 compound 2-8 3.59 21.53 212 Red Example 163 compound 2-14 3.61 19.60 218 Red Example 164 compound 2-26 3.63 20.06 202 Red Example 165 compound 2-31 3.56 21.87 186 Red Example 166 compound 1-39 compound 2-4 3.56 21.11 226 Red Example 167 compound 2-10 3.62 20.65 188 Red Example 168 compound 2-17 3.59 20.20 221 Red Example 169 compound 2-27 3.55 22.79 205 Red Example 170 compound 2-32 3.64 20.21 224 Red Example 171 compound 1-41 compound 2-6 3.84 19.74 191 Red Example 172 compound 2-11 3.86 19.76 186 Red Example 173 compound 2-18 3.82 19.40 198 Red Example 174 compound 2-28 3.85 19.50 191 Red Example 175 compound 2-34 3.84 19.89 183 Red Example 176 compound 1-42 compound 2-7 3.80 19.21 190 Red Example 177 compound 2-12 3.85 20.39 195 Red Example 178 compound 2-22 3.88 19.24 198 Red Example 179 compound 2-29 3.84 19.85 199 Red Example 180 compound 2-36 3.88 19.56 194 Red

first host second host drive voltage
(V) efficiency
(cd/A) life span
T95(hr) luminous color Example 181 compound 1-43 compound 2-1 3.77 19.27 204 Red Example 182 compound 2-8 3.70 18.41 205 Red Example 183 compound 2-14 3.78 19.40 221 Red Example 184 compound 2-26 3.77 18.20 213 Red Example 185 compound 2-31 3.73 18.02 218 Red Example 186 compound 1-44 compound 2-4 3.78 18.87 208 Red Example 187 compound 2-10 3.79 18.68 186 Red Example 188 compound 2-17 3.79 18.98 223 Red Example 189 compound 2-27 3.73 18.04 218 Red Example 190 compound 2-32 3.71 18.30 217 Red Example 191 compound 1-45 compound 2-6 3.59 21.70 194 Red Example 192 compound 2-11 3.58 19.55 212 Red Example 193 compound 2-18 3.62 21.90 219 Red Example 194 compound 2-28 3.55 22.05 216 Red Example 195 compound 2-34 3.63 22.28 197 Red Example 196 compound 1-46 compound 2-7 3.58 19.52 220 Red Example 197 compound 2-12 3.58 22.18 215 Red Example 198 compound 2-22 3.60 20.09 229 Red Example 199 compound 2-29 3.56 20.69 205 Red Example 200 compound 2-36 3.61 20.17 202 Red Example 201 compound 1-47 compound 2-1 3.84 20.17 199 Red Example 202 compound 2-8 3.80 20.48 200 Red Example 203 compound 2-14 3.87 19.77 182 Red Example 204 compound 2-26 3.81 19.57 195 Red Example 205 compound 2-31 3.81 19.24 188 Red

first host second host drive voltage
(V) efficiency
(cd/A) life span
T95(hr) luminous color Comparative Example 1 compound B-1 compound 2-1 4.19 14.86 121 Red Comparative Example 2 compound 2-8 4.06 14.94 127 Red Comparative Example 3 compound 2-14 4.03 14.08 116 Red Comparative Example 4 compound 2-26 4.15 14.58 112 Red Comparative Example 5 compound 2-31 4.01 14.51 124 Red Comparative Example 6 compound 2-4 4.15 14.71 119 Red Comparative Example 7 compound 2-10 4.05 14.22 119 Red Comparative Example 8 compound 2-17 4.10 14.77 112 Red Comparative Example 9 compound 2-27 4.14 14.02 119 Red Comparative Example 10 compound 2-32 4.05 14.62 109 Red Comparative Example 11 compound B-2 compound 2-6 4.31 14.86 112 Red Comparative Example 12 compound 2-11 4.30 14.94 132 Red Comparative Example 13 compound 2-18 4.30 14.08 118 Red Comparative Example 14 compound 2-28 4.20 14.58 120 Red Comparative Example 15 compound 2-34 4.27 14.51 122 Red Comparative Example 16 compound 2-7 4.20 14.71 111 Red Comparative Example 17 compound 2-12 4.28 14.22 126 Red Comparative Example 18 compound 2-22 4.24 14.77 122 Red Comparative Example 19 compound 2-29 4.24 14.02 120 Red Comparative Example 20 compound 2-36 4.32 14.62 114 Red Comparative Example 21 compound B-3 compound 2-1 4.42 9.95 78 Red Comparative Example 22 compound 2-8 4.35 11.71 73 Red Comparative Example 23 compound 2-14 4.43 11.53 83 Red Comparative Example 24 compound 2-26 4.35 11.74 85 Red Comparative Example 25 compound 2-31 4.41 10.48 103 Red Comparative Example 26 compound 2-4 4.49 10.02 61 Red Comparative Example 27 compound 2-10 4.31 12.61 90 Red Comparative Example 28 compound 2-17 4.43 10.78 73 Red Comparative Example 29 compound 2-27 4.43 12.78 100 Red Comparative Example 30 compound 2-32 4.31 10.47 88 Red

first host second host drive voltage
(V) efficiency
(cd/A) life span
T95(hr) luminous color Comparative Example 31 compound 1-1 compound C-1 4.48 10.93 115 Red Comparative Example 32 compound 1-4 4.44 11.98 104 Red Comparative Example 33 compound 1-7 4.45 9.65 84 Red Comparative Example 34 compound 1-13 4.47 9.89 96 Red Comparative Example 35 compound 1-19 4.37 10.41 107 Red Comparative Example 36 compound 1-23 4.50 12.70 82 Red Comparative Example 37 compound 1-28 4.50 12.82 76 Red Comparative Example 38 compound 1-32 4.38 10.28 83 Red Comparative Example 39 compound 1-38 4.34 11.85 85 Red Comparative Example 40 compound 1-41 4.37 12.97 107 Red Comparative Example 41 compound 1-44 4.30 15.16 91 Red Comparative Example 42 compound 1-2 compound C-2 4.06 15.36 149 Red Comparative Example 43 compound 1-5 4.07 15.84 141 Red Comparative Example 44 compound 1-8 4.04 15.70 131 Red Comparative Example 45 compound 1-15 4.14 16.10 139 Red Comparative Example 46 compound 1-20 4.12 15.49 141 Red Comparative Example 47 compound 1-25 4.02 16.06 138 Red Comparative Example 48 compound 1-30 4.04 16.33 145 Red Comparative Example 49 compound 1-35 4.01 15.34 139 Red Comparative Example 50 compound 1-39 4.11 15.23 148 Red Comparative Example 51 compound 1-42 4.14 16.77 128 Red Comparative Example 52 compound 1-45 4.26 15.81 114 Red Comparative Example 53 compound 1-3 compound C-3 4.28 14.41 123 Red Comparative Example 54 compound 1-6 4.20 14.39 115 Red Comparative Example 55 compound 1-9 4.27 14.65 123 Red Comparative Example 56 compound 1-17 4.33 14.99 122 Red Comparative Example 57 compound 1-22 4.26 14.53 117 Red Comparative Example 58 compound 1-26 4.34 14.76 114 Red Comparative Example 59 compound 1-31 4.25 14.46 119 Red Comparative Example 60 compound 1-36 4.35 14.93 133 Red Comparative Example 61 compound 1-40 4.23 14.59 133 Red Comparative Example 62 compound 1-43 4.35 14.40 121 Red Comparative Example 63 compound 1-47 4.26 15.80 122 Red

As shown in Tables 1 to 9, when the compound of Formula 1 and the compound of Formula 2 according to the present invention were co-deposited and used as a red light emitting layer, it was confirmed that the driving voltage decreased and the efficiency and lifespan increased compared to Comparative Example. there was. In addition, as shown in Table 8, when the compounds of Comparative Examples B-1 to B-3 and the compound of Formula 2 of the present invention were co-deposited and used as a red light emitting layer, the driving voltage was higher than the combination of the present invention, and the efficiency and lifespan were lowered. was shown. In addition, as shown in Table 9, even when the compounds of Comparative Examples C-1 to C-3 and the compound of Formula 1 of the present invention were co-deposited and used as a red light emitting layer, the driving voltage increased and the efficiency and lifespan decreased.

From these results, the reason that the driving voltage is improved and the efficiency and lifetime are increased according to the present invention is that the combination of the compound of Formula 1 as the first host and the compound of Formula 2 as the second host of the present invention is a red plate in the red light emitting layer. It was confirmed that it was due to the fact that the energy transfer to Troy was well performed. That is, the combination of the compound of Formula 1 and the compound of Formula 2 of the present invention, rather than the combination with the compound of Comparative Example, combines electrons and holes through a more stable balance in the light emitting layer to form excitons, thereby improving efficiency and lifespan. could check Therefore, it was confirmed that the driving voltage, luminous efficiency, and lifespan characteristics of the organic light emitting device could be improved when the compound of Formula 1 and the compound of Formula 2 were co-deposited and used as a host for the 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

Claims (12)

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

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

In Formula 2,
L ₄ and L ₅ are each independently a single bond, substituted or unsubstituted C _{6-60 arylene, or substituted or unsubstituted C 2} including any one or more selected from the group consisting of N, O and S _-60 heteroarylene,
Ar _{3 To} Ar ₆ are each independently substituted or unsubstituted C _{6-60 aryl, or substituted or unsubstituted C 2-60} heteroaryl including at least one selected from the group consisting of N, O and S to be.
According to claim 1,
Formula 1 is represented by any one selected from the group consisting of the following Formulas 1-1 to 1-9,
Organic light emitting device:

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

According to claim 1,
Formula 2 is represented by the following Formula 2-1 or 2-2,
Organic light emitting device:
[Formula 2-1]

[Formula 2-2]

In Formulas 2-1 to 2-2,
L ₄ , L ₅ , and Ar ₃ to Ar ₆ are each as defined in claim 1 .
8. The method of claim 7,
Formula 2-1 is represented by any one selected from the group consisting of the following 2-1-1 to 2-1-6,
Organic light emitting device:

In Formulas 2-1-1 to 2-1-6,
L ₄ , L ₅ , and Ar ₃ to Ar ₆ are each as defined in claim 1 .
8. The method of claim 7,
Formula 2-2 is represented by any one selected from the group consisting of the following 2-2-1 to 2-2-4,
Organic light emitting device:

In Formulas 2-2-1 to 2-2-4,
L ₄ , L ₅ , and Ar ₃ to Ar ₆ are each as defined in claim 1 .
According to claim 1,
L ₄ and L ₅ are each independently a single bond, or phenylene,
organic light emitting device.
According to claim 1,
Ar _{3 To} Ar ₆ are each independently phenyl, (naphthyl)phenylyl, (phenanthrenyl)phenylyl, biphenylyl, (phenyl)biphenylyl, naphthyl, (phenyl)naphthyl, phenanthrenyl, which is dibenzofuranyl, dibenzothiophenyl, or benzonaphthofuranyl;
organic light emitting device.
According to claim 1,
The compound represented by Formula 2 is any one selected from the group consisting of
Organic light emitting device:

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