KR102474921B1 - Organic light emitting device - Google Patents

Abstract

The present invention provides an organic light emitting device with improved driving voltage, efficiency and lifetime.

Description

Organic light emitting device {Organic light emitting device}

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

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

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

In the organic light emitting device as described above, the development of an organic light emitting device with improved driving voltage, efficiency, and lifespan is continuously required.

Korean Patent Publication No. 10-2000-0051826

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

The present invention provides the following organic light emitting device:

anode,

cathode, and

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

The light emitting layer includes a compound represented by Formula 1 and a compound represented by Formula 2 below.

Organic Light-Emitting Elements:

[Formula 1]

In Formula 1,

X is N, or CH, provided that at least one of X is N;

Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C _6-60 aryl; Or a C _5-60 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O and S,

R ₁ to R ₄ are each independently hydrogen; heavy hydrogen; or a substituted or unsubstituted C _6-60 aryl, or two adjacent ones bond to form a benzene ring;

R ₅ to R ₇ are each independently hydrogen; heavy hydrogen; or a substituted or unsubstituted C _6-60 aryl;

n1 is an integer from 0 to 6;

n2 and n3 are each independently an integer from 0 to 3;

[Formula 2]

In Formula 2,

A' is a benzene ring fused with two adjacent pentagonal rings,

L' ₁ and L' ₂ are each independently a single bond; Substituted or unsubstituted C _6-60 arylene; Or a C _5-60 heteroarylene containing at least one selected from the group consisting of substituted or unsubstituted N, O and S,

Ar' ₁ and Ar' ₂ are each independently a substituted or unsubstituted C _6-60 aryl; Or a C _5-60 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O and S,

R' ₁ and R' ₂ are each independently hydrogen; heavy hydrogen; or a substituted or unsubstituted C _6-60 aryl;

n'1 and n'2 are each independently an integer of 0 to 4.

The above-described organic light emitting device has excellent driving voltage, efficiency, and lifetime by including the compound represented by Formula 1 and the compound represented by Formula 2 in the light emitting layer.

1 shows an example of an organic light emitting device composed of a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4.
2 shows an example of an organic light emitting device composed of a substrate (1), an anode (2), a hole injection layer (5), a hole transport layer (6), a light emitting layer (7), an electron transport layer (8), and a cathode (4). it did
3 shows a substrate (1), an anode (2), a hole injection layer (5), a hole transport layer (6), an electron blocking layer (9), a light emitting layer (7), a hole blocking layer (10), an electron transport and injection transport layer An example of an organic light emitting element composed of (12) and a cathode (4) is shown.

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

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

means a bond connected to another substituent.

In this specification, the term "substituted or unsubstituted" means deuterium; halogen group; nitrile group; nitro group; hydroxy group; carbonyl group; ester group; imide group; amino group; phosphine oxide group; alkoxy group; aryloxy group; Alkyl thioxy group; Arylthioxy group; an alkyl sulfoxy group; aryl sulfoxy group; silyl group; boron group; an alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; Aralkenyl group; Alkyl aryl group; Alkylamine group; Aralkylamine group; heteroarylamine group; Arylamine group; Arylphosphine group; Or substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing at least one of N, O, and S atoms, or substituted or unsubstituted with two or more substituents linked to each other among the substituents exemplified above. . For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.

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

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

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

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

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

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

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

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

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

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

etc. However, it is not limited thereto.

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

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

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

anode and cathode

An anode and a cathode used in the present invention refer to electrodes used in an organic light emitting device.

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

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

light emitting layer

The light emitting layer used in the present invention means 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 light emitting layer includes a host material and a dopant material, and in the present invention, the compound represented by Formula 1 and the compound represented by Formula 2 are included as hosts.

Preferably, Formula 1 is represented by any one of Formulas 1-1 to 1-3 below:

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In Chemical Formulas 1-1 to 1-3, X, Ar ₁ , Ar ₂ , R ₁ to R ₅ , and n1 are as defined above.

Preferably all X's are N.

Preferably, Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, naphthyl, dibenzofuranyl, or dibenzothiophenyl.

Preferably, R ₅ to R ₇ are each independently hydrogen, deuterium, phenyl, biphenylyl, naphthyl, or phenanthrenyl. More preferably, R ₅ is hydrogen, deuterium, phenyl, biphenylyl, naphthyl, or phenanthrenyl, and R ₆ and R ₇ are hydrogen or deuterium.

Preferably, n1 is 0 or 1.

Preferably, n2 and n3 are each independently 0 or 1.

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

Meanwhile, the compound represented by Chemical Formula 1 can be prepared by a manufacturing method shown in Reaction Scheme 1 below.

[Scheme 1]

In Scheme 1, the definitions except for X' and X" are as defined above, and X' and X" are each independently halogen, and more preferably each independently bromo or chloro. Step 1 of Reaction Scheme 1 is a Suzuki coupling reaction, which is preferably carried out in the presence of a palladium catalyst and a base, and the reactor for the Suzuki coupling reaction can be changed as known in the art. Step 2 of Reaction Scheme 1 is an amine substitution reaction, and is preferably carried out in the presence of a palladium catalyst and a base, and the reactor for the amine substitution reaction may be modified as known in the art. The manufacturing method may be more specific in Preparation Examples to be described later.

Preferably, Formula 2 is represented by any one of Formulas 2-1 to 2-5 below:

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

In Chemical Formulas 2-1 to 2-5, L' ₁ , L' ₂ , Ar' ₁ , Ar' ₂ , R' ₁ , R' ₂ , n'1 and n'2 are as defined above.

Preferably, L' ₁ and L' ₂ are each independently a single bond, phenylene, or naphthylene.

Preferably, Ar' ₁ and Ar' ₂ are each independently phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl, dimethylfluorenyl, dibenzofuranyl, or dibenzothiophenyl.

Preferably, R' ₁ and R' ₂ are each independently hydrogen.

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

Meanwhile, the compound represented by Chemical Formula 2 can be prepared by a manufacturing method shown in Reaction Scheme 2 below.

[Scheme 2]

In Scheme 2, the definitions except for X' and X" are as defined above, and X' and X" are each independently halogen, and more preferably each independently bromo or chloro. Step 1 of Scheme 2 is an amine substitution reaction, which is preferably carried out in the presence of a palladium catalyst and a base, and the reactor for the amine substitution reaction may be modified as known in the art. Step 2 of Scheme 2 is an amine substitution reaction, which is preferably carried out in the presence of a palladium catalyst and a base, and the reactor for the amine substitution reaction may be modified as known in the art. The manufacturing method may be more specific in Preparation Examples to be described later.

Meanwhile, the weight ratio of the compound represented by Formula 1 and the compound represented by Formula 2 is 1:99 to 99:1, preferably 10:90 to 90:10, 20:80 to 80:20, 30: 70 to 70:30, or 40:60 to 60:40.

Meanwhile, the light emitting layer may include a dopant in addition to the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2.

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

hole transport layer

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

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

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

hole injection layer

The organic light emitting device 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 the hole injection material has the ability to transport holes and has a hole injection effect at the anode, an excellent hole injection effect for the light emitting layer or the light emitting material, and generated in the light emitting layer A compound that prevents migration of excitons to the electron injecting layer or electron injecting material and has excellent thin film formation ability is preferred. In addition, it is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic layer.

Specific examples of the hole injection material include metal porphyrins, oligothiophenes, arylamine-based organic materials, hexanitrilehexaazatriphenylene-based organic materials, quinacridone-based organic materials, and perylene-based organic materials. of organic matter, anthraquinone, and polyaniline and polythiophene-based conductive polymers, 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 cathode or an electron injection layer formed on 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 be received and transferred to the light emitting layer, a material having high electron mobility is suitable.

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

electron injection layer

The organic light emitting device 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 for injecting electrons from an electrode, has the ability to transport electrons, has an excellent electron injection effect from a cathode, an excellent electron injection effect for a light emitting layer or a light emitting material, and injects holes of excitons generated in the light emitting layer. It is preferable to use a compound that prevents migration to a layer and has excellent thin film forming ability.

Specific examples of materials that can be used as the electron injection layer include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preore nylidene methane, anthrone, etc. and their derivatives, metal complex compounds, nitrogen-containing 5-membered ring derivatives, etc., 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)( There are o-cresolato) gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, and bis(2-methyl-8-quinolinato)(2-naphtolato)gallium. Not limited to this.

organic light emitting device

The structure of the organic light emitting device according to the present invention is illustrated in FIG. 1 . 1 shows an example of an organic light emitting device composed of a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4. 2 is an example of an organic light emitting device composed of a substrate (1), an anode (2), a hole injection layer (5), a hole transport layer (6), a light emitting layer (7), an electron transport layer (8), and a cathode (4). is shown. 3 shows a substrate (1), an anode (2), a hole injection layer (5), a hole transport layer (6), an electron blocking layer (9), a light emitting layer (7), a hole blocking layer (10), electron transport and An example of an organic light emitting device composed of the injection layer 12 and the cathode 4 is shown. In this structure, the compound represented by Formula 1 may be included in at least one layer of the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the hole blocking layer, and the electron transport and injection layer.

The organic light emitting device according to the present invention can be manufactured by sequentially stacking the above-described components. At this time, by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation, depositing a metal or a metal oxide having conductivity or an alloy thereof on the substrate to form an anode And, after forming each of the above-described layers thereon, it can be manufactured by depositing a material that can be used as a cathode thereon. In addition to this method, an organic light emitting device may be manufactured by sequentially depositing a cathode material on a substrate and an anode material in the reverse order of the above configuration (WO 2003/012890). In addition, the light emitting layer may be formed by a solution coating method as well as a vacuum deposition method of a host and a dopant. Here, the solution coating method means spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, etc., but is not limited to these.

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

Hereinafter, a preferred embodiment is presented to aid understanding of the present invention. However, the following examples are only provided to more easily understand the present invention, and the content of the present invention is not limited thereby.

[Production Example]

Preparation Example 1: Preparation of Compound 1

In a nitrogen atmosphere, compound sub1 (15 g, 56 mmol) and compound a (15.2 g, 61.6 mmol) were added to THF (300 ml), stirred and refluxed. After dissolving potassium carbonate (23.2 g, 168.1 mmol) in water (70 ml), it was added, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.9 g, 1.7 mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound sub1-1 (16.5 g, yield 68%).

MS: [M+H] ⁺ = 434

In a nitrogen atmosphere, compound A (10 g, 46 mmol), compound sub1-1 (22 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to xylene (200 ml), stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 1 (18.4 g, yield 65%).

MS: [M+H] ⁺ = 615

Preparation Example 2: Preparation of Compound 2

In a nitrogen atmosphere, compound sub1 (15 g, 56 mmol) and compound b (15.2 g, 61.6 mmol) were added to THF (300 ml), stirred and refluxed. After dissolving potassium carbonate (23.2 g, 168.1 mmol) in water (70 ml), it was added, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.9 g, 1.7 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound sub1-2 (16 g, yield 66%).

MS: [M+H] ⁺ = 434

In a nitrogen atmosphere, compound A (10 g, 46 mmol), compound sub1-2 (22 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to xylene (200 ml), stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 2 (15.3 g, yield 54%).

MS: [M+H] ⁺ = 615

Preparation Example 3: Preparation of Compound 3

In a nitrogen atmosphere, compound B (10 g, 37.4 mmol), compound sub1-2 (17.9 g, 41.1 mmol), and sodium tert-butoxide (7.2 g, 74.8 mmol) were added to xylene (200 ml), stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 3 (12.7 g, yield 51%).

MS: [M+H] ⁺ = 665

Preparation Example 4: Preparation of Compound 4

In a nitrogen atmosphere, compound sub2 (15 g, 41.9 mmol) and compound c (11.4 g, 46.1 mmol) were added to THF (300 ml) and stirred and refluxed. Thereafter, potassium carbonate (17.4 g, 125.8 mmol) was dissolved in water (52 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.3 mmol) was added. After reacting for 11 hours, it was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound sub1-3 (17.3 g, yield 79%).

MS: [M+H] ⁺ = 524

In a nitrogen atmosphere, compound A (10 g, 46 mmol), compound sub1-3 (26.5 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to xylene (200 ml), stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 4 (21.1 g, yield 65%).

MS: [M+H] ⁺ = 705

Preparation Example 5: Preparation of Compound 5

In a nitrogen atmosphere, compound sub1 (15 g, 56 mmol) and compound d (15.2 g, 61.6 mmol) were added to THF (300 ml), stirred and refluxed. After dissolving potassium carbonate (23.2 g, 168.1 mmol) in water (70 ml), it was added, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.9 g, 1.7 mmol) was added. After reacting for 11 hours, it was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound sub1-4 (15.3 g, yield 63%).

MS: [M+H] ⁺ = 434

In a nitrogen atmosphere, compound A (10 g, 46 mmol), compound sub1-4 (22 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to xylene (200 ml), stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 5 (17 g, yield 60%).

MS: [M+H] ⁺ = 615

Preparation Example 6: Preparation of compound 6

In a nitrogen atmosphere, compound sub1 (15 g, 56 mmol) and compound e (15.2 g, 61.6 mmol) were added to THF (300 ml) and stirred and refluxed. After dissolving potassium carbonate (23.2 g, 168.1 mmol) in water (70 ml), it was added, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.9 g, 1.7 mmol) was added. After reacting for 11 hours, it was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound sub1-5 (18.9 g, yield 78%).

MS: [M+H] ⁺ = 434

In a nitrogen atmosphere, compound A (10 g, 46 mmol), compound sub1-5 (22 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to xylene (200 ml), stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 6 (14.1 g, yield 50%).

MS: [M+H] ⁺ = 615

Preparation Example 7: Preparation of Compound 7

In a nitrogen atmosphere, compound sub1 (15 g, 56 mmol) and compound f (15.2 g, 61.6 mmol) were added to THF (300 ml), stirred and refluxed. After dissolving potassium carbonate (23.2 g, 168.1 mmol) in water (70 ml), it was added, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.9 g, 1.7 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound sub1-6 (17.7 g, yield 73%).

MS: [M+H] ⁺ = 434

In a nitrogen atmosphere, compound A (10 g, 46 mmol), compound sub1-6 (22 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to xylene (200 ml), stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 7 (17.5 g, yield 62%).

MS: [M+H] ⁺ = 615

Preparation Example 8: Preparation of Compound 8

In a nitrogen atmosphere, compound B (10 g, 37.4 mmol), compound sub1-6 (17.9 g, 41.1 mmol), and sodium tert-butoxide (7.2 g, 74.8 mmol) were added to xylene (200 ml), stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 8 (16.9 g, yield 68%).

MS: [M+H] ⁺ = 665

Preparation Example 9: Preparation of Compound 9

In a nitrogen atmosphere, compound sub1 (15 g, 56 mmol) and compound g (15.2 g, 61.6 mmol) were added to THF (300 ml), stirred and refluxed. After dissolving potassium carbonate (23.2 g, 168.1 mmol) in water (70 ml), it was added, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.9 g, 1.7 mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound sub1-7 (18 g, yield 74%).

MS: [M+H] ⁺ = 434

In a nitrogen atmosphere, compound A (10 g, 46 mmol), compound sub1-7 (22 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to xylene (200 ml), stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 9 (19.8 g, yield 70%).

MS: [M+H] ⁺ = 615

Preparation Example 10: Preparation of Compound 10

In a nitrogen atmosphere, compound sub3 (15 g, 43.6 mmol) and compound h (11.8 g, 48 mmol) were added to THF (300 ml) and stirred and refluxed. Thereafter, potassium carbonate (18.1 g, 130.9 mmol) was dissolved in water (54 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.7 g, 1.3 mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound sub1-8 (14.2 g, yield 64%).

MS: [M+H] ⁺ = 510

In a nitrogen atmosphere, compound A (10 g, 46 mmol), compound sub1-8 (25.4 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to xylene (200 ml), stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 10 (18.1 g, yield 57%).

MS: [M+H] ⁺ = 691

Preparation Example 11: Preparation of Compound 11

In a nitrogen atmosphere, compound sub1 (15 g, 56 mmol) and compound i (15.2 g, 61.6 mmol) were added to THF (300 ml), stirred and refluxed. After dissolving potassium carbonate (23.2 g, 168.1 mmol) in water (70 ml), it was added, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.9 g, 1.7 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound sub1-9 (18.9 g, yield 78%).

MS: [M+H] ⁺ = 434

In a nitrogen atmosphere, compound A (10 g, 46 mmol), compound sub1-9 (22 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to xylene (200 ml), stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 11 (16.7 g, yield 59%).

MS: [M+H] ⁺ = 615

Preparation Example 12: Preparation of Compound 12

In a nitrogen atmosphere, compound sub1 (15 g, 56 mmol) and compound j (15.2 g, 61.6 mmol) were added to THF (300 ml), stirred and refluxed. After dissolving potassium carbonate (23.2 g, 168.1 mmol) in water (70 ml), it was added, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.9 g, 1.7 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound sub1-10 (15.5 g, yield 64%).

MS: [M+H] ⁺ = 434

In a nitrogen atmosphere, compound A (10 g, 46 mmol), compound sub1-10 (22 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to xylene (200 ml), stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 12 (16.7 g, yield 59%).

MS: [M+H] ⁺ = 615

Preparation Example 13: Preparation of Compound 13

In a nitrogen atmosphere, compound sub4 (15 g, 47.2 mmol) and compound k (12.8 g, 51.9 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (19.6 g, 141.6 mmol) was dissolved in water (59 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.7 g, 1.4 mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound sub1-11 (15.1 g, yield 66%).

MS: [M+H] ⁺ = 484

In a nitrogen atmosphere, compound A (10 g, 46 mmol), compound sub1-11 (24.5 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to xylene (200 ml), stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 13 (15.9 g, yield 52%).

MS: [M+H] ⁺ = 665

Preparation Example 14: Preparation of Compound 14

In a nitrogen atmosphere, compound sub5 (15 g, 41.9 mmol) and compound 1 (11.4 g, 46.1 mmol) were added to THF (300 ml) and stirred and refluxed. Thereafter, potassium carbonate (17.4 g, 125.8 mmol) was dissolved in water (52 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.3 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound sub1-12 (14.7 g, yield 67%).

MS: [M+H] ⁺ = 524

In a nitrogen atmosphere, compound A (10 g, 46 mmol), compound sub1-12 (26.5 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to xylene (200 ml), stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 14 (20.1 g, yield 62%).

MS: [M+H] ⁺ = 705

Preparation Example 15: Preparation of Compound 15

In a nitrogen atmosphere, compound sub2 (15 g, 41.9 mmol) and compound m (11.4 g, 46.1 mmol) were added to THF (300 ml) and stirred and refluxed. Thereafter, potassium carbonate (17.4 g, 125.8 mmol) was dissolved in water (52 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.3 mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound sub1-13 (17.1 g, yield 78%).

MS: [M+H] ⁺ = 524

In a nitrogen atmosphere, compound C (10 g, 37.4 mmol), compound sub1-13 (21.6 g, 41.2 mmol), and sodium tert-butoxide (7.2 g, 74.8 mmol) were added to xylene (200 ml), stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 15 (13.2 g, yield 50%).

MS: [M+H] ⁺ = 705

Preparation Example 16: Preparation of Compound 16

In a nitrogen atmosphere, compound sub6 (15 g, 40.8 mmol) and compound n (11.1 g, 44.9 mmol) were added to THF (300 ml) and stirred and refluxed. Thereafter, potassium carbonate (16.9 g, 122.3 mmol) was dissolved in water (51 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added. After reacting for 11 hours, it was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound sub1-14 (15.4 g, yield 71%).

MS: [M+H] ⁺ = 534

In a nitrogen atmosphere, compound A (10 g, 46 mmol), compound sub1-14 (27 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to xylene (200 ml), stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 16 (19.4 g, yield 59%).

MS: [M+H] ⁺ = 715

Preparation Example 17: Preparation of Compound 17

In a nitrogen atmosphere, compound sub4 (15 g, 47.2 mmol) and compound o (12.8 g, 51.9 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (19.6 g, 141.6 mmol) was dissolved in water (59 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.7 g, 1.4 mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound sub1-15 (16.6 g, yield 73%).

MS: [M+H] ⁺ = 484

In a nitrogen atmosphere, compound A (10 g, 46 mmol), compound sub1-15 (24.5 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to xylene (200 ml), stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 17 (18 g, yield 59%).

MS: [M+H] ⁺ = 665

Preparation Example 18: Preparation of Compound 18

In a nitrogen atmosphere, compound sub7 (15 g, 47.2 mmol) and compound p (12.8 g, 51.9 mmol) were added to THF (300 ml) and stirred and refluxed. Thereafter, potassium carbonate (19.6 g, 141.6 mmol) was dissolved in water (59 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.7 g, 1.4 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound sub1-16 (16.9 g, yield 74%).

MS: [M+H] ⁺ = 484

In a nitrogen atmosphere, compound A (10 g, 46 mmol), compound sub1-16 (24.5 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to xylene (200 ml), stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 18 (18.3 g, yield 60%).

MS: [M+H] ⁺ = 665

Preparation Example 19: Preparation of Compound 19

In a nitrogen atmosphere, compound sub3 (15 g, 43.6 mmol) and compound b (11.8 g, 48 mmol) were added to THF (300 ml) and stirred and refluxed. Thereafter, potassium carbonate (18.1 g, 130.9 mmol) was dissolved in water (54 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.7 g, 1.3 mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound sub1-17 (17.1 g, yield 77%).

MS: [M+H] ⁺ = 510

In a nitrogen atmosphere, compound A (10 g, 46 mmol), compound sub1-17 (25.4 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to xylene (200 ml), stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 19 (21 g, yield 66%).

MS: [M+H] ⁺ = 691

Preparation Example 20: Preparation of compound 20

In a nitrogen atmosphere, compound sub8 (15 g, 35.7 mmol) and compound p (9.7 g, 39.3 mmol) were added to THF (300 ml) and stirred and refluxed. Thereafter, potassium carbonate (14.8 g, 107.2 mmol) was dissolved in water (44 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.1 mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound sub1-18 (13 g, yield 62%).

MS: [M+H] ⁺ = 586

In a nitrogen atmosphere, compound A (10 g, 46 mmol), compound sub1-18 (29.7 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to xylene (200 ml), stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 20 (24.7 g, yield 70%).

MS: [M+H] ⁺ = 767

Preparation Example 21: Preparation of Compound 21

In a nitrogen atmosphere, compound sub4 (15 g, 47.2 mmol) and compound q (12.8 g, 51.9 mmol) were added to THF (300 ml) and stirred and refluxed. Thereafter, potassium carbonate (19.6 g, 141.6 mmol) was dissolved in water (59 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.7 g, 1.4 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound sub1-19 (17.8 g, yield 78%).

MS: [M+H] ⁺ = 484

In a nitrogen atmosphere, compound A (10 g, 46 mmol), compound sub1-19 (24.5 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to xylene (200 ml), stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 21 (16.8 g, yield 55%).

MS: [M+H] ⁺ = 665

Preparation Example 22: Preparation of compound 22

In a nitrogen atmosphere, compound sub1 (15 g, 56 mmol) and compound k (15.2 g, 61.6 mmol) were added to THF (300 ml), stirred and refluxed. After dissolving potassium carbonate (23.2 g, 168.1 mmol) in water (70 ml), it was added, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.9 g, 1.7 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound sub1-20 (23.4 g, yield 80%).

MS: [M+H] ⁺ = 524

In a nitrogen atmosphere, compound A (10 g, 46 mmol), compound sub1-20 (26.5 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to xylene (200 ml), stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 22 (16.2 g, yield 50%).

MS: [M+H] ⁺ = 705

Preparation Example 23: Preparation of compound 23

In a nitrogen atmosphere, compound sub9 (15 g, 41.9 mmol) and compound i (11.4 g, 46.1 mmol) were added to THF (300 ml) and stirred and refluxed. Thereafter, potassium carbonate (17.4 g, 125.8 mmol) was dissolved in water (52 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.3 mmol) was added. After reacting for 11 hours, it was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound sub1-21 (14.3 g, yield 65%).

MS: [M+H] ⁺ = 524

In a nitrogen atmosphere, compound D (10 g, 37.4 mmol), compound sub1-21 (21.6 g, 41.1 mmol), and sodium tert-butoxide (7.2 g, 74.8 mmol) were added to xylene (200 ml), stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 23 (17.5 g, yield 62%).

MS: [M+H] ⁺ = 755

Preparation Example 24: Preparation of Compound 24

In a nitrogen atmosphere, compound sub10 (15 g, 43.6 mmol) and compound r (11.8 g, 48 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (18.1 g, 130.9 mmol) was dissolved in water (54 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.7 g, 1.3 mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound sub1-22 (16 g, yield 72%).

MS: [M+H] ⁺ = 510

In a nitrogen atmosphere, compound A (10 g, 46 mmol), compound sub1-22 (25.8 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to xylene (200 ml), stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 24 (22.2 g, yield 70%).

MS: [M+H] ⁺ = 691

Preparation Example 25: Preparation of Compound 25

In a nitrogen atmosphere, compound sub10 (15 g, 43.6 mmol) and compound s (11.8 g, 48 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (18.1 g, 130.9 mmol) was dissolved in water (54 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.7 g, 1.3 mmol) was added. After reacting for 11 hours, it was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound sub1-23 (15.8 g, yield 71%).

MS: [M+H] ⁺ = 510

In a nitrogen atmosphere, compound A (10 g, 46 mmol), compound sub1-23 (25.8 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to xylene (200 ml), stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 25 (21.3 g, yield 67%).

MS: [M+H] ⁺ = 691

Preparation Example 26: Preparation of compound 26

In a nitrogen atmosphere, compound sub2 (15 g, 41.9 mmol) and compound t (11.4 g, 46.1 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (17.4 g, 125.8 mmol) was dissolved in water (52 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.3 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound sub1-24 (14 g, yield 64%).

MS: [M+H] ⁺ = 524

In a nitrogen atmosphere, compound A (10 g, 46 mmol), compound sub1-24 (26.5 g, 50.6 mmol), and sodium tert-butoxide (8.8 g, 92.1 mmol) were added to xylene (200 ml), stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 26 (22.7 g, yield 70%).

MS: [M+H] ⁺ = 705

Preparation Example 27: Preparation of Compound 27

In a nitrogen atmosphere, compound E (10 g, 39 mmol), compound sub11 (9.1 g, 39 mmol), and sodium tert-butoxide (7.5 g, 78 mmol) were added to xylene (200 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound E-1 (10.8 g, yield 68%).

MS: [M+H] ⁺ = 409

In a nitrogen atmosphere, compound E-1 (10 g, 24.5 mmol), compound sub12 (6.3 g, 26.9 mmol), and sodium tert-butoxide (4.7 g, 49 mmol) were added to xylene (200 ml), stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 27 (8.2 g, yield 60%).

MS: [M+H] ⁺ = 561

Preparation Example 28: Preparation of compound 28

In a nitrogen atmosphere, compound E (10 g, 39 mmol), compound sub13 (11 g, 39 mmol), and sodium tert-butoxide (7.5 g, 78 mmol) were added to xylene (200 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound E-2 (9.8 g, yield 55%).

MS: [M+H] ⁺ = 459

In a nitrogen atmosphere, compound E-2 (10 g, 21.8 mmol), compound sub14 (5 g, 24 mmol), and sodium tert-butoxide (4.2 g, 43.6 mmol) were added to xylene (200 ml), stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 28 (7.1 g, yield 56%).

MS: [M+H] ⁺ = 585

Preparation Example 29: Preparation of Compound 29

In a nitrogen atmosphere, compound F (10 g, 39 mmol), compound sub15 (6.1 g, 39 mmol), and sodium tert-butoxide (7.5 g, 78 mmol) were added to xylene (200 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound F-1 (8.3 g, yield 64%).

MS: [M+H] ⁺ = 333

In a nitrogen atmosphere, compound F-1 (10 g, 30.1 mmol), compound sub16 (10.2 g, 33.1 mmol), and sodium tert-butoxide (5.8 g, 60.2 mmol) were added to xylene (200 ml), stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 29 (9.9 g, yield 59%).

MS: [M+H] ⁺ = 561

Preparation Example 30: Preparation of compound 30

In a nitrogen atmosphere, compound E (10 g, 39 mmol), compound sub17 (12.1 g, 39 mmol), and sodium tert-butoxide (7.5 g, 78 mmol) were added to xylene (200 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound E-3 (9.6 g, yield 51%).

MS: [M+H] ⁺ = 485

In a nitrogen atmosphere, compound E-3 (10 g, 20.6 mmol), compound sub18 (4.7 g, 22.7 mmol), and sodium tert-butoxide (4 g, 41.3 mmol) were added to xylene (200 ml), stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 30 (7.8 g, yield 62%).

MS: [M+H] ⁺ = 611

Preparation Example 31: Preparation of Compound 31

In a nitrogen atmosphere, compound F (10 g, 39 mmol), compound sub14 (17.8 g, 85.8 mmol), and sodium tert-butoxide (15 g, 156.1 mmol) were added to xylene (200 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.8 g, 1.6 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 31 (11.3 g, yield 57%).

MS: [M+H] ⁺ = 509

Preparation Example 32: Preparation of Compound 32

In a nitrogen atmosphere, compound F (10 g, 39 mmol), compound sub12 (9.1 g, 39 mmol), and sodium tert-butoxide (7.5 g, 78 mmol) were added to xylene (200 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound F-2 (9.6 g, yield 60%).

MS: [M+H] ⁺ = 409

In a nitrogen atmosphere, compound F-2 (10 g, 24.5 mmol), compound sub19 (6.7 g, 26.9 mmol), and sodium tert-butoxide (4.7 g, 49 mmol) were added to xylene (200 ml), stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 32 (8.2 g, yield 58%).

MS: [M+H] ⁺ = 575

Preparation Example 33: Preparation of Compound 33

In a nitrogen atmosphere, compound F-2 (10 g, 24.5 mmol), compound sub20 (7.6 g, 26.9 mmol), and sodium tert-butoxide (4.7 g, 49 mmol) were added to xylene (200 ml), stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 33 (8.1 g, yield 54%).

MS: [M+H] ⁺ = 611

Preparation Example 34: Preparation of compound 34

In a nitrogen atmosphere, compound F-2 (10 g, 24.5 mmol), compound sub21 (7.6 g, 26.9 mmol), and sodium tert-butoxide (4.7 g, 49 mmol) were added to xylene (200 ml), stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 34 (8.7 g, yield 58%).

MS: [M+H] ⁺ = 611

Preparation Example 35: Preparation of Compound 35

In a nitrogen atmosphere, compound G (10 g, 39 mmol), compound sub22 (9.6 g, 39 mmol), and sodium tert-butoxide (7.5 g, 78 mmol) were added to xylene (200 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound G-1 (10.2 g, yield 62%).

MS: [M+H] ⁺ = 423

In a nitrogen atmosphere, compound G-1 (10 g, 23.7 mmol), compound sub14 (5.4 g, 26 mmol), and sodium tert-butoxide (4.5 g, 47.3 mmol) were added to xylene (200 ml), stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 35 (8.6 g, yield 66%).

MS: [M+H] ⁺ = 549

Preparation Example 36: Preparation of Compound 36

In a nitrogen atmosphere, compound G (10 g, 39 mmol), compound sub23 (12.1 g, 39 mmol), and sodium tert-butoxide (7.5 g, 78 mmol) were added to xylene (200 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound G-2 (12.8 g, yield 68%).

MS: [M+H] ⁺ = 485

In a nitrogen atmosphere, compound G-2 (10 g, 20.6 mmol), compound sub12 (5.3 g, 22.7 mmol), and sodium tert-butoxide (4 g, 41.3 mmol) were added to xylene (200 ml), stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 36 (7 g, yield 53%).

MS: [M+H] ⁺ = 637

Preparation Example 37: Preparation of Compound 37

In a nitrogen atmosphere, compound G (10 g, 39 mmol), compound sub14 (8.1 g, 39 mmol), and sodium tert-butoxide (7.5 g, 78 mmol) were added to xylene (200 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound G-3 (9.7 g, yield 65%).

MS: [M+H] ⁺ = 383

In a nitrogen atmosphere, compound G-3 (10 g, 26.1 mmol), compound sub11 (6.7 g, 28.8 mmol), and sodium tert-butoxide (5 g, 52.3 mmol) were added to xylene (200 ml), stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 37 (9.1 g, yield 65%).

MS: [M+H] ⁺ = 535

Preparation Example 38: Preparation of Compound 38

In a nitrogen atmosphere, compound G (10 g, 39 mmol), compound sub15 (6.1 g, 39 mmol), and sodium tert-butoxide (7.5 g, 78 mmol) were added to xylene (200 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound G-4 (6.9 g, yield 53%).

MS: [M+H] ⁺ = 333

In a nitrogen atmosphere, compound G-4 (10 g, 30.1 mmol), compound sub24 (8.7 g, 33.1 mmol), and sodium tert-butoxide (5.8 g, 60.2 mmol) were added to xylene (200 ml), stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 38 (8.4 g, yield 54%).

MS: [M+H] ⁺ = 515

Preparation Example 39: Preparation of compound 39

In a nitrogen atmosphere, compound G (10 g, 39 mmol), compound sub19 (9.6 g, 39 mmol), and sodium tert-butoxide (7.5 g, 78 mmol) were added to xylene (200 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound G-5 (10.2 g, yield 62%).

MS: [M+H] ⁺ = 423

In a nitrogen atmosphere, compound G-5 (10 g, 23.7 mmol), compound sub21 (7.4 g, 26 mmol), and sodium tert-butoxide (4.5 g, 47.3 mmol) were added to xylene (200 ml), stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 39 (8.3 g, yield 56%).

MS: [M+H] ⁺ = 625

Preparation Example 40: Preparation of compound 40

In a nitrogen atmosphere, compound G (10 g, 39 mmol), compound sub25 (9.6 g, 39 mmol), and sodium tert-butoxide (7.5 g, 78 mmol) were added to xylene (200 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound G-6 (9.9 g, yield 60%).

MS: [M+H] ⁺ = 423

In a nitrogen atmosphere, compound G-6 (10 g, 23.7 mmol), compound sub26 (7.4 g, 26 mmol), and sodium tert-butoxide (4.5 g, 47.3 mmol) were added to xylene (200 ml), stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 40 (8.1 g, yield 55%).

MS: [M+H] ⁺ = 625

Preparation Example 41: Preparation of Compound 41

In a nitrogen atmosphere, compound G-4 (10 g, 30.1 mmol), compound sub27 (8.7 g, 33.1 mmol), and sodium tert-butoxide (5.8 g, 60.2 mmol) were added to xylene (200 ml), stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 41 (9.1 g, yield 59%).

MS: [M+H] ⁺ = 515

Preparation Example 42: Preparation of Compound 42

In a nitrogen atmosphere, compound H (10 g, 39 mmol), compound sub11 (20 g, 85.8 mmol), and sodium tert-butoxide (15 g, 156.1 mmol) were added to xylene (200 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.8 g, 1.6 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 42 (14.6 g, yield 67%).

MS: [M+H] ⁺ = 561

Preparation Example 43: Preparation of Compound 43

In a nitrogen atmosphere, compound H (10 g, 39 mmol), compound sub23 (12.1 g, 39 mmol), and sodium tert-butoxide (7.5 g, 78 mmol) were added to xylene (200 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound H-1 (13.2 g, yield 70%).

MS: [M+H] ⁺ = 485

In a nitrogen atmosphere, compound H-1 (10 g, 20.6 mmol), compound sub15 (3.6 g, 22.7 mmol), and sodium tert-butoxide (4 g, 41.3 mmol) were added to xylene (200 ml), stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 43 (7.7 g, yield 67%).

MS: [M+H] ⁺ = 561

Preparation Example 44: Preparation of Compound 44

In a nitrogen atmosphere, compound H (10 g, 39 mmol), compound sub11 (9.1 g, 39 mmol), and sodium tert-butoxide (7.5 g, 78 mmol) were added to xylene (200 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound H-2 (8.8 g, yield 55%).

MS: [M+H] ⁺ = 409

In a nitrogen atmosphere, compound H-2 (10 g, 24.5 mmol), compound sub13 (7.6 g, 26.9 mmol), and sodium tert-butoxide (4.7 g, 49 mmol) were added to xylene (200 ml), stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 44 (10.5 g, yield 70%).

MS: [M+H] ⁺ = 611

Preparation Example 45: Preparation of Compound 45

In a nitrogen atmosphere, compound H (10 g, 39 mmol), compound sub28 (10.7 g, 39 mmol), and sodium tert-butoxide (7.5 g, 78 mmol) were added to xylene (200 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound H-3 (10 g, yield 57%).

MS: [M+H] ⁺ = 449

In a nitrogen atmosphere, compound H-3 (10 g, 22.3 mmol), compound sub15 (3.9 g, 24.5 mmol), and sodium tert-butoxide (4.3 g, 44.6 mmol) were added to xylene (200 ml), stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 45 (7.4 g, yield 63%).

MS: [M+H] ⁺ = 525

Preparation Example 46: Preparation of Compound 46

In a nitrogen atmosphere, compound H (10 g, 39 mmol), compound sub19 (9.6 g, 39 mmol), and sodium tert-butoxide (7.5 g, 78 mmol) were added to xylene (200 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound H-4 (8.4 g, yield 51%).

MS: [M+H] ⁺ = 423

In a nitrogen atmosphere, compound H-4 (10 g, 22.6 mmol), compound sub11 (5.8 g, 24.9 mmol), and sodium tert-butoxide (4.3 g, 45.2 mmol) were added to xylene (200 ml), stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 46 (8.6 g, yield 66%).

MS: [M+H] ⁺ = 575

Preparation Example 47: Preparation of Compound 47

In a nitrogen atmosphere, compound I (10 g, 39 mmol), compound sub16 (12.1 g, 39 mmol), and sodium tert-butoxide (7.5 g, 78 mmol) were added to xylene (200 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound I-1 (13.1 g, yield 60%).

MS: [M+H] ⁺ = 561

In a nitrogen atmosphere, compound I-1 (10 g, 17.8 mmol), compound sub12 (4.6 g, 19.6 mmol), and sodium tert-butoxide (3.4 g, 35.7 mmol) were added to xylene (200 ml), stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 47 (7.2 g, yield 57%).

MS: [M+H] ⁺ = 713

Preparation Example 48: Preparation of Compound 48

In a nitrogen atmosphere, compound I (10 g, 39 mmol), compound sub14 (8.1 g, 39 mmol), and sodium tert-butoxide (7.5 g, 78 mmol) were added to xylene (200 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound I-2 (8.1 g, yield 54%).

MS: [M+H] ⁺ = 383

In a nitrogen atmosphere, compound I-2 (10 g, 26.1 mmol), compound sub17 (8.9 g, 28.8 mmol), and sodium tert-butoxide (5 g, 52.3 mmol) were added to xylene (200 ml), stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 48 (8.1 g, yield 51%).

MS: [M+H] ⁺ = 611

Preparation Example 49: Preparation of compound 49

In a nitrogen atmosphere, compound I (10 g, 39 mmol), compound sub29 (12.1 g, 39 mmol), and sodium tert-butoxide (7.5 g, 78 mmol) were added to xylene (200 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound I-3 (12.3 g, yield 65%).

MS: [M+H] ⁺ = 485

In a nitrogen atmosphere, compound I-3 (10 g, 20.6 mmol), compound sub11 (5.3 g, 22.7 mmol), and sodium tert-butoxide (4 g, 41.3 mmol) were added to xylene (200 ml), stirred and refluxed. . Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 49 (7.7 g, yield 59%).

MS: [M+H] ⁺ = 637

[Example]

Example 1: Manufacturing of organic light emitting device

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

The following compound HI-1 was formed to a thickness of 1150 Å as a hole injection layer on the prepared ITO transparent electrode, but the following compound A-1 was p-doped at a concentration of 1.5%. A hole transport layer having a thickness of 800 Å was formed by vacuum depositing the following HT-1 compound on the hole injection layer. An electron blocking layer having a thickness of 150 Å was formed on the hole transport layer by vacuum depositing the following EB-1 compound. Compound 1 (first host), compound 28 (second host), and the following compound Dp-7 (dopant) were vacuum deposited on the electron suppression layer at a weight ratio of 49:49:2 to obtain a film thickness of 400 Å. A red light emitting layer was formed. A hole blocking layer having a thickness of 30 Å was formed on the light emitting layer by vacuum depositing the following HB-1 compound. An electron injection and transport layer having a thickness of 300 Å was formed on the hole-blocking layer by vacuum depositing the following ET-1 compound and the following LiQ compound in a weight ratio of 2:1. A negative electrode was formed by sequentially depositing lithium fluoride (LiF) to a thickness of 12 Å and aluminum to a thickness of 1,000 Å on the electron injection and transport layer.

In the above process, the deposition rate of the organic material was maintained at 0.4 ~ 0.7 Å / sec, the deposition rate of lithium fluoride on the negative electrode was maintained at 0.3 Å / sec, and the deposition rate of aluminum was 2 Å / sec, and the vacuum degree during deposition was 2 × 10 ^-7 Maintaining ~ 5ⅹ10 ^-6 torr, an organic light emitting device was manufactured.

Examples 2 to 104

An organic light emitting device was manufactured in the same manner as in Example 1, except that the compounds listed in Tables 1 to 3 were used instead of Compound 1 and Compound 28, respectively.

Comparative Examples 1 to 15

An organic light emitting device was manufactured in the same manner as in Example 1, except that the compounds shown in Table 4 were used instead of Compound 1 and Compound 28, respectively. In each comparative example, the second host was not used, and the light emitting layer was prepared using the first host and the dopant at a weight ratio of 98:2.

Comparative Examples 16 to 63

An organic light emitting device was manufactured in the same manner as in Example 1, except that the compounds shown in Tables 5 and 6 were used instead of Compound 1 and Compound 28, respectively. In Tables 5 and 6, each compound is as follows.

When current was applied to the organic light emitting devices prepared in the above Examples and Comparative Examples, voltage, efficiency, and lifetime were measured, and the results are shown in Tables 1 to 6 below. The lifetime T95 means the time required for the luminance to decrease from the initial luminance (5,000 nit) to 95%.

division 1st host 2nd host driving voltage
(V@10mA/cm ² ) efficiency
(cd/A@10mA/cm ² ) Lifetime T95
(hr@10mA/cm ² ) luminescent color Example 1 compound 1 compound 28 3.56 23.3 263 Red Example 2 compound 1 compound 32 3.48 22.4 247 Red Example 3 compound 1 compound 37 3.47 24.5 288 Red Example 4 compound 1 compound 42 3.46 23.7 265 Red Example 5 compound 2 compound 27 3.68 22.2 223 Red Example 6 compound 2 compound 34 3.73 21.5 236 Red Example 7 compound 2 compound 38 3.71 21.1 227 Red Example 8 compound 2 compound 46 3.74 22.4 241 Red Example 8 compound 3 compound 31 3.71 22.3 223 Red Example 10 compound 3 compound 39 3.73 21.5 212 Red Example 11 compound 3 compound 43 3.76 21.3 237 Red Example 12 compound 3 compound 47 3.70 21.7 221 Red Example 13 compound 4 compound 29 3.62 20.5 223 Red Example 14 compound 4 compound 35 3.7` 22.1 230 Red Example 15 compound 4 compound 45 3.72 21.7 227 Red Example 16 compound 4 compound 49 3.76 20.6 241 Red Example 17 compound 5 compound 28 3.57 24.7 253 Red Example 18 compound 5 compound 32 3.41 23.8 277 Red Example 19 compound 5 compound 37 3.40 24.3 292 Red Example 20 compound 5 compound 42 3.48 25.0 253 Red Example 21 compound 6 compound 27 3.77 21.5 233 Red Example 22 compound 6 compound 34 3.70 22.2 245 Red Example 23 compound 6 compound 38 3.83 23.1 231 Red Example 24 compound 6 compound 46 3.80 22.4 247 Red Example 25 compound 7 compound 31 3.81 21.4 238 Red Example 26 compound 7 compound 39 3.79 21.7 229 Red Example 27 compound 7 compound 43 3.72 20.8 243 Red Example 28 compound 7 compound 47 3.70 20.5 234 Red Example 29 compound 8 compound 29 3.72 25.9 284 Red Example 30 compound 8 compound 35 3.80 24.1 281 Red Example 31 compound 8 compound 45 3.78 23.9 290 Red Example 32 compound 8 compound 49 3.82 24.4 273 Red Example 33 compound 9 compound 28 3.88 20.3 231 Red Example 34 compound 9 compound 32 3.80 21.5 244 Red Example 35 compound 9 compound 37 3.71 21.3 227 Red Example 36 compound 9 compound 42 3.72 20.4 234 Red

division 1st host 2nd host drive voltage
(V@10mA/cm ² ) efficiency
(cd/A@10mA/cm ² ) Lifetime T95
(hr@10mA/cm ² ) luminescent color Example 37 compound 10 compound 27 3.68 22.1 241 Red Example 38 compound 10 compound 34 3.70 20.1 234 Red Example 39 compound 10 compound 38 3.64 20.8 242 Red Example 40 compound 10 compound 46 3.60 21.0 238 Red Example 41 compound 11 compound 28 3.69 20.3 243 Red Example 42 compound 11 compound 32 3.57 20.7 253 Red Example 43 compound 11 compound 37 3.52 20.0 261 Red Example 44 compound 11 compound 42 3.51 20.5 244 Red Example 45 compound 12 compound 27 3.62 21.6 261 Red Example 46 compound 12 compound 34 3.63 21.0 272 Red Example 47 compound 12 compound 38 3.68 21.4 248 Red Example 48 compound 12 compound 46 3.54 21.8 253 Red Example 49 compound 13 compound 31 3.60 23.2 231 Red Example 50 compound 13 compound 39 3.64 22.3 248 Red Example 51 compound 13 compound 43 3.63 21.8 237 Red Example 52 compound 13 compound 47 3.72 20.1 250 Red Example 53 compound 14 compound 29 3.68 21.5 264 Red Example 54 compound 14 compound 35 3.82 21.0 251 Red Example 55 compound 14 compound 45 3.90 22.3 247 Red Example 56 compound 14 compound 49 3.74 22.9 230 Red Example 57 compound 15 compound 28 3.54 21.3 264 Red Example 58 compound 15 compound 32 3.60 22.0 275 Red Example 59 compound 15 compound 37 3.62 21.4 258 Red Example 60 compound 15 compound 42 3.57 22.1 280 Red Example 61 compound 16 compound 27 3.71 21.0 234 Red Example 62 compound 16 compound 34 3.70 20.4 247 Red Example 63 compound 16 compound 38 3.62 20.3 249 Red Example 64 compound 16 compound 46 3.64 20.7 233 Red Example 65 compound 17 compound 31 3.58 21.8 252 Red Example 66 compound 17 compound 39 3.47 23.1 253 Red Example 67 compound 17 compound 43 3.49 21.5 228 Red Example 68 compound 17 compound 47 3.50 22.2 231 Red Example 69 compound 18 compound 29 3.62 23.4 245 Red Example 70 compound 18 compound 35 3.74 21.0 260 Red Example 71 compound 18 compound 45 3.68 22.4 263 Red Example 72 compound 18 compound 49 3.62 21.8 257 Red

division 1st host 2nd host drive voltage
(V@10mA/cm ² ) efficiency
(cd/A@10mA/cm ² ) Lifetime T95
(hr@10mA/cm ² ) luminescent color Example 73 compound 19 compound 28 3.41 22.4 230 Red Example 74 compound 19 compound 32 3.48 21.8 243 Red Example 75 compound 19 compound 37 3.45 21.0 232 Red Example 76 compound 19 compound 42 3.54 21.3 251 Red Example 77 compound 20 compound 27 3.60 24.0 262 Red Example 78 compound 20 compound 34 3.47 23.2 274 Red Example 79 compound 20 compound 38 3.58 24.4 237 Red Example 80 compound 20 compound 46 3.51 22.1 249 Red Example 81 compound 21 compound 28 3.62 21.4 264 Red Example 82 compound 21 compound 32 3.73 23.2 244 Red Example 83 compound 21 compound 37 3.61 23.4 260 Red Example 84 compound 21 compound 42 3.62 22.8 267 Red Example 85 compound 22 compound 27 3.60 21.1 271 Red Example 86 compound 22 compound 34 3.64 21.4 280 Red Example 87 compound 22 compound 38 3.71 23.5 284 Red Example 88 compound 22 compound 46 3.65 22.4 273 Red Example 89 compound 23 compound 31 3.60 23.0 264 Red Example 90 compound 23 compound 39 3.63 24.2 260 Red Example 91 compound 23 compound 43 3.67 22.4 271 Red Example 92 compound 23 compound 47 3.64 21.6 263 Red Example 93 compound 24 compound 29 3.60 23.0 260 Red Example 94 compound 24 compound 35 3.56 22.5 254 Red Example 95 compound 24 compound 45 3.48 23.4 251 Red Example 96 compound 24 compound 49 3.43 22.7 248 Red Example 97 compound 25 compound 31 3.52 24.2 257 Red Example 98 compound 25 compound 39 3.49 23.5 240 Red Example 99 compound 25 compound 43 3.59 24.8 249 Red Example 100 compound 25 compound 47 3.55 23.0 243 Red Example 101 compound 26 compound 29 3.61 22.4 260 Red Example 102 compound 26 compound 35 3.64 22.1 262 Red Example 103 compound 26 compound 45 3.53 23.0 268 Red Example 104 compound 26 compound 49 3.50 22.6 243 Red

division 1st host 2nd host efficiency
(cd/A@10mA/cm ² ) Lifetime T95
(hr@10mA/cm ² ) luminescent color Comparative Example 1 compound 1 (unused) 18.8 173 Red Comparative Example 2 compound 3 (unused) 19.9 162 Red Comparative Example 3 compound 4 (unused) 19.0 168 Red Comparative Example 4 compound 5 (unused) 19.7 204 Red Comparative Example 5 compound 6 (unused) 17.9 158 Red Comparative Example 6 compound 8 (unused) 19.3 201 Red Comparative Example 7 compound 9 (unused) 18.7 187 Red Comparative Example 8 compound 11 (unused) 18.5 164 Red Comparative Example 9 compound 12 (unused) 18.1 155 Red Comparative Example 10 compound 15 (unused) 17.3 158 Red Comparative Example 11 compound 17 (unused) 18.0 150 Red Comparative Example 12 compound 20 (unused) 17.4 144 Red Comparative Example 13 compound 22 (unused) 18.1 143 Red Comparative Example 14 compound 25 (unused) 17.9 157 Red Comparative Example 15 compound 26 (unused) 18.0 151 Red

division 1st host 2nd host drive voltage
(V@10mA/cm ² ) efficiency
(cd/A@10mA/cm ² ) Lifetime T95
(hr@10mA/cm ² ) luminescent color Comparative Example 16 compound C-1 compound 28 3.95 18.1 181 Red Comparative Example 17 compound C-1 compound 32 3.94 18.3 192 Red Comparative Example 18 compound C-1 compound 37 4.02 19.8 197 Red Comparative Example 19 compound C-1 compound 42 3.92 19.8 184 Red Comparative Example 20 compound C-2 compound 27 4.10 20.5 173 Red Comparative Example 21 compound C-2 compound 34 4.12 19.9 178 Red Comparative Example 22 compound C-2 compound 38 4.05 19.4 164 Red Comparative Example 23 compound C-2 compound 46 4.01 18.2 190 Red Comparative Example 24 compound C-3 compound 31 3.92 19.2 204 Red Comparative Example 25 compound C-3 compound 39 4.10 19.3 209 Red Comparative Example 26 compound C-3 compound 43 4.02 19.9 190 Red Comparative Example 27 compound C-3 compound 47 3.95 18.3 201 Red Comparative Example 28 compound C-4 compound 29 3.97 18.4 174 Red Comparative Example 29 compound C-4 compound 35 3.94 17.8 178 Red Comparative Example 30 compound C-4 compound 45 3.90 17.2 170 Red Comparative Example 31 compound C-4 compound 49 3.95 16.8 169 Red Comparative Example 32 compound C-5 compound 28 4.02 19.4 182 Red Comparative Example 33 compound C-5 compound 32 4.07 18.0 194 Red Comparative Example 34 compound C-5 compound 37 4.06 17.1 180 Red Comparative Example 35 compound C-5 compound 42 4.05 18.3 194 Red Comparative Example 36 compound C-6 compound 27 4.02 17.4 184 Red Comparative Example 37 compound C-6 compound 34 4.00 17.8 203 Red Comparative Example 38 compound C-6 compound 38 3.95 18.8 192 Red Comparative Example 39 compound C-6 compound 46 3.87 18.2 202 Red Comparative Example 40 compound C-7 compound 31 3.90 17.6 181 Red Comparative Example 41 compound C-7 compound 39 3.92 18.3 178 Red Comparative Example 42 compound C-7 compound 43 3.95 17.4 193 Red Comparative Example 43 compound C-7 compound 47 4.02 16.8 182 Red Comparative Example 44 compound C-8 compound 29 4.11 17.1 203 Red Comparative Example 45 compound C-8 compound 35 4.07 16.8 194 Red Comparative Example 46 compound C-8 compound 45 4.14 18.2 190 Red Comparative Example 47 compound C-8 compound 49 4.08 17.4 207 Red Comparative Example 48 compound C-9 compound 28 4.20 18.6 193 Red Comparative Example 49 compound C-9 compound 32 4.17 19.0 184 Red Comparative Example 50 compound C-9 compound 37 4.22 18.8 188 Red Comparative Example 51 compound C-9 compound 42 4.20 18.5 171 Red

division 1st host 2nd host driving voltage
(V@10mA/cm ² ) efficiency
(cd/A@10mA/cm ² ) Lifetime T95
(hr@10mA/cm ² ) luminescent color Comparative Example 52 Compound C-10 compound 27 4.08 17.3 186 Red Comparative Example 53 Compound C-10 compound 34 4.01 18.3 183 Red Comparative Example 54 Compound C-10 compound 38 4.00 18.9 177 Red Comparative Example 55 Compound C-10 compound 46 3.95 18.7 190 Red Comparative Example 56 compound C-11 compound 31 4.00 16.0 203 Red Comparative Example 57 compound C-11 compound 39 3.94 16.1 194 Red Comparative Example 58 compound C-11 compound 43 3.96 17.3 207 Red Comparative Example 59 compound C-11 compound 47 4.03 19.0 205 Red Comparative Example 60 compound C-12 compound 29 3.99 19.3 183 Red Comparative Example 61 compound C-12 compound 35 3.94 18.7 209 Red Comparative Example 62 compound C-12 compound 45 3.97 17.5 190 Red Comparative Example 63 compound C-12 compound 49 4.05 17.1 188 Red

As shown in Tables 1 to 6, the organic light emitting device of the embodiment in which the compound represented by Formula 1 and the compound represented by Formula 2 of the present invention are simultaneously used as host materials of the light emitting layer are compounds represented by Formulas 1 and 2. Compared to the organic light emitting device of Comparative Example in which only one or both were used, excellent light emitting efficiency and significantly improved lifespan characteristics were exhibited. Specifically, the device according to the example exhibited higher efficiency and longer lifetime than the device of Comparative Example employing the compound represented by Formula 1 as a single host. In addition, the device according to the embodiment has improved efficiency and lifespan characteristics compared to the device of Comparative Example employing Comparative Example compounds C-1 to C-12 as first hosts and the compound represented by Formula 2 as a second host. It became. Through this, it is confirmed that when the combination of the first compound represented by Chemical Formula 1 and the second compound represented by Chemical Formula 2 is used as a host, energy is effectively transferred to the red dopant in the red emission layer. It can be determined that this is because the compound represented by Chemical Formula 1 has high stability for electrons and holes, and also, as the compound represented by Chemical Formula 2 is used simultaneously, the amount of holes increases and electrons and holes in the red light emitting layer increase. This is due to maintaining a more stable balance.

Therefore, when the compound represented by Formula 1 and the compound represented by Formula 2 of the present invention are simultaneously used as host materials of the organic light emitting device, the driving voltage, luminous efficiency and/or lifetime characteristics of the organic light emitting device can be improved. was able to confirm

1: substrate 2: anode
3: light emitting layer 4: cathode
5: hole injection layer 6: hole transport layer
7: light emitting layer 8: electron transport layer
9: electron blocking layer 10: hole blocking layer
11: electron transport and injection layer

Claims (13)

anode,
cathode, and
Including a light emitting layer between the anode and the cathode,
The light emitting layer includes a compound represented by Formula 1 and a compound represented by Formula 2 below.
Organic Light-Emitting Elements:
[Formula 1]

In Formula 1,
X is all N,
Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C _6-60 aryl; Or a C _5-60 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O and S,
R ₁ to R ₄ are each independently hydrogen; or deuterium, or two adjacent ones bond to form a benzene ring;
R ₅ is hydrogen, deuterium, phenyl, biphenylyl, naphthyl, or phenanthrenyl;
R ₆ and R ₇ are hydrogen or deuterium;
n1 is an integer from 0 to 6;
n2 and n3 are each independently an integer from 0 to 3;
[Formula 2]

In Formula 2,
A' is a benzene ring fused with two adjacent pentagonal rings,
L' ₁ and L' ₂ are each independently a single bond, phenylene, or naphthylene;
Ar' ₁ and Ar' ₂ are each independently phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl, dimethylfluorenyl, dibenzofuranyl, or dibenzothiophenyl;
R' ₁ and R' ₂ are each independently hydrogen; or deuterium;
n'1 and n'2 are each independently an integer of 0 to 4.
According to claim 1,
Formula 1 is represented by any one of the following Formulas 1-1 to 1-3,
Organic Light-Emitting Elements:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In Formulas 1-1 to 1-3,
X, Ar ₁ , Ar ₂ , R ₁ to R ₅ , and n1 are as defined in claim 1.
delete According to claim 1,
Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, naphthyl, dibenzofuranyl, or dibenzothiophenyl;
organic light emitting device.
delete According to claim 1,
n1 is 0 or 1;
organic light emitting device.
According to claim 1,
n2 and n3 are each independently 0 or 1;
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 Elements:

According to claim 1,
Formula 2 is represented by any one of the following Formulas 2-1 to 2-5,
Organic Light-Emitting Elements:
[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

In Formulas 2-1 to 2-5,
L' ₁ , L' ₂ , Ar' ₁ , Ar' ₂ , R' ₁ , R' ₂ , n'1 and n'2 are as defined in claim 1.
delete delete According to claim 1,
R' ₁ and R' ₂ are each independently hydrogen,
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 Elements:

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