KR102500849B1 - Novel compound and organic light emitting device comprising the same - Google Patents

Abstract

The present invention provides a novel compound and an organic light emitting device using the same.

Description

Novel compound and organic light emitting device using the same

The present invention relates to a novel compound and an organic light emitting device including the same.

In general, the 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.

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

Korean Patent Publication No. 10-2000-0051826

The present invention relates to a novel compound and an organic light emitting device including the same.

The present invention provides a compound represented by Formula 1 below:

[Formula 1]

In Formula 1,

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

Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C _6-60 aryl; Or a C _2-60 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O and S,

R ₁ to R ₄ are all hydrogen or deuterium; Or two adjacent R ₁ to R ₄ are bonded to form a benzene ring, the others are hydrogen or deuterium,

R ₅ is hydrogen or deuterium;

R ₆ are each independently hydrogen or deuterium;

n is an integer from 1 to 3;

In addition, the present invention is a first electrode; a second electrode provided to face the first electrode; and one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the compound represented by Chemical Formula 1. do.

The compound represented by Chemical Formula 1 may be used as a material for an organic layer of an organic light emitting diode, and may improve efficiency, low driving voltage, and/or lifespan characteristics of an organic light emitting diode. In particular, the compound represented by Chemical Formula 1 may be used as a material for hole injection, hole transport, hole injection and transport, electron suppression, light emission, electron transport, or electron injection.

1 shows an example of an organic light emitting device including a substrate 1, an anode 2, an organic material layer 3, and a cathode 4.
2 shows a substrate (1), an anode (2), a hole injection layer (5), a hole transport layer (6), an electron blocking layer (7), a light emitting layer (8), a hole blocking layer (9), an electron transport layer (10) , An example of an organic light emitting device composed of an electron injection layer 11 and a cathode 4 is shown.

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

The present invention provides a compound represented by Formula 1 above.

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 groups; 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.

In Formula 1, preferably, all X's are N.

Preferably, Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, naphthyl, phenanthrenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, or 9-phenylcarbazolyl. More preferably, at least one of Ar ₁ and Ar ₂ is phenyl.

Preferably, R ₅ is hydrogen.

Preferably, R ₆ is hydrogen.

On the other hand, two adjacent R ₁ to R ₄ are bonded to form a benzene ring, and the rest are hydrogen or deuterium, specifically, R ₁ and R ₂ are bonded, R ₂ and R ₃ are bonded, or R ₃ and R ₄ combine to form a benzene ring. For example, when two adjacent ones of R ₁ to R ₄ are bonded to form a benzene ring, Formula 1 is represented by one of Formulas 1-1 to 1-3 below.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

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

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

[Scheme 1]

In Scheme 1, the definitions except for X' are as defined above, and X' is halogen, and more preferably fluoro, chloro, or bromo.

The above reaction 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 can be changed as known in the art. The manufacturing method may be more specific in Preparation Examples to be described later.

In addition, the present invention provides an organic light emitting device including the compound represented by Formula 1 above. In one example, the present invention provides a first electrode; a second electrode provided to face the first electrode; and one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the compound represented by Chemical Formula 1. do.

The organic material layer of the organic light emitting device of the present invention may have a single-layer structure, or may have a multi-layer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like as organic layers. However, the structure of the organic light emitting device is not limited thereto and may include fewer organic layers.

Also, the organic layer may include a light emitting layer, and the light emitting layer includes the compound represented by Chemical Formula 1. In particular, the compound according to the present invention can be used as a host of the light emitting layer.

In addition, the organic material layer may include a hole injection layer, a hole transport layer, or an electron blocking layer, and the hole injection layer, hole transport layer, or electron blocking layer includes the compound represented by Formula 1 above.

In addition, the electron transport layer, the electron injection layer, or the layer simultaneously transporting and injecting electrons includes the compound represented by Formula 1.

Also, the organic light emitting device according to the present invention may be a normal type organic light emitting device in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate. In addition, the organic light emitting device according to the present invention may be an organic light emitting device of an inverted type in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate. For example, the structure of an organic light emitting device according to an embodiment of the present invention is illustrated in FIGS. 1 and 2 .

1 shows an example of an organic light emitting device including a substrate 1, an anode 2, an organic material layer 3, and a cathode 4. In this structure, the compound represented by Chemical Formula 1 may be included in the organic material layer.

2 shows a substrate (1), an anode (2), a hole injection layer (5), a hole transport layer (6), an electron blocking layer (7), a light emitting layer (8), a hole blocking layer (9), an electron transport layer (10) , An example of an organic light emitting device composed of an electron injection layer 11 and a cathode 4 is shown. In such a structure, the compound represented by Formula 1 may be included in one or more of the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transport layer, and the electron injection layer.

The organic light emitting device according to the present invention may be manufactured using materials and methods known in the art, except that at least one of the organic layers includes the compound represented by Chemical Formula 1. Also, when the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.

For example, the organic light emitting device according to the present invention may be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate. 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 After forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer thereon, and depositing a material that can be used as a cathode thereon, it can be prepared. In addition to this method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

In addition, the compound represented by Chemical Formula 1 may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light emitting device. 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.

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

In one example, the first electrode is an anode and the second electrode is a cathode, or the first electrode is a cathode and the second electrode is an anode.

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.

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. 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.

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 include, but are not limited to, arylamine-based organic materials, conductive polymers, and block copolymers having both conjugated and non-conjugated parts.

The light emitting material is a material capable of emitting light in the visible ray region by receiving and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); carbazole-based compounds; dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; compounds of the benzoxazole, benzthiazole and benzimidazole series; poly(p-phenylenevinylene) (PPV)-based polymers; spiro compounds; Polyfluorene, rubrene, etc., but are not limited thereto.

The light emitting layer may include a host material and a dopant material. The host material includes a condensed aromatic ring derivative or a compound containing a hetero ring. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc., and heterocyclic-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type furan compounds, pyrimidine derivatives, etc., but are not limited thereto.

Dopant materials include 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.

The electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer. As the electron transport material, a material capable of receiving electrons from the cathode and transferring them to the light emitting layer is suitable. do. Specific examples 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.

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. A compound that prevents migration to a layer and has excellent thin film forming ability is preferred. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preonylidene methane, anthrone, etc. and their derivatives, metals complex compounds and nitrogen-containing 5-membered ring derivatives, but are not limited thereto.

Examples of the metal complex compound include 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.

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.

In addition, the compound represented by Chemical Formula 1 may be included in an organic solar cell or an organic transistor in addition to an organic light emitting device.

Preparation of the compound represented by Chemical Formula 1 and the organic light emitting device including the same will be described in detail in the following examples. However, the following examples are intended to illustrate the present invention, and the scope of the present invention is not limited thereto.

[Example]

Example 1: Preparation of Compound 1

In a nitrogen atmosphere, Compound Sub 1 (15 g, 26.8 mmol) and Intermediate A (7.9 g, 29.5 mmol) were put in THF (300 ml) and stirred and refluxed. After dissolving potassium carbonate (14.8 g, 107.2 mmol) in water (44 ml), it was added, and after stirring sufficiently, tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.8 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 prepare 7.5 g of Compound 1. (Yield 42%, MS: [M+H] ⁺ = 665)

Example 2: Preparation of Compound 2

In a nitrogen atmosphere, Compound Sub 2 (15 g, 48.1 mmol) and Intermediate A (14.2 g, 52.9 mmol) were put in THF (300 ml) and stirred and refluxed. After dissolving potassium carbonate (26.6 g, 192.2 mmol) in water (80 ml), it was added, and after sufficiently stirring, tetrakis(triphenylphosphine)palladium(0) (1.7 g, 1.4 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 prepare 20.6 g of Compound 2. (Yield 60%, MS: [M+H] ⁺ = 715)

Example 3: Preparation of Compound 3

In a nitrogen atmosphere, Compound Sub 3 (15 g, 27.3 mmol) and Intermediate A (8 g, 30 mmol) were added to THF (300 ml) and stirred and refluxed. Thereafter, potassium carbonate (15.1 g, 109.2 mmol) was dissolved in water (45 ml), and after stirring sufficiently, tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.8 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 9 g of Compound 3. (Yield 46%, MS: [M+H] ⁺ = 715)

Example 4: Preparation of Compound 4

In a nitrogen atmosphere, Compound Sub 4 (15 g, 38.1 mmol) and Intermediate A (11.2 g, 42 mmol) were put in THF (300 ml) and stirred and refluxed. After dissolving potassium carbonate (21.1 g, 152.6 mmol) in water (63 ml), it was added, and after sufficiently stirring, tetrakis(triphenylphosphine)palladium(0) (1.3 g, 1.1 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 prepare 9 g of Compound 4. (Yield 33%, MS: [M+H] ⁺ = 715)

Example 5: Preparation of Compound 5

In a nitrogen atmosphere, Compound Sub 5 (15 g, 26.8 mmol) and Intermediate A (9.4 g, 29.5 mmol) were put in THF (300 ml) and stirred and refluxed. After dissolving potassium carbonate (14.8 g, 107.2 mmol) in water (44 ml), it was added, and after stirring sufficiently, tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.8 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 prepare 10.5 g of Compound 5. (Yield 55%, MS: [M+H] ⁺ = 716)

Example 6: Preparation of Compound 6

In a nitrogen atmosphere, Compound Sub 6 (15 g, 24.6 mmol) and Intermediate B (8.6 g, 27.1 mmol) were put in THF (300 ml) and stirred and refluxed. After dissolving potassium carbonate (13.6 g, 98.4 mmol) in water (41 ml), it was added, and after stirring sufficiently, tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.7 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 prepare 12.2 g of Compound 6. (Yield 65%, MS: [M+H] ⁺ = 766)

Example 7: Preparation of Compound 7

In a nitrogen atmosphere, Compound Sub 7 (15 g, 24.6 mmol) and Intermediate B (8.6 g, 27.1 mmol) were put in THF (300 ml) and stirred and refluxed. After dissolving potassium carbonate (13.6 g, 98.4 mmol) in water (41 ml), it was added, and after stirring sufficiently, tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.7 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 8.7 g of compound 7. (Yield 46%, MS: [M+H] ⁺ = 766)

Example 8: Preparation of Compound 8

In a nitrogen atmosphere, Compound Sub 8 (15 g, 24.6 mmol) and Intermediate B (8.6 g, 27.1 mmol) were put in THF (300 ml) and stirred and refluxed. After dissolving potassium carbonate (13.6 g, 98.4 mmol) in water (41 ml), it was added, and after stirring sufficiently, tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.7 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 7.3 g of Compound 8. (Yield 39%, MS: [M+H] ⁺ = 766)

Example 9: Preparation of compound 9

In a nitrogen atmosphere, Compound Sub 9 (15 g, 26.8 mmol) and Intermediate C (9.4 g, 29.5 mmol) were added to THF (300 ml) and stirred and refluxed. After dissolving potassium carbonate (14.8 g, 107.2 mmol) in water (44 ml), it was added, and after stirring sufficiently, tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.8 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 10.3 g of Compound 9. (Yield 54%, MS: [M+H] ⁺ = 716)

Example 10: Preparation of compound 10

In a nitrogen atmosphere, Compound Sub 10 (15 g, 24.6 mmol) and Intermediate C (8.6 g, 27.1 mmol) were put in THF (300 ml) and stirred and refluxed. After dissolving potassium carbonate (13.6 g, 98.4 mmol) in water (41 ml), it was added, and after stirring sufficiently, tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.7 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 prepare 14.5 g of Compound 10. (Yield 77%, MS: [M+H] ⁺ = 766)

Example 11: Preparation of Compound 11

In a nitrogen atmosphere, Compound Sub 11 (15 g, 24.6 mmol) and Intermediate C (8.6 g, 27.1 mmol) were put in THF (300 ml) and stirred and refluxed. After dissolving potassium carbonate (13.6 g, 98.4 mmol) in water (41 ml), it was added, and after stirring sufficiently, tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.7 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 prepare 5.6 g of Compound 11. (Yield 30%, MS: [M+H] ⁺ = 766)

Example 12: Preparation of compound 12

In a nitrogen atmosphere, Compound Sub 12 (15 g, 24.6 mmol) and Intermediate C (8.6 g, 27.1 mmol) were put in THF (300 ml) and stirred and refluxed. After dissolving potassium carbonate (13.6 g, 98.4 mmol) in water (41 ml), it was added, and after stirring sufficiently, tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.7 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 prepare 7.9 g of Compound 12. (Yield 42%, MS: [M+H] ⁺ = 766)

Example 13: Preparation of compound 13

In a nitrogen atmosphere, Compound Sub 13 (15 g, 26.8 mmol) and Intermediate D (10.2 g, 29.5 mmol) were put in THF (300 ml) and stirred and refluxed. After dissolving potassium carbonate (14.8 g, 107.2 mmol) in water (44 ml), it was added, and after stirring sufficiently, tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.8 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 prepare 10.3 g of Compound 13. (Yield 54%, MS: [M+H] ⁺ = 716)

Example 14: Preparation of compound 14

In a nitrogen atmosphere, Compound Sub 14 (15 g, 24.6 mmol) and Intermediate D (9.4 g, 27.1 mmol) were put in THF (300 ml) and stirred and refluxed. After dissolving potassium carbonate (13.6 g, 98.4 mmol) in water (41 ml), it was added, and after stirring sufficiently, tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.7 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 prepare 13.4 g of Compound 14. (Yield 69%, MS: [M+H] ⁺ = 792)

Example 15: Preparation of compound 15

Compound Sub 15 (15 g, 24.6 mmol) and Intermediate D (9.4 g, 27.1 mmol) were added to THF (300 ml) under a nitrogen atmosphere and stirred and refluxed. After dissolving potassium carbonate (13.6 g, 98.4 mmol) in water (41 ml), it was added, and after stirring sufficiently, tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.7 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 prepare 7.8 g of Compound 15. (Yield 40%, MS: [M+H] ⁺ = 792)

Example 16: Preparation of compound 16

In a nitrogen atmosphere, Compound Sub 16 (15 g, 24.6 mmol) and Intermediate D (9.4 g, 27.1 mmol) were put in THF (300 ml) and stirred and refluxed. After dissolving potassium carbonate (13.6 g, 98.4 mmol) in water (41 ml), it was added, and after stirring sufficiently, tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.7 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 prepare 8.2 g of Compound 16. (Yield 42%, MS: [M+H] ⁺ = 792)

Example 17: Preparation of compound 17

In a nitrogen atmosphere, Compound Sub 17 (15 g, 26.8 mmol) and Intermediate E (10.2 g, 29.5 mmol) were put in THF (300 ml) and stirred and refluxed. After dissolving potassium carbonate (14.8 g, 107.2 mmol) in water (44 ml), it was added, and after stirring sufficiently, tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.8 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 prepare 9.8 g of Compound 17. (Yield 51%, MS: [M+H] ⁺ = 716)

Example 18: Preparation of compound 18

In a nitrogen atmosphere, Compound Sub 18 (15 g, 24.6 mmol) and Intermediate E (9.4 g, 27.1 mmol) were put in THF (300 ml) and stirred and refluxed. After dissolving potassium carbonate (13.6 g, 98.4 mmol) in water (41 ml), it was added, and after stirring sufficiently, tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.7 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 prepare 13.4 g of compound 18. (Yield 69%, MS: [M+H] ⁺ = 792)

Example 19: Preparation of compound 19

In a nitrogen atmosphere, Compound Sub 19 (15 g, 24.6 mmol) and Intermediate E (9.4 g, 27.1 mmol) were added to THF (300 ml) and stirred and refluxed. After dissolving potassium carbonate (13.6 g, 98.4 mmol) in water (41 ml), it was added, and after stirring sufficiently, tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.7 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 prepare 6.2 g of Compound 19. (Yield 32%, MS: [M+H] ⁺ = 792)

Example 20: Preparation of compound 20

In a nitrogen atmosphere, Compound Sub 20 (15 g, 24.6 mmol) and Intermediate E (9.4 g, 27.1 mmol) were put in THF (300 ml) and stirred and refluxed. After dissolving potassium carbonate (13.6 g, 98.4 mmol) in water (41 ml), it was added, and after stirring sufficiently, tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.7 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 prepare 8.2 g of Compound 20. (Yield 42%, MS: [M+H] ⁺ = 792)

Example 21: Preparation of compound 21

In a nitrogen atmosphere, Compound Sub 21 (15 g, 26.8 mmol) and Intermediate F (12.8 g, 29.5 mmol) were put in THF (300 ml) and stirred and refluxed. After dissolving potassium carbonate (14.8 g, 107.2 mmol) in water (44 ml), it was added, and after stirring sufficiently, tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.8 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 prepare 11.1 g of compound 21. (Yield 50%, MS: [M+H] ⁺ = 831)

Example 22: Preparation of compound 22

In a nitrogen atmosphere, Compound Sub 22 (15 g, 24.6 mmol) and Intermediate F (11.7 g, 27.1 mmol) were put in THF (300 ml) and stirred and refluxed. After dissolving potassium carbonate (13.6 g, 98.4 mmol) in water (41 ml), it was added, and after stirring sufficiently, tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.7 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 prepare 16.7 g of Compound 22. (Yield 77%, MS: [M+H] ⁺ = 881)

Example 23: Preparation of compound 23

In a nitrogen atmosphere, Compound Sub 23 (15 g, 24.6 mmol) and Intermediate F (11.7 g, 27.1 mmol) were put in THF (300 ml) and stirred and refluxed. After dissolving potassium carbonate (13.6 g, 98.4 mmol) in water (41 ml), it was added, and after stirring sufficiently, tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.7 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 prepare 10.4 g of Compound 23. (Yield 48%, MS: [M+H] ⁺ = 881)

Example 24: Preparation of compound 24

In a nitrogen atmosphere, Compound Sub 24 (15 g, 24.6 mmol) and Intermediate F (11.7 g, 27.1 mmol) were put in THF (300 ml) and stirred and refluxed. After dissolving potassium carbonate (13.6 g, 98.4 mmol) in water (41 ml), it was added, and after stirring sufficiently, tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.7 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 prepare 7.4 g of Compound 24. (Yield 34%, MS: [M+H] ⁺ = 881)

Example 25: Preparation of compound 25

In a nitrogen atmosphere, Compound Sub 25 (15 g, 26.8 mmol) and Intermediate G (10.6 g, 29.5 mmol) were put in THF (300 ml) and stirred and refluxed. After dissolving potassium carbonate (14.8 g, 107.2 mmol) in water (44 ml), it was added, and after stirring sufficiently, tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.8 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 prepare 11 g of compound 25. (Yield 48%, MS: [M+H] ⁺ = 856)

Example 26: Preparation of compound 26

Compound Sub 26 (15 g, 24.6 mmol) and Intermediate G (9.7 g, 27.1 mmol) were added to THF (300 ml) under nitrogen atmosphere and stirred and refluxed. After dissolving potassium carbonate (13.6 g, 98.4 mmol) in water (41 ml), it was added, and after stirring sufficiently, tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.7 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 prepare 15.3 g of Compound 26. (Yield 77%, MS: [M+H] ⁺ = 806)

Example 27: Preparation of compound 27

Compound Sub 27 (15 g, 24.6 mmol) and Intermediate G (9.7 g, 27.1 mmol) were added to THF (300 ml) under nitrogen atmosphere and stirred and refluxed. After dissolving potassium carbonate (13.6 g, 98.4 mmol) in water (41 ml), it was added, and after stirring sufficiently, tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.7 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 5.9 g of compound 27. (Yield 30%, MS: [M+H] ⁺ = 806)

Example 28: Preparation of compound 28

Compound Sub 28 (15 g, 24.6 mmol) and Intermediate G (9.7 g, 27.1 mmol) were added to THF (300 ml) under nitrogen atmosphere and stirred and refluxed. After dissolving potassium carbonate (13.6 g, 98.4 mmol) in water (41 ml), it was added, and after stirring sufficiently, tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.7 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 prepare 9.5 g of Compound 28. (Yield 48%, MS: [M+H] ⁺ = 806)

Example 29: Preparation of compound 29

Compound Sub 29 (15 g, 26.8 mmol) and Intermediate H (10.6 g, 29.5 mmol) were added to THF (300 ml) under a nitrogen atmosphere and stirred and refluxed. After dissolving potassium carbonate (14.8 g, 107.2 mmol) in water (44 ml), it was added, and after stirring sufficiently, tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.8 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 11.5 g of Compound 29. (Yield 50%, MS: [M+H] ⁺ = 856)

Example 30: Preparation of compound 30

Compound Sub 30 (15 g, 24.6 mmol) and Intermediate H (9.7 g, 27.1 mmol) were added to THF (300 ml) under a nitrogen atmosphere and stirred and refluxed. After dissolving potassium carbonate (13.6 g, 98.4 mmol) in water (41 ml), it was added, and after stirring sufficiently, tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.7 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 prepare 11.9 g of compound 30. (Yield 60%, MS: [M+H] ⁺ = 806)

Example 31: Preparation of Compound 31

Compound Sub 31 (15 g, 24.6 mmol) and Intermediate H (9.7 g, 27.1 mmol) were added to THF (300 ml) under a nitrogen atmosphere and stirred and refluxed. After dissolving potassium carbonate (13.6 g, 98.4 mmol) in water (41 ml), it was added, and after stirring sufficiently, tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.7 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 obtain 9.7 g of compound 31. (Yield 49%, MS: [M+H] ⁺ = 806)

Example 32: Preparation of compound 32

Compound Sub 32 (15 g, 24.6 mmol) and Intermediate H (9.7 g, 27.1 mmol) were put in THF (300 ml) under a nitrogen atmosphere and stirred and refluxed. After dissolving potassium carbonate (13.6 g, 98.4 mmol) in water (41 ml), it was added, and after stirring sufficiently, tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.7 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 prepare 9.1 g of compound 32. (Yield 46%, MS: [M+H] ⁺ = 806)

Example 33: Preparation of compound 33

In a nitrogen atmosphere, Compound Sub 33 (15 g, 26.8 mmol) and Intermediate I (10.8 g, 29.5 mmol) were put in THF (300 ml) and stirred and refluxed. After dissolving potassium carbonate (14.8 g, 107.2 mmol) in water (44 ml), it was added, and after stirring sufficiently, tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.8 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 again dissolved in chloroform, washed twice with water, and 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 9.6 g of compound 33. (Yield 47%, MS: [M+H] ⁺ = 766)

Example 34: Preparation of Compound 34

In a nitrogen atmosphere, Compound Sub 34 (15 g, 24.6 mmol) and Intermediate I (10 g, 27.1 mmol) were put in THF (300 ml) and stirred and refluxed. After dissolving potassium carbonate (13.6 g, 98.4 mmol) in water (41 ml), it was added, and after stirring sufficiently, tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.7 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 prepare 13.4 g of Compound 34. (Yield 67%, MS: [M+H] ⁺ = 816)

Example 35: Preparation of compound 35

In a nitrogen atmosphere, Compound Sub 35 (15 g, 24.6 mmol) and Intermediate I (10 g, 27.1 mmol) were put in THF (300 ml) and stirred and refluxed. After dissolving potassium carbonate (13.6 g, 98.4 mmol) in water (41 ml), it was added, and after stirring sufficiently, tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.7 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 prepare 6 g of Compound 35. (Yield 30%, MS: [M+H] ⁺ = 816)

Example 36: Preparation of compound 36

In a nitrogen atmosphere, Compound Sub 36 (15 g, 24.6 mmol) and Intermediate I (10 g, 27.1 mmol) were put in THF (300 ml) and stirred and refluxed. After dissolving potassium carbonate (13.6 g, 98.4 mmol) in water (41 ml), it was added, and after stirring sufficiently, tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.7 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 prepare 8.6 g of compound 36. (Yield 43%, MS: [M+H] ⁺ = 816)

Example 37: Preparation of compound 37

In a nitrogen atmosphere, Compound Sub 37 (15 g, 26.8 mmol) and Intermediate A (7.9 g, 29.5 mmol) were put in THF (300 ml) and stirred and refluxed. After dissolving potassium carbonate (14.8 g, 107.2 mmol) in water (44 ml), it was added, and after stirring sufficiently, tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.8 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 prepare 8.2 g of compound 37. (Yield 46%, MS: [M+H] ⁺ = 666)

Example 38: Preparation of compound 38

In a nitrogen atmosphere, Compound Sub 38 (15 g, 24.6 mmol) and Intermediate A (7.2 g, 27.1 mmol) were put in THF (300 ml) and stirred and refluxed. After dissolving potassium carbonate (13.6 g, 98.4 mmol) in water (41 ml), it was added, and after stirring sufficiently, tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.7 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 12 g of compound 38. (Yield 68%, MS: [M+H] ⁺ = 716)

Example 39: Preparation of compound 39

In a nitrogen atmosphere, Compound Sub 39 (15 g, 24.6 mmol) and Intermediate A (7.2 g, 27.1 mmol) were put in THF (300 ml) and stirred and refluxed. After dissolving potassium carbonate (13.6 g, 98.4 mmol) in water (41 ml), it was added, and after stirring sufficiently, tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.7 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 prepare 7.4 g of compound 39. (Yield 42%, MS: [M+H] ⁺ = 716)

Example 40: Preparation of compound 40

In a nitrogen atmosphere, Compound Sub 40 (15 g, 24.6 mmol) and Intermediate A (7.2 g, 27.1 mmol) were put in THF (300 ml) and stirred and refluxed. After dissolving potassium carbonate (13.6 g, 98.4 mmol) in water (41 ml), it was added, and after stirring sufficiently, tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.7 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 8.1 g of Compound 40. (Yield 46%, MS: [M+H] ⁺ = 716)

Example 41: Preparation of compound 41

In a nitrogen atmosphere, Compound Sub 41 (15 g, 26.8 mmol) and Intermediate B (9.4 g, 29.5 mmol) were put in THF (300 ml) and stirred and refluxed. After dissolving potassium carbonate (14.8 g, 107.2 mmol) in water (44 ml), it was added, and after stirring sufficiently, tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.8 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 prepare 10.7 g of Compound 41. (Yield 56%, MS: [M+H] ⁺ = 716)

Example 42: Preparation of Compound 42

In a nitrogen atmosphere, Compound Sub 42 (15 g, 24.6 mmol) and Intermediate B (8.6 g, 27.1 mmol) were put in THF (300 ml) and stirred and refluxed. After dissolving potassium carbonate (13.6 g, 98.4 mmol) in water (41 ml), it was added, and after stirring sufficiently, tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.7 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 prepare 10.9 g of Compound 42. (Yield 58%, MS: [M+H] ⁺ = 766)

Example 43: Preparation of compound 43

In a nitrogen atmosphere, Compound Sub 43 (15 g, 24.6 mmol) and Intermediate B (8.6 g, 27.1 mmol) were put in THF (300 ml) and stirred and refluxed. After dissolving potassium carbonate (13.6 g, 98.4 mmol) in water (41 ml), it was added, and after stirring sufficiently, tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.7 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 prepare 8.5 g of Compound 43. (Yield 45%, MS: [M+H] ⁺ = 766)

Example 44: Preparation of compound 44

In a nitrogen atmosphere, Compound Sub 44 (15 g, 24.6 mmol) and Intermediate B (8.6 g, 27.1 mmol) were put in THF (300 ml) and stirred and refluxed. After dissolving potassium carbonate (13.6 g, 98.4 mmol) in water (41 ml), it was added, and after stirring sufficiently, tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.7 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 6.2 g of Compound 44. (Yield 33%, MS: [M+H] ⁺ = 766)

Example 45: Preparation of Compound 45

In a nitrogen atmosphere, Compound Sub 45 (15 g, 26.8 mmol) and Intermediate C (9.4 g, 29.5 mmol) were put in THF (300 ml) and stirred and refluxed. After dissolving potassium carbonate (14.8 g, 107.2 mmol) in water (44 ml), it was added, and after stirring sufficiently, tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.8 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 7.7 g of Compound 45. (Yield 40%, MS: [M+H] ⁺ = 716)

Example 46: Preparation of compound 46

In a nitrogen atmosphere, Compound Sub 46 (15 g, 24.6 mmol) and Intermediate C (8.6 g, 27.1 mmol) were put in THF (300 ml) and stirred and refluxed. After dissolving potassium carbonate (13.6 g, 98.4 mmol) in water (41 ml), it was added, and after stirring sufficiently, tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.7 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 prepare 10 g of compound 46. (Yield 53%, MS: [M+H] ⁺ = 766)

Example 47: Preparation of compound 47

In a nitrogen atmosphere, Compound Sub 47 (15 g, 24.6 mmol) and Intermediate C (8.6 g, 27.1 mmol) were put in THF (300 ml) and stirred and refluxed. After dissolving potassium carbonate (13.6 g, 98.4 mmol) in water (41 ml), it was added, and after stirring sufficiently, tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.7 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 10.7 g of Compound 47. (Yield 57%, MS: [M+H] ⁺ = 766)

Example 48: Preparation of compound 48

In a nitrogen atmosphere, Compound Sub 48 (15 g, 24.6 mmol) and Intermediate C (8.6 g, 27.1 mmol) were put in THF (300 ml) and stirred and refluxed. After dissolving potassium carbonate (13.6 g, 98.4 mmol) in water (41 ml), it was added, and after stirring sufficiently, tetrakis(triphenylphosphine)palladium(0) (0.9 g, 0.7 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 prepare 6.8 g of Compound 48. (Yield 36%, MS: [M+H] ⁺ = 766)

[Experimental example]

Experimental Example 1

A glass substrate coated with ITO (indium tin oxide) 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. Subsequently, an electron blocking layer was formed to a thickness of 150 Å by vacuum depositing the following EB-1 compound on the hole transport layer. Subsequently, Compound 1 prepared in Experimental Example 1 and the following Dp-39 compound were vacuum deposited on the EB-1 deposited film in a weight ratio of 98:2 to form a light emitting layer with a thickness of 400 Å. The following HB-1 compound was vacuum deposited on the light emitting layer to form a hole blocking layer with a thickness of 30 Å. On the hole blocking layer, the following ET-1 compound and the following LiQ compound were vacuum deposited at a weight ratio of 2:1 to form an electron injection and transport layer with a thickness of 300 Å. 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 0.3 Å/sec, and the deposition rate of aluminum was 2 Å/sec, and the vacuum level during deposition was 2×10 ^-7 Maintaining ~ 5ⅹ10 ^-6 torr, an organic light emitting device was manufactured.

Experimental Examples 2 to 40

An organic light emitting diode was manufactured in the same manner as in Experimental Example 1, except that the compounds listed in Tables 1 and 2 were used instead of Compound 1.

Comparative Experimental Examples 1 to 10

An organic light emitting device was manufactured in the same manner as in Experimental Example 1, except that the compounds shown in Table 3 were used instead of Compound 1. The compounds listed in Table 3 below are each as follows.

A current was applied to the organic light emitting devices prepared in the Experimental Examples and Comparative Experimental Examples to measure driving voltage, current efficiency, and lifetime, and the results are shown in Tables 1 to 3 below. T95 means the time required for the luminance to decrease from the initial luminance to 95%.

Experimental example host substance drive voltage
(V@10mA/cm ² ) current efficiency
(cd/A@10mA/cm ² ) Life (T95)
(hr@10mA/cm ² ) Experimental Example 1 compound 1 4.33 23.52 181 Experimental Example 2 compound 2 4.45 24.25 200 Experimental Example 3 compound 3 4.21 25.36 183 Experimental Example 4 compound 4 4.81 24.33 175 Experimental Example 5 compound 5 4.63 26.14 192 Experimental Example 6 compound 6 4.43 23.96 184 Experimental Example 7 compound 7 4.92 24.31 177 Experimental Example 8 compound 8 4.22 23.61 205 Experimental Example 9 compound 9 4.15 26.01 183 Experimental Example 10 compound 10 4.37 25.99 183 Experimental Example 11 compound 11 4.43 23.44 179 Experimental Example 12 compound 12 4.40 26.10 195 Experimental Example 13 compound 13 4.52 24.61 184 Experimental Example 14 compound 14 4.21 25.31 201 Experimental Example 15 compound 15 4.53 26.13 189 Experimental Example 16 compound 16 4.20 23.82 179 Experimental Example 17 compound 17 4.23 22.22 183 Experimental Example 18 compound 18 4.15 23.22 192 Experimental Example 19 compound 19 4.34 24.60 186 Experimental Example 20 compound 20 4.40 23.93 175

Experimental example host substance drive voltage
(V@10mA/cm ² ) current efficiency
(cd/A@10mA/cm ² ) Life (T95)
(hr@10mA/cm ² ) Experimental Example 21 compound 21 4.25 23.48 175 Experimental Example 22 compound 22 4.44 24.25 188 Experimental Example 23 compound 23 4.61 26.23 182 Experimental Example 24 compound 24 4.53 24.83 192 Experimental Example 25 compound 25 4.18 26.73 193 Experimental Example 26 compound 26 4.25 24.33 186 Experimental Example 27 compound 27 4.23 23.58 175 Experimental Example 28 compound 28 4.35 23.59 182 Experimental Example 29 compound 29 4.33 24.98 197 Experimental Example 30 compound 30 4.41 26.03 185 Experimental Example 31 compound 31 4.53 27.80 196 Experimental Example 32 compound 32 4.51 26.83 178 Experimental Example 33 compound 33 4.29 25.91 198 Experimental Example 34 compound 34 4.36 24.78 200 Experimental Example 35 compound 35 4.36 23.82 193 Experimental Example 36 compound 36 4.43 25.60 183 Experimental Example 37 compound 37 4.22 24.93 182 Experimental Example 38 compound 38 4.29 25.34 185 Experimental Example 39 compound 39 4.37 26.58 172 Experimental Example 40 compound 40 4.51 25.70 188

Experimental example host substance drive voltage
(V@10mA/cm ² ) current efficiency
(cd/A@10mA/cm ² ) Life (T95)
(hr@10mA/cm ² ) Comparative Experimental Example 1 RH-1 5.68 15.08 57 Comparative Experimental Example 2 RH-2 5.55 14.14 65 Comparative Experimental Example 3 RH-3 5.63 14.55 65 Comparative Experimental Example 4 RH-4 5.54 14.35 59 Comparative Experimental Example 5 RH-5 5.15 14.46 61 Comparative Experimental Example 6 RH-6 5.82 14.58 76 Comparative Experimental Example 7 RH-7 5.39 15.21 71 Comparative Experimental Example 8 RH-8 5.23 13.75 68 Comparative Experimental Example 9 RH-9 5.99 12.63 61 Comparative Experimental Example 10 RH-10 5.11 14.51 70

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

Claims (8)

A compound represented by Formula 1 below:
[Formula 1]

In Formula 1,
X is N, or CH, provided that at least two of X are N;
Ar ₁ is phenyl;
Ar ₂ is phenyl, biphenylyl, naphthyl, phenanthrenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, or 9-phenylcarbazolyl;
R ₁ to R ₄ are all hydrogen or deuterium; Or two adjacent R ₁ to R ₄ are bonded to form a benzene ring, the others are hydrogen or deuterium,
R ₅ is hydrogen or deuterium;
R ₆ are each independently hydrogen or deuterium;
n is an integer from 1 to 3;
According to claim 1,
all X's are N;
compound.
delete delete According to claim 1,
R ₅ is hydrogen;
compound.
According to claim 1,
R ₆ is hydrogen;
compound.
According to claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of
compound:

a first electrode; a second electrode provided to face the first electrode; and one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers is one of claims 1, 2, and 5 to 7. An organic light emitting device comprising the compound according to any one of claims.

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