KR20210023774A - 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. The compound represented by chemical formula 1 can be used as a material for an organic material layer of the organic light emitting device, and thus can improve efficiency, lower driving voltage, and/or improve lifespan characteristics in the organic light emitting device.

Description

Novel compound and organic light emitting device comprising the same

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

In general, the organic light emission phenomenon refers to a phenomenon in which electrical energy is converted into light energy by using an organic material. An organic light-emitting device using the organic light-emitting phenomenon has a wide viewing angle, excellent contrast, and 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 and a cathode, and an organic material layer between the anode and the cathode. The organic material layer is often made of a multilayer structure made of different materials in order to increase the efficiency and stability of the organic light emitting device.For example, it may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, etc. In the structure of such an 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 excitons are formed when the injected holes and electrons meet. When it falls back to the ground, it glows.

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

Korean Patent Publication No. 10-2000-0051826

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

The present invention provides a compound represented by the following formula (1):

[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 substituted or unsubstituted C 2-60} heteroaryl including any one or more selected from the group consisting of N, O and S,

All of R ₁ to R ₄ are hydrogen or deuterium; Or _{two adjacent two of R 1} to R ₄ are bonded to form a benzene ring, and the remainder is hydrogen or deuterium,

R ₅ is hydrogen or deuterium,

Each R ₆ is independently hydrogen or deuterium,

n is an integer of 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 a compound represented by Formula 1 do.

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

1 shows an example of an organic light-emitting device comprising 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 suppression layer (7), a light emitting layer (8), a hole suppression layer (9), an electron transport layer (10). , An example of an organic light-emitting device comprising an electron injection layer 11 and a cathode 4 is shown.

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

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

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

Means a bond connected to another substituent.

In the present specification, the term "substituted or unsubstituted" refers to 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; Alkyl sulfoxy group; Arylsulfoxy group; Silyl group; Boron group; Alkyl group; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; Aralkenyl group; Alkylaryl group; Alkylamine group; Aralkylamine group; Heteroarylamine group; Arylamine group; Arylphosphine group; Or it means substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing one or more of N, O, and S atoms, or substituted or unsubstituted with two or more substituents connected among the above-exemplified substituents. . For example, "a substituent to which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, or may be interpreted as a substituent to 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 a C1-C25 linear, branched or cyclic alkyl group or an aryl group having 6 to 25 carbon atoms in the oxygen of 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 it 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 trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, etc. However, it is not limited thereto.

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, and the like, but is not limited thereto.

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

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. 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, cycloheptylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but are not limited thereto.

In the present specification, the alkenyl group may be a linear or branched chain, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to an exemplary 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, and the like, but are not limited thereto.

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

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

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

Can be, 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 a heterogeneous element, and the number of carbon atoms is not particularly limited, but it is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, acridyl group , Pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group , Carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, isoxazolyl group, thiiadia There are a zolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but are not limited thereto.

In the present specification, the aryl group among the aralkyl group, aralkenyl group, alkylaryl group, and arylamine group is the same as the example of the aryl group described above. In the present specification, the alkyl group among the aralkyl group, the alkylaryl group and the alkylamine group is the same as the example of the aforementioned alkyl group. In the present specification, for heteroaryl among heteroarylamines, the description of the aforementioned heterocyclic group may be applied. In the present specification, the alkenyl group of the aralkenyl group is the same as the example 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 aforementioned heterocyclic group 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 bonding of two substituents. In the present specification, the heterocycle is not a monovalent group, and the description of the aforementioned heterocyclic group may be applied, except that two substituents are bonded to each other and formed.

In Formula 1, preferably, all of X are N.

Preferably, Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, naphthyl, 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 two of R 1} to R ₄ are bonded to form a benzene ring, and the remainder is hydrogen or deuterium, specifically R ₁ and R ₂ are bonded, R ₂ and R ₃ are bonded, or R _{It means that 3} and R ₄ combine to form a benzene ring. For example, when _{two adjacent two of R 1} to R ₄ are bonded to form a benzene ring, Formula 1 is represented by any one of the following Formulas 1-1 to 1-3.

[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 an organic light-emitting device including the compound represented by Formula 1 above. For 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 a compound represented by Formula 1 do.

The organic material layer of the organic light emitting device of the present invention may have a single-layer structure, but may have a multilayer 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 an organic material layer. However, the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic layers.

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

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

In addition, the electron transport layer, the electron injection layer, or the layer that simultaneously transports and injects electrons includes the compound represented by Formula 1 above.

In addition, 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 inverted type organic light-emitting device 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 comprising a substrate 1, an anode 2, an organic material layer 3, and a cathode 4. In such a structure, the compound represented by 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 suppression layer (7), a light emitting layer (8), a hole suppression layer (9), an electron transport layer (10). , An example of an organic light-emitting device comprising 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 suppression layer, the light-emitting layer, the hole suppression layer, the electron transport layer, and the electron injection layer.

The organic light-emitting device according to the present invention may be manufactured by materials and methods known in the art, except that at least one of the organic material layers includes the compound represented by Chemical Formula 1. In addition, 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, using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, the anode is formed by depositing a metal or a conductive metal oxide or an alloy thereof on the substrate. And, 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, it can be prepared by depositing a material that can be used as a cathode thereon. In addition to this method, an organic light-emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

In addition, the compound represented by 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 refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, roll coating, and the like, but is not limited thereto.

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

For example, the first electrode is an anode, 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 large work function is preferable so that holes can be smoothly injected into the organic material 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;} Poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), conductive polymers such as polypyrrole and polyaniline, and the like, but are not limited thereto.

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

The hole injection layer is a layer that injects holes from the electrode, and has the ability to transport holes as a hole injection material, so that it has a hole injection effect at the anode, an excellent hole injection effect for the light emitting layer or the light emitting material, and is generated from the light emitting layer. A compound that prevents the movement of excitons to the electron injection layer or the electron injection material and has excellent ability to form a thin film is preferable. It is preferable that the HOMO (highest occupied molecular orbital) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of hole injection materials include metal porphyrin, oligothiophene, arylamine-based organic substances, hexanitrile hexaazatriphenylene-based organic substances, quinacridone-based organic substances, and perylene-based organic substances. Organic substances, anthraquinone, 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 holes to the light emitting layer.As a hole transport material, a material capable of transporting holes from the anode or the hole injection layer to the light emitting layer and having high mobility for holes This is suitable. Specific examples include an arylamine-based organic material, a conductive polymer, and a block copolymer including a conjugated portion and a non-conjugated portion, but are not limited thereto.

As the light-emitting material, a material capable of emitting light in a visible light region by transporting 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 of 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compound; Benzoxazole, benzthiazole, and benzimidazole-based compounds; Poly(p-phenylenevinylene) (PPV)-based polymer; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited thereto.

The emission layer may include a host material and a dopant material. Host materials include condensed aromatic ring derivatives or heterocyclic-containing compounds. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Dopant materials include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, periflanthene and the like having an arylamino group, and the styrylamine compound is substituted or unsubstituted As a compound in which at least one arylvinyl group is substituted on the arylamine, one or two or more substituents selected from the group consisting of aryl group, silyl group, alkyl group, cycloalkyl group, and arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, and styryltetraamine, but are not limited thereto. In addition, examples of the metal complex include, but are not limited to, an iridium complex and a platinum complex.

The electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the emission layer. As an electron transport material, a material capable of injecting electrons from the cathode and transferring them to the emission layer, and a material having high mobility for electrons is suitable. Do. Specific examples include Al complex of 8-hydroxyquinoline; Complexes containing Alq _3; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto. The electron transport layer 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 that have a low work function and are followed by an aluminum layer or a silver layer. Specifically, they are cesium, barium, calcium, ytterbium, and samarium, and in each case an aluminum layer or a silver layer follows.

The electron injection layer is a layer that injects electrons from the electrode, has the ability to transport electrons, has an electron injection effect from the cathode, an excellent electron injection effect for the light emitting layer or the light emitting material, and hole injection of excitons generated in the light emitting layer A compound that prevents migration to the layer and is excellent in thin film forming ability is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, preorenylidene methane, anthrone, etc. 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)( o-cresolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtholato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtholato)gallium, etc. It is 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-sided emission type depending on the material used.

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

The preparation of the compound represented by 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 for illustrating 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 added to THF (300 ml) and stirred and refluxed. Then, potassium carbonate (14.8 g, 107.2 mmol) was dissolved in water (44 ml) and stirred sufficiently, and then tetrakis (triphenylphosphine) palladium (0) (0.9 g, 0.8 mmol) was added. After the reaction for 10 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 1 (7.5 g). (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 added to THF (300 ml), followed by stirring and refluxing. Then, potassium carbonate (26.6 g, 192.2 mmol) was dissolved in water (80 ml) and stirred sufficiently, and then tetrakis (triphenylphosphine) palladium (0) (1.7 g, 1.4 mmol) was added. After the reaction for 10 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 2 (20.6 g). (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), followed by stirring and refluxing. Then, potassium carbonate (15.1 g, 109.2 mmol) was dissolved in water (45 ml) and stirred sufficiently, and then tetrakis (triphenylphosphine) palladium (0) (0.9 g, 0.8 mmol) was added. After the reaction for 11 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 3 (9 g). (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 added to THF (300 ml), followed by stirring and refluxing. Then, potassium carbonate (21.1 g, 152.6 mmol) was dissolved in water (63 ml), stirred sufficiently, and tetrakis (triphenylphosphine) palladium (0) (1.3 g, 1.1 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 4 (9 g). (Yield 33%, MS: [M+H] ⁺ = 715)

Example 5: Preparation of compound 5

In a nitrogen atmosphere, compound Sub 1 (15 g, 26.8 mmol) and intermediate B (9.4 g, 29.5 mmol) were added to THF (300 ml), followed by stirring and refluxing. Then, potassium carbonate (14.8 g, 107.2 mmol) was dissolved in water (44 ml) and stirred sufficiently, and then tetrakis (triphenylphosphine) palladium (0) (0.9 g, 0.8 mmol) was added. After the reaction for 10 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 5 (10.5 g). (Yield 55%, MS: [M+H] ⁺ = 716)

Example 6: Preparation of compound 6

In a nitrogen atmosphere, compound Sub 2 (15 g, 24.6 mmol) and intermediate B (8.6 g, 27.1 mmol) were added to THF (300 ml) and stirred and refluxed. Then, potassium carbonate (13.6 g, 98.4 mmol) was dissolved in water (41 ml) and stirred sufficiently, and then tetrakis (triphenylphosphine) palladium (0) (0.9 g, 0.7 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 6 (12.2 g). (Yield 65%, MS: [M+H] ⁺ = 766)

Example 7: Preparation of compound 7

In a nitrogen atmosphere, compound Sub 3 (15 g, 24.6 mmol) and intermediate B (8.6 g, 27.1 mmol) were added to THF (300 ml) and stirred and refluxed. Then, potassium carbonate (13.6 g, 98.4 mmol) was dissolved in water (41 ml) and stirred sufficiently, and then tetrakis (triphenylphosphine) palladium (0) (0.9 g, 0.7 mmol) was added. After the reaction for 12 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 7 (8.7 g). (Yield 46%, MS: [M+H] ⁺ = 766)

Example 8: Preparation of compound 8

In a nitrogen atmosphere, compound Sub 4 (15 g, 24.6 mmol) and intermediate B (8.6 g, 27.1 mmol) were added to THF (300 ml), followed by stirring and refluxing. Then, potassium carbonate (13.6 g, 98.4 mmol) was dissolved in water (41 ml) and stirred sufficiently, and then tetrakis (triphenylphosphine) palladium (0) (0.9 g, 0.7 mmol) was added. After the reaction for 12 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 8 (7.3 g). (Yield 39%, MS: [M+H] ⁺ = 766)

Example 9: Preparation of compound 9

In a nitrogen atmosphere, compound Sub 1 (15 g, 26.8 mmol) and intermediate C (9.4 g, 29.5 mmol) were added to THF (300 ml), followed by stirring and refluxing. Then, potassium carbonate (14.8 g, 107.2 mmol) was dissolved in water (44 ml) and stirred sufficiently, and then tetrakis (triphenylphosphine) palladium (0) (0.9 g, 0.8 mmol) was added. After the reaction for 12 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 9 (10.3 g). (Yield 54%, MS: [M+H] ⁺ = 716)

Example 10: Preparation of compound 10

In a nitrogen atmosphere, compound Sub 2 (15 g, 24.6 mmol) and intermediate C (8.6 g, 27.1 mmol) were added to THF (300 ml), followed by stirring and refluxing. Subsequently, potassium carbonate (13.6 g, 98.4 mmol) was dissolved in water (41 ml), stirred sufficiently, and tetrakis (triphenylphosphine) palladium (0) (0.9 g, 0.7 mmol) was added. After the reaction for 11 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 10 (14.5 g). (Yield 77%, MS: [M+H] ⁺ = 766)

Example 11: Preparation of compound 11

In a nitrogen atmosphere, compound Sub 3 (15 g, 24.6 mmol) and intermediate C (8.6 g, 27.1 mmol) were added to THF (300 ml), followed by stirring and refluxing. Subsequently, potassium carbonate (13.6 g, 98.4 mmol) was dissolved in water (41 ml), stirred sufficiently, and tetrakis (triphenylphosphine) palladium (0) (0.9 g, 0.7 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 11 (5.6 g). (Yield 30%, MS: [M+H] ⁺ = 766)

Example 12: Preparation of compound 12

In a nitrogen atmosphere, compound Sub 4 (15 g, 24.6 mmol) and intermediate C (8.6 g, 27.1 mmol) were added to THF (300 ml), followed by stirring and refluxing. Then, potassium carbonate (13.6 g, 98.4 mmol) was dissolved in water (41 ml) and stirred sufficiently, and then tetrakis (triphenylphosphine) palladium (0) (0.9 g, 0.7 mmol) was added. After the reaction for 10 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 12 (7.9 g). (Yield 42%, MS: [M+H] ⁺ = 766)

Example 13: Preparation of compound 13

In a nitrogen atmosphere, compound Sub 1 (15 g, 26.8 mmol) and intermediate D (10.2 g, 29.5 mmol) were added to THF (300 ml), followed by stirring and refluxing. Then, potassium carbonate (14.8 g, 107.2 mmol) was dissolved in water (44 ml) and stirred sufficiently, and then tetrakis (triphenylphosphine) palladium (0) (0.9 g, 0.8 mmol) was added. After the reaction for 10 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 13 (10.3 g). (Yield 54%, MS: [M+H] ⁺ = 716)

Example 14: Preparation of compound 14

In a nitrogen atmosphere, compound Sub 2 (15 g, 24.6 mmol) and intermediate D (9.4 g, 27.1 mmol) were added to THF (300 ml), followed by stirring and refluxing. Subsequently, potassium carbonate (13.6 g, 98.4 mmol) was dissolved in water (41 ml), stirred sufficiently, and tetrakis (triphenylphosphine) palladium (0) (0.9 g, 0.7 mmol) was added. After the reaction for 10 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 14 (13.4 g). (Yield 69%, MS: [M+H] ⁺ = 792)

Example 15: Preparation of compound 15

In a nitrogen atmosphere, compound Sub 3 (15 g, 24.6 mmol) and intermediate D (9.4 g, 27.1 mmol) were added to THF (300 ml), followed by stirring and refluxing. Subsequently, potassium carbonate (13.6 g, 98.4 mmol) was dissolved in water (41 ml), stirred sufficiently, and tetrakis (triphenylphosphine) palladium (0) (0.9 g, 0.7 mmol) was added. After the reaction for 11 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 15 (7.8 g). (Yield 40%, MS: [M+H] ⁺ = 792)

Example 16: Preparation of compound 16

In a nitrogen atmosphere, compound Sub 4 (15 g, 24.6 mmol) and intermediate D (9.4 g, 27.1 mmol) were added to THF (300 ml), followed by stirring and refluxing. Then, potassium carbonate (13.6 g, 98.4 mmol) was dissolved in water (41 ml) and stirred sufficiently, and then tetrakis (triphenylphosphine) palladium (0) (0.9 g, 0.7 mmol) was added. After the reaction for 11 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 16 (8.2 g). (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 added to THF (300 ml), followed by stirring and refluxing. Then, potassium carbonate (14.8 g, 107.2 mmol) was dissolved in water (44 ml) and stirred sufficiently, and then tetrakis (triphenylphosphine) palladium (0) (0.9 g, 0.8 mmol) was added. After the reaction for 10 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 17 (9.8 g). (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 added to THF (300 ml), followed by stirring and refluxing. Then, potassium carbonate (13.6 g, 98.4 mmol) was dissolved in water (41 ml) and stirred sufficiently, and then tetrakis (triphenylphosphine) palladium (0) (0.9 g, 0.7 mmol) was added. After the reaction for 11 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 18 (13.4 g). (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), followed by stirring and refluxing. Then, potassium carbonate (13.6 g, 98.4 mmol) was dissolved in water (41 ml) and stirred sufficiently, and then tetrakis (triphenylphosphine) palladium (0) (0.9 g, 0.7 mmol) was added. After the reaction for 10 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 19 (6.2 g). (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 added to THF (300 ml) and stirred and refluxed. Then, potassium carbonate (13.6 g, 98.4 mmol) was dissolved in water (41 ml) and stirred sufficiently, and then tetrakis (triphenylphosphine) palladium (0) (0.9 g, 0.7 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 20 (8.2 g). (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 added to THF (300 ml), followed by stirring and refluxing. Then, potassium carbonate (14.8 g, 107.2 mmol) was dissolved in water (44 ml) and stirred sufficiently, and then tetrakis (triphenylphosphine) palladium (0) (0.9 g, 0.8 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 21 (11.1 g). (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 added to THF (300 ml), followed by stirring and refluxing. Then, potassium carbonate (13.6 g, 98.4 mmol) was dissolved in water (41 ml) and stirred sufficiently, and then tetrakis (triphenylphosphine) palladium (0) (0.9 g, 0.7 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 22 (16.7 g). (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 added to THF (300 ml) and stirred and refluxed. Then, potassium carbonate (13.6 g, 98.4 mmol) was dissolved in water (41 ml) and stirred sufficiently, and then tetrakis (triphenylphosphine) palladium (0) (0.9 g, 0.7 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 23 (10.4 g). (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 added to THF (300 ml), followed by stirring and refluxing. Then, potassium carbonate (13.6 g, 98.4 mmol) was dissolved in water (41 ml) and stirred sufficiently, and then tetrakis (triphenylphosphine) palladium (0) (0.9 g, 0.7 mmol) was added. After the reaction for 10 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 24 (7.4 g). (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 added to THF (300 ml) and stirred and refluxed. Then, potassium carbonate (14.8 g, 107.2 mmol) was dissolved in water (44 ml) and stirred sufficiently, and then tetrakis (triphenylphosphine) palladium (0) (0.9 g, 0.8 mmol) was added. After the reaction for 10 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 25 (11 g). (Yield 48%, MS: [M+H] ⁺ = 856)

Example 26: Preparation of compound 26

In a nitrogen atmosphere, compound Sub 26 (15 g, 24.6 mmol) and intermediate G (9.7 g, 27.1 mmol) were added to THF (300 ml), followed by stirring and refluxing. Then, potassium carbonate (13.6 g, 98.4 mmol) was dissolved in water (41 ml) and stirred sufficiently, and then tetrakis (triphenylphosphine) palladium (0) (0.9 g, 0.7 mmol) was added. After the reaction for 11 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 26 (15.3 g). (Yield 77%, MS: [M+H] ⁺ = 806)

Example 27: Preparation of compound 27

In a nitrogen atmosphere, compound Sub 27 (15 g, 24.6 mmol) and intermediate G (9.7 g, 27.1 mmol) were added to THF (300 ml), followed by stirring and refluxing. Then, potassium carbonate (13.6 g, 98.4 mmol) was dissolved in water (41 ml) and stirred sufficiently, and then tetrakis (triphenylphosphine) palladium (0) (0.9 g, 0.7 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 27 (5.9 g). (Yield 30%, MS: [M+H] ⁺ = 806)

Example 28: Preparation of compound 28

In a nitrogen atmosphere, compound Sub 28 (15 g, 24.6 mmol) and intermediate G (9.7 g, 27.1 mmol) were added to THF (300 ml), followed by stirring and refluxing. Then, potassium carbonate (13.6 g, 98.4 mmol) was dissolved in water (41 ml) and stirred sufficiently, and then tetrakis (triphenylphosphine) palladium (0) (0.9 g, 0.7 mmol) was added. After the reaction for 11 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 28 (9.5 g). (Yield 48%, MS: [M+H] ⁺ = 806)

Example 29: Preparation of compound 29

In a nitrogen atmosphere, compound Sub 29 (15 g, 26.8 mmol) and intermediate H (10.6 g, 29.5 mmol) were added to THF (300 ml), followed by stirring and refluxing. Then, potassium carbonate (14.8 g, 107.2 mmol) was dissolved in water (44 ml) and stirred sufficiently, and then tetrakis (triphenylphosphine) palladium (0) (0.9 g, 0.8 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 29 (11.5 g). (Yield 50%, MS: [M+H] ⁺ = 856)

Example 30: Preparation of compound 30

In a nitrogen atmosphere, compound Sub 30 (15 g, 24.6 mmol) and intermediate H (9.7 g, 27.1 mmol) were added to THF (300 ml), followed by stirring and refluxing. Subsequently, potassium carbonate (13.6 g, 98.4 mmol) was dissolved in water (41 ml), stirred sufficiently, and tetrakis (triphenylphosphine) palladium (0) (0.9 g, 0.7 mmol) was added. After the reaction for 11 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 30 (11.9 g). (Yield 60%, MS: [M+H] ⁺ = 806)

Example 31: Preparation of compound 31

In a nitrogen atmosphere, compound Sub 31 (15 g, 24.6 mmol) and intermediate H (9.7 g, 27.1 mmol) were added to THF (300 ml), followed by stirring and refluxing. Then, potassium carbonate (13.6 g, 98.4 mmol) was dissolved in water (41 ml) and stirred sufficiently, and then tetrakis (triphenylphosphine) palladium (0) (0.9 g, 0.7 mmol) was added. After the reaction for 12 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 31 (9.7 g). (Yield 49%, MS: [M+H] ⁺ = 806)

Example 32: Preparation of compound 32

In a nitrogen atmosphere, compound Sub 32 (15 g, 24.6 mmol) and intermediate H (9.7 g, 27.1 mmol) were added to THF (300 ml), followed by stirring and refluxing. Then, potassium carbonate (13.6 g, 98.4 mmol) was dissolved in water (41 ml) and stirred sufficiently, and then tetrakis (triphenylphosphine) palladium (0) (0.9 g, 0.7 mmol) was added. After the reaction for 11 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 32 (9.1 g). (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 added to THF (300 ml), followed by stirring and refluxing. Then, potassium carbonate (14.8 g, 107.2 mmol) was dissolved in water (44 ml) and stirred sufficiently, and then tetrakis (triphenylphosphine) palladium (0) (0.9 g, 0.8 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 33 (9.6 g). (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 added to THF (300 ml), followed by stirring and refluxing. Then, potassium carbonate (13.6 g, 98.4 mmol) was dissolved in water (41 ml) and stirred sufficiently, and then tetrakis (triphenylphosphine) palladium (0) (0.9 g, 0.7 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 34 (13.4 g). (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 added to THF (300 ml), followed by stirring and refluxing. Then, potassium carbonate (13.6 g, 98.4 mmol) was dissolved in water (41 ml) and stirred sufficiently, and then tetrakis (triphenylphosphine) palladium (0) (0.9 g, 0.7 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 35 (6 g). (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 added to THF (300 ml) and stirred and refluxed. Then, potassium carbonate (13.6 g, 98.4 mmol) was dissolved in water (41 ml) and stirred sufficiently, and then tetrakis (triphenylphosphine) palladium (0) (0.9 g, 0.7 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 36 (8.6 g). (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 added to THF (300 ml) and stirred and refluxed. Then, potassium carbonate (14.8 g, 107.2 mmol) was dissolved in water (44 ml) and stirred sufficiently, and then tetrakis (triphenylphosphine) palladium (0) (0.9 g, 0.8 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 37 (8.2 g). (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 added to THF (300 ml), followed by stirring and refluxing. Subsequently, potassium carbonate (13.6 g, 98.4 mmol) was dissolved in water (41 ml), stirred sufficiently, and tetrakis (triphenylphosphine) palladium (0) (0.9 g, 0.7 mmol) was added. After the reaction for 12 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 38 (12 g). (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 added to THF (300 ml) and stirred and refluxed. Subsequently, potassium carbonate (13.6 g, 98.4 mmol) was dissolved in water (41 ml), stirred sufficiently, and tetrakis (triphenylphosphine) palladium (0) (0.9 g, 0.7 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 39 (7.4 g). (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 added to THF (300 ml) and stirred and refluxed. Subsequently, potassium carbonate (13.6 g, 98.4 mmol) was dissolved in water (41 ml), stirred sufficiently, and tetrakis (triphenylphosphine) palladium (0) (0.9 g, 0.7 mmol) was added. After the reaction for 12 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 40 (8.1 g). (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 added to THF (300 ml) and stirred and refluxed. Then, potassium carbonate (14.8 g, 107.2 mmol) was dissolved in water (44 ml) and stirred sufficiently, and then tetrakis (triphenylphosphine) palladium (0) (0.9 g, 0.8 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 41 (10.7 g). (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 added to THF (300 ml) and stirred and refluxed. Subsequently, potassium carbonate (13.6 g, 98.4 mmol) was dissolved in water (41 ml), stirred sufficiently, and tetrakis (triphenylphosphine) palladium (0) (0.9 g, 0.7 mmol) was added. After the reaction for 10 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 42 (10.9 g). (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 added to THF (300 ml) and stirred and refluxed. Subsequently, potassium carbonate (13.6 g, 98.4 mmol) was dissolved in water (41 ml), stirred sufficiently, and tetrakis (triphenylphosphine) palladium (0) (0.9 g, 0.7 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 43 (8.5 g). (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 added to THF (300 ml) and stirred and refluxed. Subsequently, potassium carbonate (13.6 g, 98.4 mmol) was dissolved in water (41 ml), stirred sufficiently, and tetrakis (triphenylphosphine) palladium (0) (0.9 g, 0.7 mmol) was added. After the reaction for 10 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 44 (6.2 g). (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 added to THF (300 ml), followed by stirring and refluxing. Then, potassium carbonate (14.8 g, 107.2 mmol) was dissolved in water (44 ml) and stirred sufficiently, and then tetrakis (triphenylphosphine) palladium (0) (0.9 g, 0.8 mmol) was added. After the reaction for 11 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 45 (7.7 g). (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 added to THF (300 ml) and stirred and refluxed. Subsequently, potassium carbonate (13.6 g, 98.4 mmol) was dissolved in water (41 ml), stirred sufficiently, and tetrakis (triphenylphosphine) palladium (0) (0.9 g, 0.7 mmol) was added. After the reaction for 11 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 46 (10 g). (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 added to THF (300 ml) and stirred and refluxed. Then, potassium carbonate (13.6 g, 98.4 mmol) was dissolved in water (41 ml) and stirred sufficiently, and then tetrakis (triphenylphosphine) palladium (0) (0.9 g, 0.7 mmol) was added. After the reaction for 11 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 47 (10.7 g). (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 added to THF (300 ml) and stirred and refluxed. Then, potassium carbonate (13.6 g, 98.4 mmol) was dissolved in water (41 ml) and stirred sufficiently, and then tetrakis (triphenylphosphine) palladium (0) (0.9 g, 0.7 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 48 (6.8 g). (Yield 36%, MS: [M+H] ⁺ = 766)

[Experimental Example]

Experimental Example 1

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

The HI-1 compound was formed as a hole injection layer on the prepared ITO transparent electrode to a thickness of 1150 Å, but the compound A-1 was doped at a concentration of 1.5 wt%. The following HT-1 compound was vacuum-deposited on the hole injection layer to form a hole transport layer with a thickness of 800 Å. Subsequently, the following EB-1 compound was vacuum-deposited on the hole transport layer to form an electron blocking layer with a thickness of 150 Å. Subsequently, on the electron blocking layer, the compound 1 prepared in Example 1 and the following Dp-39 compound were vacuum-deposited at 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 emission layer to form a hole blocking layer with a thickness of 30 Å. Subsequently, the following ET-1 compound and the following LiQ compound were vacuum-deposited at a weight ratio of 2:1 on the hole blocking layer to form an electron injection and transport layer with a thickness of 300 Å. Lithium fluoride (LiF) in a thickness of 12 Å and aluminum in a thickness of 1,000 Å were sequentially deposited on the electron injection and transport layer to form a cathode.

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 at the negative electrode was 0.3 Å/sec, and the deposition rate of aluminum was 2 Å/sec. ^{Maintaining -7} ~ 5 × 10 ^-6 torr, an organic light emitting device was manufactured.

Experimental Examples 2 to 40

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

By applying a current to the organic light emitting device prepared in the Experimental Examples and Comparative Experimental Examples, driving voltage, current efficiency and life were measured, and the results are shown in Tables 1 to 3 below. T95 refers to the time it takes for the luminance to decrease to 95% from the initial luminance.

Experimental example Host material Driving 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 22.50 191 Experimental Example 2 Compound 2 4.45 24.35 187 Experimental Example 3 Compound 3 4.21 25.36 173 Experimental Example 4 Compound 4 4.82 24.33 165 Experimental Example 5 Compound 5 4.63 26.14 152 Experimental Example 6 Compound 6 4.43 23.36 154 Experimental Example 7 Compound 7 4.72 24.33 167 Experimental Example 8 Compound 8 4.22 23.31 185 Experimental Example 9 Compound 9 4.13 23.01 169 Experimental Example 10 Compound 10 4.33 25.99 183 Experimental Example 11 Compound 11 4.43 23.24 163 Experimental Example 12 Compound 12 4.20 26.10 188 Experimental Example 13 Compound 13 4.52 24.61 174 Experimental Example 14 Compound 14 4.31 25.31 188 Experimental Example 15 Compound 15 4.53 25.13 180 Experimental Example 16 Compound 16 4.21 23.82 170 Experimental Example 17 Compound 17 4.23 22.22 169 Experimental Example 18 Compound 18 4.15 23.22 182 Experimental Example 19 Compound 19 4.33 24.60 186 Experimental Example 20 Compound 20 4.40 23.93 175

Experimental example Host material Driving 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 4.42 24.25 171 Experimental Example 23 Compound 23 4.61 26.24 182 Experimental Example 24 Compound 24 4.53 24.83 192 Experimental Example 25 Compound 25 4.38 26.73 193 Experimental Example 26 Compound 26 4.25 24.33 186 Experimental Example 27 Compound 27 4.43 23.38 177 Experimental Example 28 Compound 28 4.35 24.59 180 Experimental Example 29 Compound 29 4.33 24.98 195 Experimental Example 30 Compound 30 4.41 26.03 188 Experimental Example 31 Compound 31 4.63 26.80 199 Experimental Example 32 Compound 32 4.51 26.83 183 Experimental Example 33 Compound 33 4.29 25.99 198 Experimental Example 34 Compound 34 4.36 23.44 200 Experimental Example 35 Compound 35 4.56 26.10 193 Experimental Example 36 Compound 36 4.43 24.61 183 Experimental Example 37 Compound 37 4.22 25.31 182 Experimental Example 38 Compound 38 4.22 26.13 185 Experimental Example 39 Compound 39 4.32 23.82 176 Experimental Example 40 Compound 40 4.50 25.73 188

Experimental example Host material Driving voltage
(V@10mA/cm ² ) Current efficiency
(cd/A@10mA/cm ² ) Life (T95)
(hr@10mA/cm ² ) Comparative Experimental Example 1 RH-1 5.45 14.99 47 Comparative Experiment 2 RH-2 5.52 14.14 55 Comparative Experiment 3 RH-3 5.63 14.55 66 Comparative Experimental Example 4 RH-4 5.54 14.35 54 Comparative Experimental Example 5 RH-5 5.13 14.46 63 Comparative Experiment 6 RH-6 5.82 14.58 72 Comparative Experimental Example 7 RH-7 5.32 16.21 73 Comparative Experimental Example 8 RH-8 5.43 12.35 69 Comparative Experimental Example 9 RH-9 5.95 11.63 61 Comparative Experimental Example 10 RH-10 5.14 14.52 70

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

Claims (8)

Compound represented by the following formula (1):
[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 substituted or unsubstituted C 2-60} heteroaryl including any one or more selected from the group consisting of N, O and S,
All of R ₁ to R ₄ are hydrogen or deuterium; Or _{two adjacent two of R 1} to R ₄ are bonded to form a benzene ring, and the remainder is hydrogen or deuterium,
R ₅ is hydrogen or deuterium,
Each R ₆ is independently hydrogen or deuterium,
n is an integer of 1 to 3.
The method of claim 1,
X is all N,
compound.
The method of claim 1,
Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, naphthyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, or 9-phenylcarbazolyl,
compound.
The method of claim 3,
At least one of Ar ₁ and Ar _{2 is phenyl,}
compound.
The method of claim 1,
R ₅ is hydrogen,
compound.
The method of claim 1,
R ₆ is hydrogen,
compound.
The method of claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of the following,
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 contains the compound according to any one of claims 1 to 7 That is, an organic light emitting device.

Images