KR102486518B1 - 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 O or S;

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

Ar is a substituted or unsubstituted C _6-60 aryl; Or a C2-60 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O and S,

R ₁ and R ₂ are substituted or unsubstituted C _1-60 alkyl; or a substituted or unsubstituted C _6-60 aryl, or R ₁ and R ₂ are bonded together to form a substituted or unsubstituted C _6-60 aromatic ring;

R ₃ is hydrogen or deuterium;

n1 is an integer from 1 to 4;

n2 is 1 or 2;

n3 is an integer from 1 to 5;

n4 is an integer from 1 to 4;

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, light emission, electron transport, or electron injection.

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

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

또는

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

or

means a bond connected to another substituent.

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

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

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

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

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

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

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

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

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

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

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

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

etc. However, it is not limited thereto.

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

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

In Formula 1, one or more hydrogens may be substituted with deuterium.

Preferably, Formula 1 is represented by any one selected from the group consisting of Formulas 1-1 to 1-4 below:

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Chemical Formulas 1-1 to 1-4, X, L, Ar, R ₁ , R ₂ , R ₃ , n1, n2, n3 and n4 are as defined above.

Preferably, L is a single bond; or phenylene. More preferably, L is a single bond; or 1,4-phenylene.

Preferably, Ar is phenyl, naphthyl, dimethylfluorenyl, dibenzofuranyl, or dibenzothiophenyl.

을 형성한다. R₁ 및 R₂가 함께 결합하여

을 형성한다는 의미는 하기의 구조를 가지는 화합물을 의미한다.Preferably, R ₁ and R ₂ are methyl; or phenyl, or R ₁ and R ₂ are bonded together

form R ₁ and R ₂ are bonded together

The meaning of forming means a compound having the following structure.

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

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

[Scheme 1]

Step 1 of Scheme 1 is an amine substitution reaction, which is preferably carried out in the presence of a palladium catalyst and a base, and the reactor for the amine substitution reaction may be modified as known in the art. Step 2 of Reaction Scheme 1 is a Suzuki coupling reaction, which is preferably carried out in the presence of a palladium catalyst and a base, and the reactor for the Suzuki coupling reaction can be changed as known in the art. 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.

In addition, the organic material layer may include an electron blocking layer, and the electron blocking layer includes the compound represented by Chemical Formula 1.

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 dopant of the light emitting layer.

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

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.

In addition, the organic material layer may include a light emitting layer and an electron transport layer, and the electron transport layer may include the compound represented by Chemical 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 composed of a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4. In this structure, the compound represented by Chemical Formula 1 may be included in the light emitting layer.

2 shows an example of an organic light emitting device composed of a substrate (1), an anode (2), a hole injection layer (5), a hole transport layer (6), a light emitting layer (7), an electron transport layer (8), and a cathode (4). it did In this structure, the compound represented by Formula 1 may be included in at least one layer of the hole injection layer, the hole transport layer, the light emitting layer, and the electron transport layer.

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

The organic light emitting device according to the present invention 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 electron suppression layer serves to improve the efficiency of the organic light emitting device by suppressing electrons injected from the cathode to be transferred toward the anode without recombination in the light emitting layer.

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 A (10 g, 32.5 mmol), compound sub1 (8.8 g, 35.8 mmol), and sodium tert-butoxide (6.2 g, 65 mmol) were added to toluene (200 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.7 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound subA-1 (8.1 g, yield 53%).

MS: [M+H] ⁺ = 472

In a nitrogen atmosphere, compound subA-1 (15 g, 31.8 mmol) and compound D (7.4 g, 35 mmol) were added to dioxane (300 ml), stirred and refluxed. Thereafter, potassium phosphate (17.6 g, 127.1 mmol) was dissolved in water (53 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 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 compound 1 (11.9 g, yield 62%).

MS: [M+H] ⁺ = 604

Example 2: Preparation of Compound 2

In a nitrogen atmosphere, compound subA-1 (15 g, 31.8 mmol) and compound E (8 g, 35 mmol) were added to dioxane (300 ml), stirred and refluxed. Thereafter, potassium phosphate (17.6 g, 127.1 mmol) was dissolved in water (53 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1 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 compound 2 (11.8 g, yield 60%).

MS: [M+H] ⁺ = 620

Example 3: Preparation of Compound 3

In a nitrogen atmosphere, compound A (10 g, 32.5 mmol), compound sub2 (10.6 g, 35.8 mmol), and sodium tert-butoxide (6.2 g, 65 mmol) were added to toluene (200 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.7 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound subA-2 (8.6 g, yield 51%).

MS: [M+H] ⁺ = 522

In a nitrogen atmosphere, compound subA-2 (15 g, 28.7 mmol) and compound E (7.2 g, 31.6 mmol) were added to dioxane (300 ml), stirred and refluxed. Thereafter, potassium phosphate (15.9 g, 114.9 mmol) was dissolved in water (48 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.9 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 compound 3 (9.4 g, yield 49%).

MS: [M+H] ⁺ = 670

Example 4: Preparation of Compound 4

In a nitrogen atmosphere, compound A (10 g, 32.5 mmol), compound sub3 (12.9 g, 35.8 mmol), and sodium tert-butoxide (6.2 g, 65 mmol) were added to toluene (200 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.7 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound subA-3 (9.9 g, yield 52%).

MS: [M+H] ⁺ = 588

In a nitrogen atmosphere, compound subA-3 (15 g, 25.5 mmol) and compound D (5.9 g, 28.1 mmol) were added to dioxane (300 ml), stirred and refluxed. Thereafter, potassium phosphate (14.1 g, 102 mmol) was dissolved in water (42 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.4 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 compound 4 (5.5 g, yield 30%).

MS: [M+H] ⁺ = 720

Example 5: Preparation of Compound 5

In a nitrogen atmosphere, compound subA-3 (15 g, 25.5 mmol) and compound E (6.4 g, 28.1 mmol) were added to dioxane (300 ml) and stirred and refluxed. Thereafter, potassium phosphate (14.1 g, 102 mmol) was dissolved in water (42 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.4 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 compound 5 (14.1 g, yield 75%).

MS: [M+H] ⁺ = 736

Example 6: Preparation of Compound 6

In a nitrogen atmosphere, compound B (10 g, 23.2 mmol), compound sub4 (4.3 g, 25.5 mmol), and sodium tert-butoxide (4.5 g, 46.3 mmol) were added to toluene (200 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound subB-1 (7.6 g, yield 63%).

MS: [M+H] ⁺ = 520

In a nitrogen atmosphere, compound subB-1 (15 g, 28.8 mmol) and compound F (7.2 g, 31.7 mmol) were added to dioxane (300 ml), stirred and refluxed. Thereafter, potassium phosphate (15.9 g, 115.4 mmol) was dissolved in water (48 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.9 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 compound 6 (11.5 g, yield 60%).

MS: [M+H] ⁺ = 668

Example 7: Preparation of Compound 7

In a nitrogen atmosphere, compound subB-1 (15 g, 28.8 mmol) and compound G (6.7 g, 31.7 mmol) were added to dioxane (300 ml), stirred and refluxed. Thereafter, potassium phosphate (15.9 g, 115.4 mmol) was dissolved in water (48 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.9 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 compound 7 (13.5 g, yield 72%).

MS: [M+H] ⁺ = 652

Example 8: Preparation of Compound 8

In a nitrogen atmosphere, compound B (10 g, 23.2 mmol), compound sub1 (6.3 g, 25.5 mmol), and sodium tert-butoxide (4.5 g, 46.3 mmol) were added to toluene (200 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound subB-2 (8.7 g, yield 63%).

MS: [M+H] ⁺ = 596

In a nitrogen atmosphere, compound subB-2 (15 g, 25.2 mmol) and compound G (5.9 g, 27.7 mmol) were added to dioxane (300 ml), stirred and refluxed. Thereafter, potassium phosphate (13.9 g, 100.6 mmol) was dissolved in water (42 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.4 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 obtain compound 8 (8.1 g, yield 44%).

MS: [M+H] ⁺ = 728

Example 9: Preparation of compound 9

In a nitrogen atmosphere, compound B (10 g, 23.2 mmol), compound sub5 (7.5 g, 25.5 mmol), and sodium tert-butoxide (4.5 g, 46.3 mmol) were added to toluene (200 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound subB-3 (9.3 g, yield 62%).

MS: [M+H] ⁺ = 646

In a nitrogen atmosphere, compound subB-3 (15 g, 23.2 mmol) and compound G (5.4 g, 25.5 mmol) were added to dioxane (300 ml) and stirred and refluxed. Thereafter, potassium phosphate (12.8 g, 92.8 mmol) was dissolved in water (38 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.4 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 obtain compound 9 (6.1 g, yield 34%).

MS: [M+H] ⁺ = 778

Example 10: Preparation of compound 10

In a nitrogen atmosphere, compound B (10 g, 23.2 mmol), compound sub6 (6.3 g, 25.5 mmol), and sodium tert-butoxide (4.5 g, 46.3 mmol) were added to toluene (200 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound subB-4 (7.6 g, yield 55%).

MS: [M+H] ⁺ = 596

In a nitrogen atmosphere, compound subB-4 (15 g, 25.2 mmol) and compound H (6.3 g, 27.7 mmol) were added to dioxane (300 ml), stirred and refluxed. Thereafter, potassium phosphate (13.9 g, 100.6 mmol) was dissolved in water (42 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.4 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 compound 10 (12.9 g, yield 69%).

MS: [M+H] ⁺ = 744

Example 11: Preparation of Compound 11

In a nitrogen atmosphere, compound C (10 g, 23.3 mmol), compound sub7 (7 g, 25.6 mmol), and sodium tert-butoxide (4.5 g, 46.5 mmol) were added to toluene (200 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound subC-1 (12.3 g, yield 70%).

MS: [M+H] ⁺ = 756

In a nitrogen atmosphere, compound subC-1 (15 g, 24 mmol) and compound G (5.6 g, 26.4 mmol) were added to dioxane (300 ml), stirred and refluxed. Thereafter, potassium phosphate (13.3 g, 96.1 mmol) was dissolved in water (40 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.4 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 compound 11 (12.3 g, yield 68%).

MS: [M+H] ⁺ = 756

Example 12: Preparation of compound 12

In a nitrogen atmosphere, compound subC-1 (15 g, 24 mmol) and compound F (6 g, 26.4 mmol) were added to dioxane (300 ml), stirred and refluxed. Thereafter, potassium phosphate (13.3 g, 96.1 mmol) was dissolved in water (40 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.4 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 compound 12 (11.7 g, yield 63%).

MS: [M+H] ⁺ = 772

Example 13: Preparation of compound 13

In a nitrogen atmosphere, compound C (10 g, 23.3 mmol), compound sub8 (8.2 g, 25.6 mmol), and sodium tert-butoxide (4.5 g, 46.5 mmol) were added to toluene (200 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound subC-2 (10.4 g, yield 67%).

MS: [M+H] ⁺ = 670

In a nitrogen atmosphere, compound subC-2 (15 g, 22.4 mmol) and compound G (5.2 g, 24.6 mmol) were added to dioxane (300 ml), stirred and refluxed. Thereafter, potassium phosphate (12.4 g, 89.5 mmol) was dissolved in water (37 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 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 compound 13 (5.6 g, yield 31%).

MS: [M+H] ⁺ = 802

Example 14: Preparation of compound 14

In a nitrogen atmosphere, compound C (10 g, 23.3 mmol), compound sub9 (8.2 g, 25.6 mmol), and sodium tert-butoxide (4.5 g, 46.5 mmol) were added to toluene (200 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound subC-3 (7.9 g, yield 51%).

MS: [M+H] ⁺ = 670

In a nitrogen atmosphere, compound subC-3 (15 g, 22.4 mmol) and compound F (5.6 g, 24.6 mmol) were added to dioxane (300 ml), stirred and refluxed. Thereafter, potassium phosphate (12.4 g, 89.5 mmol) was dissolved in water (37 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 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 compound 14 (7.1 g, yield 39%).

MS: [M+H] ⁺ = 818

Example 15: Preparation of compound 15

In a nitrogen atmosphere, compound C (10 g, 23.3 mmol), compound sub10 (7.6 g, 25.6 mmol), and sodium tert-butoxide (4.5 g, 46.5 mmol) were added to toluene (200 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound subC-4 (8.1 g, yield 54%).

MS: [M+H] ⁺ = 644

In a nitrogen atmosphere, compound subC-4 (15 g, 22.6 mmol) and compound G (5.3 g, 24.8 mmol) were added to dioxane (300 ml), stirred and refluxed. Thereafter, potassium phosphate (12.5 g, 90.3 mmol) was dissolved in water (37 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 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 compound 15 (10.5 g, yield 60%).

MS: [M+H] ⁺ = 776

Example 16: Preparation of compound 16

In a nitrogen atmosphere, compound subC-4 (15 g, 23.3 mmol) and compound F (5.8 g, 25.6 mmol) were added to dioxane (300 ml), stirred and refluxed. Thereafter, potassium phosphate (12.9 g, 93.1 mmol) was dissolved in 39 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.4 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 compound 16 (14.4 g, yield 78%).

MS: [M+H] ⁺ = 792

Example 17: Preparation of compound 17

In a nitrogen atmosphere, compound C (10 g, 23.3 mmol), compound sub1 (6.3 g, 25.6 mmol), and sodium tert-butoxide (4.5 g, 46.5 mmol) were added to toluene (200 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound subC-5 (8.1 g, yield 59%).

MS: [M+H] ⁺ = 594

In a nitrogen atmosphere, compound subC-5 (15 g, 25.2 mmol) and compound I (5.9 g, 27.8 mmol) were added to dioxane (300 ml), stirred and refluxed. Thereafter, potassium phosphate (14 g, 101 mmol) was dissolved in water (42 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.4 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 compound 17 (13 g, yield 71%).

MS: [M+H] ⁺ = 726

Example 18: Preparation of compound 18

In a nitrogen atmosphere, compound C (10 g, 23.3 mmol), compound sub11 (8.6 g, 25.6 mmol), and sodium tert-butoxide (4.5 g, 46.5 mmol) were added to toluene (200 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound subC-6 (9.5 g, yield 60%).

MS: [M+H] ⁺ = 684

In a nitrogen atmosphere, compound subC-6 (15 g, 21.9 mmol) and compound F (5.5 g, 24.1 mmol) were added to dioxane (300 ml), stirred and refluxed. Thereafter, potassium phosphate (12.1 g, 87.7 mmol) was dissolved in water (36 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 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 compound 18 (7.3 g, yield 40%).

MS: [M+H] ⁺ = 832

[Experimental example]

Experimental Example 1

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

The following compound HI-1 was formed to a thickness of 1150 Å as a hole injection layer on the prepared ITO transparent electrode, but the following compound A-1 was p-doped at a concentration of 1.5%. A hole transport layer having a thickness of 800 Å was formed by vacuum depositing the following HT-1 compound on the hole injection layer. An electron blocking layer having a thickness of 150 Å was formed on the hole transport layer by vacuum depositing Compound 1 previously prepared. A red light emitting layer having a thickness of 400 Å was formed on the electron-suppressing layer by vacuum depositing a compound of RH-1 and a compound of Dp-7 in a weight ratio of 98:2. A hole blocking layer having a thickness of 30 Å was formed on the light emitting layer by vacuum depositing the following HB-1 compound. An electron injection and transport layer having a thickness of 300 Å was formed on the hole-blocking layer by vacuum depositing the following ET-1 compound and the following LiQ compound in a weight ratio of 2:1. A negative electrode was formed by sequentially depositing lithium fluoride (LiF) to a thickness of 12 Å and aluminum to a thickness of 1,000 Å on the electron injection and transport layer.

In the above process, the deposition rate of the organic material was maintained at 0.4 to 0.7 Å/sec, the deposition rate of lithium fluoride on the anode was 0.3 Å/sec, and the deposition rate of aluminum was 2 Å/sec, and the vacuum level during deposition was 2×10 Maintaining ^-7 to 5×10 ^-6 torr, an organic light emitting device was fabricated.

Experimental Examples 2 to 18

An organic light emitting device was manufactured in the same manner as in Experimental Example 1, except that the compound shown in Table 1 was used instead of Compound 1.

Comparative Experimental Examples 1 to 13

An organic light emitting device was manufactured in the same manner as in Experimental Example 1, except for using the compound shown in Table 2 instead of Compound 1. The compounds listed in Table 2 below are each as follows.

When current was applied to the organic light emitting device prepared in the Experimental Example and Comparative Experimental Example, voltage, efficiency, and lifetime (T95) were measured, and the results are shown in Tables 1 and 2 below. The lifetime T95 means the time required for the luminance to decrease from the initial luminance (6000 nit) to 95%.

compound
(electron suppression layer) drive voltage
(V@10mA/cm ² ) efficiency
(cd/A@10mA/cm ² ) Lifetime T95
(hr@10mA/cm ² ) luminescent color Experimental Example 1 compound 1 3.63 23.5 163 Red Experimental Example 2 compound 2 3.60 24.7 167 Red Experimental Example 3 compound 3 3.72 24.8 169 Red Experimental Example 4 compound 4 3.68 25.1 171 Red Experimental Example 5 compound 5 3.54 24.3 163 Red Experimental Example 6 compound 6 3.65 23.3 167 Red Experimental Example 7 compound 7 3.73 23.9 181 Red Experimental Example 8 compound 8 3.71 24.5 192 Red Experimental Example 9 compound 9 3.68 24.3 188 Red Experimental Example 10 compound 10 3.50 25.1 190 Red Experimental Example 11 compound 11 3.75 24.8 193 Red Experimental Example 12 compound 12 3.64 25.3 185 Red Experimental Example 13 compound 13 3.60 23.9 194 Red Experimental Example 14 compound 14 3.53 24.1 161 Red Experimental Example 15 compound 15 3.55 26.0 168 Red Experimental Example 16 compound 16 3.58 25.2 167 Red Experimental Example 17 compound 17 3.63 23.6 188 Red Experimental Example 18 compound 18 3.59 23.9 176 Red

compound
(electron suppression layer) drive voltage
(V@10mA/cm ² ) efficiency
(cd/A@10mA/cm ² ) Lifetime T95
(hr@10mA/cm ² ) luminescent color Comparative Experimental Example 1 EB-1 4.13 21.2 136 Red Comparative Experimental Example 2 C-1 3.88 19.5 93 Red Comparative Experimental Example 3 C-2 3.89 19.2 74 Red Comparative Experimental Example 4 C-3 3.83 18.1 89 Red Comparative Experimental Example 5 C-4 3.82 18.3 95 Red Comparative Experimental Example 6 C-5 4.15 18.4 71 Red Comparative Experimental Example 7 C-6 4.17 18.2 83 Red Comparative Experimental Example 8 C-7 4.00 20.4 137 Red Comparative Experimental Example 9 C-8 4.09 20.3 145 Red Comparative Experimental Example 10 C-9 4.18 19.2 121 Red Comparative Experimental Example 11 C-10 4.13 19.0 135 Red Comparative Experimental Example 12 C-11 3.98 20.3 118 Red Comparative Experimental Example 13 C-12 3.90 20.1 142 Red

As shown in Tables 1 and 2, when the compound of the present invention was used as an electron suppression layer, the driving voltage was significantly lowered compared to the comparative material, and the efficiency was also significantly increased, indicating that the energy from the host to the red dopant It was found that the transfer worked well. In addition, it was found that the lifetime characteristics can be greatly improved while maintaining high efficiency, which is due to the higher electron and hole stability of the compound of the present invention than the comparative compound. In conclusion, it can be confirmed that the driving voltage, luminous efficiency and lifetime characteristics of the organic light emitting device can be improved when the compound of the present invention is used as a host of the red light emitting layer.

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

Claims (8)

A compound represented by any one selected from the group consisting of Formulas 1-2 to 1-4:
[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Formulas 1-2 to 1-4,
X is O or S;
L is a single bond; or a substituted or unsubstituted C _6-60 arylene;
Ar is 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 and R ₂ are bonded together

form,
R ₃ is hydrogen or deuterium;
n1 is an integer from 1 to 4;
n2 is 1 or 2;
n3 is an integer from 1 to 5;
n4 is an integer from 1 to 4;
delete According to claim 1,
L is a single bond; or phenylene,
compound.
According to claim 1,
Ar is phenyl, naphthyl, dimethylfluorenyl, dibenzofuranyl, or dibenzothiophenyl;
compound.
delete 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 any one of claims 1, 3, 4, and 6. comprising a compound according to one claim,
The organic material layer containing the compound is an electron blocking layer,
organic light emitting device. delete

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