KR102573176B1 - Organic light emitting device - Google Patents

Abstract

The present invention provides an organic light emitting device.

Description

Organic light emitting device {Organic light emitting device}

The present invention relates to an organic light emitting device.

In general, the organic light emitting phenomenon refers to a phenomenon in which 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 an organic light emitting diode having improved driving voltage, efficiency and lifetime.

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

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

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

Organic Light-Emitting Elements:

[Formula 1]

In Formula 1,

L ₁ is a single bond; or a substituted or unsubstituted C _6-60 arylene;

L ₂ and L ₃ are each independently a single bond; or a substituted or unsubstituted C _6-60 arylene;

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

R is hydrogen, deuterium, or substituted or unsubstituted C _6-60 aryl;

[Formula 2]

In Formula 2,

L ₄ and L ₅ are each independently a single bond; or a substituted or unsubstituted C _6-60 arylene;

Ar ₃ to Ar ₆ are each independently substituted or unsubstituted C _6-60 aryl; Or a C _5-60 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O and S.

The organic light emitting device described above is excellent in driving voltage, efficiency and lifetime.

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 a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 3, an electron transport layer 7, an electron injection layer 8, and a cathode 4. It shows an example of an organic light emitting device made of.

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

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.

In the present specification, the fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure. When the fluorenyl group is substituted, etc. However, it is not limited thereto.

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

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

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

anode and cathode

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

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

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

light emitting layer

The light emitting layer used in the present invention means a layer capable of emitting light in the visible ray region by combining holes and electrons transferred from the anode and the cathode. In general, the light emitting layer includes a host material and a dopant material, and in the present invention, the compound represented by Formula 1 and the compound represented by Formula 2 are included as hosts.

Preferably, Formula 1 is represented by any one of Formulas 1-1 to 1-4 below.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Chemical Formulas 1-1 to 1-4, L ₁ to L ₃ , Ar ₁ , Ar ₂ and R are as defined above.

Preferably, L ₁ is a single bond, phenylene, or naphthylene. More preferably, L ₁ is a single bond; , or am.

Preferably, L ₂ and L ₃ are each independently a single bond, phenylene, or naphthylene.

Preferably, Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, triphenylenyl, naphthylphenyl, phenylnaphthyl, dimethylfluorenyl, dibenzophenone ranyl, dibenzothiophenyl, carbazol-9-yl, or 9-phenyl-9H-carbazolyl; Ar ₁ and Ar ₂ are each independently unsubstituted or substituted with one or more deuterium atoms.

Preferably, R is hydrogen, deuterium, phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, dibenzofuranyl, or dibenzothiophenyl.

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

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

[Scheme 1]

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

Each of the above reactions is a Suzuki coupling reaction, and 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 Formula 2, preferably, L ₄ and L ₅ are each independently a single bond; or phenylene.

Preferably, Ar ₃ to Ar ₆ are each independently selected from phenyl, biphenylyl, naphthyl, phenylnaphthyl, naphthylphenyl, dimethylfluorenyl, dibenzofuranyl, (dibenzofuranyl)phenyl, dibenzo thiophenyl, or (dibenzothiophenyl)phenyl.

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

In addition, the present invention provides a method for preparing the compound represented by Formula 2 as shown in Reaction Scheme 2 below.

[Scheme 2]

In Scheme 2, each definition is as defined above.

The above reaction is a Suzuki coupling reaction, which is preferably carried out in the presence of a palladium catalyst and a base, and a reactor for the Suzuki coupling reaction can be changed as known in the art. In addition, in Scheme 2, when L ₅ or L ₆ is a single bond, each of -L ₅ -B(OH) ₂ and -L ₆ -B(OH) ₂ may be -H, in which case amine substitution do it in reaction The manufacturing method may be more specific in Preparation Examples to be described later.

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

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

hole transport layer

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

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

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

hole injection layer

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

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

Specific examples of the hole injection material include metal porphyrins, oligothiophenes, arylamine-based organic materials, hexanitrilehexaazatriphenylene-based organic materials, quinacridone-based organic materials, and perylene-based organic materials. of organic matter, anthraquinone, and polyaniline and polythiophene-based conductive polymers, but are not limited thereto.

electron transport layer

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

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

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

electron injection layer

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

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

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

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato) aluminum, tris(2-methyl-8-hydroxyquinolinato) aluminum, tris(8-hydroxyquinolinato) gallium, bis(10-hydroxybenzo[h] Quinolinato) beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)( There are o-cresolato) gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, and bis(2-methyl-8-quinolinato)(2-naphtolato)gallium. Not limited to this.

organic light emitting device

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

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

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

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

Manufacturing of the organic light emitting device according to the present invention 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.

[Production Example]

Preparation Example 1-1

In a nitrogen atmosphere, compound Trz1 (15 g, 40.8 mmol) and compound A (11.2 g, 42.8 mmol) were added to THF (300 ml), stirred and refluxed. After dissolving potassium carbonate (16.9 g, 122.3 mmol) in water (51 ml), it was added, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.9 g of compound 1-1. (Yield 71%, MS: [M+H] ⁺ = 550)

Preparation Example 1-2

In a nitrogen atmosphere, compound Trz2 (15 g, 35.9 mmol) and compound A (9.9 g, 37.7 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (14.9 g, 107.7 mmol) was dissolved in water (45 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.1 g of Compound 1-2. (Yield 61%, MS: [M+H] ⁺ = 600)

Preparation Example 1-3

In a nitrogen atmosphere, compound Trz3 (15 g, 35.7 mmol) and compound A (9.8 g, 37.5 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (14.8 g, 107.2 mmol) was dissolved in water (44 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.7 g of compound 1-3. (Yield 73%, MS: [M+H] ⁺ = 602)

Preparation Example 1-4

In a nitrogen atmosphere, compound Trz4 (15 g, 38.1 mmol) and compound A (10.5 g, 40 mmol) were added to THF (300 ml), stirred and refluxed. After dissolving potassium carbonate (15.8 g, 114.3 mmol) in water (47 ml), it was added, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.8 g of compound 1-4. (Yield 63%, MS: [M+H] ⁺ = 576)

Preparation Example 1-5

In a nitrogen atmosphere, compound Trz5 (15 g, 38.1 mmol) and compound A (10.5 g, 40 mmol) were added to THF (300 ml), stirred and refluxed. After dissolving potassium carbonate (15.8 g, 114.3 mmol) in water (47 ml), it was added, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.6 g of compound 1-5. (Yield 62%, MS: [M+H] ⁺ = 576)

Preparation Example 1-6

In a nitrogen atmosphere, compound Trz6 (15 g, 41.9 mmol) and compound A (11.5 g, 44 mmol) were added to THF (300 ml), stirred and refluxed. After dissolving potassium carbonate (17.4 g, 125.8 mmol) in water (52 ml), it was added, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14 g of compound 1-6. (Yield 62%, MS: [M+H] ⁺ = 540)

Production Example 1-7

In a nitrogen atmosphere, compound Trz7 (15 g, 39.1 mmol) and compound A (10.8 g, 41 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (16.2 g, 117.2 mmol) was dissolved in water (49 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.1 g of compound 1-7. (Yield 64%, MS: [M+H] ⁺ = 566)

Production Example 1-8

In a nitrogen atmosphere, compound Trz8 (15 g, 34.6 mmol) and compound A (9.5 g, 36.4 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (14.4 g, 103.9 mmol) was dissolved in water (43 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 11 hours, it was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.5 g of compound 1-8. (Yield 68%, MS: [M+H] ⁺ = 615)

Production Example 1-9

In a nitrogen atmosphere, compound Trz9 (15 g, 38.1 mmol) and compound A (10.5 g, 40 mmol) were added to THF (300 ml), stirred and refluxed. After dissolving potassium carbonate (15.8 g, 114.3 mmol) in water (47 ml), it was added, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 17.5 g of compound 1-9. (Yield 80%, MS: [M+H] ⁺ = 576)

Production Example 1-10

In a nitrogen atmosphere, compound Trz10 (15 g, 34.6 mmol) and compound A (9.5 g, 36.3 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (14.3 g, 103.7 mmol) was dissolved in water (43 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 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 14 g of compound 1-10. (Yield 65%, MS: [M+H] ⁺ = 626)

Preparation Example 1-11

In a nitrogen atmosphere, compound Trz11 (15 g, 56 mmol) and compound B (16.6 g, 56 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (15.5 g, 112.1 mmol) was dissolved in water (46 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 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 19.5 g of compound subB-1. (Yield 72%, MS: [M+H] ⁺ = 484)

In a nitrogen atmosphere, compound subB-1 (15 g, 31 mmol) and compound sub1 (5.6 g, 32.5 mmol) were added to THF (300 ml) and stirred and refluxed. Thereafter, potassium carbonate (12.9 g, 93 mmol) was dissolved in water (39 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 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 14.3 g of compound 1-11. (Yield 80%, MS: [M+H] ⁺ = 576)

Production Example 1-12

In a nitrogen atmosphere, compound Trz9 (15 g, 38.1 mmol) and compound B (11.3 g, 38.1 mmol) were added to THF (300 ml), stirred and refluxed. After dissolving potassium carbonate (10.5 g, 76.2 mmol) in water (32 ml), it was added, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.7 g of compound subB-2. (Yield 72%, MS: [M+H] ⁺ = 610)

In a nitrogen atmosphere, compound subB-2 (15 g, 24.6 mmol) and compound sub2 (3.1 g, 25.8 mmol) were added to THF (300 ml) and stirred and refluxed. After dissolving potassium carbonate (10.2 g, 73.8 mmol) in water (31 ml), it was added, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 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 11.7 g of compound 1-12. (Yield 73%, MS: [M+H] ⁺ = 652)

Production Example 1-13

In a nitrogen atmosphere, compound subB-1 (15 g, 31 mmol) and compound sub3 (6.9 g, 32.5 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (12.9 g, 93 mmol) was dissolved in water (39 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 11 hours, it was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.7 g of compound 1-13. (Yield 72%, MS: [M+H] ⁺ = 616)

Production Example 1-14

In a nitrogen atmosphere, compound subB-1 (15 g, 31 mmol) and compound sub4 (7.4 g, 32.5 mmol) were added to THF (300 ml) and stirred and refluxed. Thereafter, potassium carbonate (12.9 g, 93 mmol) was dissolved in water (39 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.9 g of compound 1-14. (Yield 71%, MS: [M+H] ⁺ = 633)

Production Example 1-15

In a nitrogen atmosphere, compound Trz11 (15 g, 56 mmol) and compound C (16.6 g, 56 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (15.5 g, 112.1 mmol) was dissolved in water (46 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 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 16.2 g of compound subC-1. (Yield 60%, MS: [M+H] ⁺ = 484)

In a nitrogen atmosphere, compound subC-1 (15 g, 31 mmol) and compound sub5 (6.9 g, 32.5 mmol) were added to THF (300 ml) and stirred and refluxed. Thereafter, potassium carbonate (12.9 g, 93 mmol) was dissolved in water (39 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.8 g of compound 1-15. (Yield 67%, MS: [M+H] ⁺ = 616)

Production Example 1-16

In a nitrogen atmosphere, compound Trz12 (15 g, 40.1 mmol) and compound B (11.9 g, 40.1 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (11.1 g, 80.2 mmol) was dissolved in water (33 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 11 hours, it was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.7 g of compound subB-3. (Yield 62%, MS: [M+H] ⁺ = 590)

In a nitrogen atmosphere, compound subB-3 (15 g, 25.4 mmol) and compound sub6 (5.3 g, 26.7 mmol) were added to THF (300 ml) and stirred and refluxed. Thereafter, potassium carbonate (10.5 g, 76.3 mmol) was dissolved in water (32 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.8 g of compound 1-16. (Yield 60%, MS: [M+H] ⁺ = 708)

Production Example 1-17

In a nitrogen atmosphere, compound Trz13 (15 g, 43.6 mmol) and compound C (12.9 g, 43.6 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (12.1 g, 87.3 mmol) was dissolved in 36 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.8 g of compound subC-2. (Yield 69%, MS: [M+H] ⁺ = 560)

In a nitrogen atmosphere, compound subC-2 (15 g, 26.8 mmol) and compound sub1 (4.8 g, 28.1 mmol) were added to THF (300 ml) and stirred and refluxed. Thereafter, potassium carbonate (11.1 g, 80.3 mmol) was dissolved in water (33 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 11 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 14 g of compound 1-17. (Yield 80%, MS: [M+H] ⁺ = 652)

Production Example 1-18

In a nitrogen atmosphere, compound Trz6 (15 g, 41.9 mmol) and compound D (12.4 g, 41.9 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (11.6 g, 83.8 mmol) was dissolved in 35 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 17.3 g of compound subD-1. (Yield 72%, MS: [M+H] ⁺ = 574)

In a nitrogen atmosphere, compound subD-1 (15 g, 26.1 mmol) and compound sub2 (3.3 g, 27.4 mmol) were added to THF (300 ml) and stirred and refluxed. After dissolving potassium carbonate (10.8 g, 78.4 mmol) in water (33 ml), it was added, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.5 g of compound 1-18. (Yield 62%, MS: [M+H] ⁺ = 652)

Production Example 1-19

In a nitrogen atmosphere, compound Trz14 (15 g, 31 mmol) and compound C (9.2 g, 31 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (8.6 g, 62 mmol) was dissolved in water (26 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.2 g of compound subC-3. (Yield 61%, MS: [M+H] ⁺ = 700)

In a nitrogen atmosphere, compound subC-3 (15 g, 21.4 mmol) and compound sub2 (2.7 g, 22.5 mmol) were added to THF (300 ml) and stirred and refluxed. Thereafter, potassium carbonate (8.9 g, 64.3 mmol) was dissolved in water (27 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 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 10.3 g of compound 1-19. (Yield 65%, MS: [M+H] ⁺ = 742)

Preparation Example 1-20

In a nitrogen atmosphere, compound Trz15 (15 g, 35.7 mmol) and compound E (9.8 g, 37.5 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (14.8 g, 107.2 mmol) was dissolved in water (44 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.7 g of compound 1-20. (Yield 73%, MS: [M+H] ⁺ = 602)

Preparation Example 1-21

In a nitrogen atmosphere, compound Trz16 (15 g, 35.7 mmol) and compound E (9.8 g, 37.5 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (14.8 g, 107.2 mmol) was dissolved in water (44 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14 g of compound 1-21. (Yield 65%, MS: [M+H] ⁺ = 602)

Preparation Example 1-22

In a nitrogen atmosphere, compound Trz17 (15 g, 38.1 mmol) and compound E (10.5 g, 40 mmol) were added to THF (300 ml), stirred and refluxed. After dissolving potassium carbonate (15.8 g, 114.3 mmol) in water (47 ml), it was added, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.6 g of compound 1-22. (Yield 62%, MS: [M+H] ⁺ = 576)

Preparation Example 1-23

In a nitrogen atmosphere, compound Trz18 (15 g, 39.1 mmol) and compound E (10.8 g, 41 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (16.2 g, 117.2 mmol) was dissolved in water (49 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.9 g of compound 1-23. (Yield 63%, MS: [M+H] ⁺ = 566)

Preparation Example 1-24

In a nitrogen atmosphere, compound Trz19 (15 g, 35.9 mmol) and compound F (9.9 g, 37.7 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (14.9 g, 107.7 mmol) was dissolved in water (45 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 11 hours, it was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.8 g of compound 1-24. (Yield 64%, MS: [M+H] ⁺ = 600)

Preparation Example 1-25

In a nitrogen atmosphere, compound Trz20 (15 g, 38.1 mmol) and compound F (10.5 g, 40 mmol) were added to THF (300 ml), stirred and refluxed. After dissolving potassium carbonate (15.8 g, 114.3 mmol) in water (47 ml), it was added, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 11 hours, it was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.4 g of compound 1-25. (Yield 61%, MS: [M+H] ⁺ = 576)

Preparation Example 1-26

In a nitrogen atmosphere, compound Trz21 (15 g, 41.9 mmol) and compound F (11.5 g, 44 mmol) were added to THF (300 ml), stirred and refluxed. After dissolving potassium carbonate (17.4 g, 125.8 mmol) in water (52 ml), it was added, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.1 g of compound 1-26. (Yield 67%, MS: [M+H] ⁺ = 540)

Preparation Example 1-27

In a nitrogen atmosphere, compound Trz22 (15 g, 42 mmol) and compound F (11.6 g, 44.1 mmol) were added to THF (300 ml) and stirred and refluxed. Thereafter, potassium carbonate (17.4 g, 126.1 mmol) was dissolved in water (52 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.2 g of compound 1-27. (Yield 67%, MS: [M+H] ⁺ = 539)

Preparation Example 1-28

In a nitrogen atmosphere, compound Trz23 (15 g, 38.1 mmol) and compound G (10.5 g, 40 mmol) were added to THF (300 ml), stirred and refluxed. After dissolving potassium carbonate (15.8 g, 114.3 mmol) in water (47 ml), it was added, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.9 g of compound 1-28. (Yield 77%, MS: [M+H] ⁺ = 576)

Preparation Example 1-29

In a nitrogen atmosphere, compound Trz24 (15 g, 38.1 mmol) and compound G (10.5 g, 40 mmol) were added to THF (300 ml), stirred and refluxed. After dissolving potassium carbonate (15.8 g, 114.3 mmol) in water (47 ml), it was added, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 11 hours, it was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.3 g of compound 1-29. (Yield 70%, MS: [M+H] ⁺ = 576)

Preparation Example 1-30

In a nitrogen atmosphere, compound Trz25 (15 g, 35.4 mmol) and compound G (9.7 g, 37.2 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (14.7 g, 106.2 mmol) was dissolved in water (44 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.3 g of compound 1-30. (Yield 62%, MS: [M+H] ⁺ = 606)

Preparation Example 2-1

In a nitrogen atmosphere, compound H (15 g, 51.4 mmol) and compound sub7 (19 g, 52 mmol) were added to THF (300 ml) and stirred and refluxed. Thereafter, potassium carbonate (14.2 g, 102.9 mmol) was dissolved in water (43 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 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 21.6 g of compound subH-1. (Yield 79%, MS: [M+H] ⁺ = 532)

In a nitrogen atmosphere, compound subH-1 (10 g, 18.8 mmol), compound amine 1 (3.3 g, 19.7 mmol), and sodium tert-butoxide (2.3 g, 24.4 mmol) were added to xylene (200 ml), stirred and refluxed. did. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. When the reaction was completed after 5 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.9 g of compound 2-1. (Yield 63%, MS: [M+H] ⁺ = 665)

Preparation Example 2-2

In a nitrogen atmosphere, compound subH-1 (10 g, 18.8 mmol), compound amine 2 (4.8 g, 19.7 mmol), and sodium tert-butoxide (2.3 g, 24.4 mmol) were added to xylene (200 ml), stirred and refluxed. did. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. When the reaction was completed after 5 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 8.6 g of compound 2-2. (Yield 62%, MS: [M+H] ⁺ = 741)

Preparation Example 2-3

In a nitrogen atmosphere, compound H (15 g, 51.4 mmol) and compound sub8 (21.6 g, 52 mmol) were added to THF (300 ml) and stirred and refluxed. Thereafter, potassium carbonate (14.2 g, 102.9 mmol) was dissolved in water (43 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.9 g of compound subH-2. (Yield 70%, MS: [M+H] ⁺ = 582)

In a nitrogen atmosphere, compound subH-2 (10 g, 17.2 mmol), compound amine 1 (3.1 g, 18 mmol), and sodium tert-butoxide (2.1 g, 22.3 mmol) were added to xylene (200 ml), stirred and refluxed. did. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. When the reaction was completed after 5 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.3 g of compound 2-3. (Yield 51%, MS: [M+H] ⁺ = 715)

Preparation Example 2-4

In a nitrogen atmosphere, compound H (15 g, 51.4 mmol) and compound sub9 (17.6 g, 52 mmol) were added to THF (300 ml) and stirred and refluxed. Thereafter, potassium carbonate (14.2 g, 102.9 mmol) was dissolved in water (43 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 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 17.7 g of compound subH-3. (Yield 68%, MS: [M+H] ⁺ = 506)

In a nitrogen atmosphere, compound subH-3 (10 g, 19.8 mmol), compound amine 3 (4.6 g, 20.7 mmol), and sodium tert-butoxide (2.5 g, 25.7 mmol) were added to xylene (200 ml), stirred and refluxed. did. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. When the reaction was completed after 5 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.8 g of compound 2-4. (Yield 50%, MS: [M+H] ⁺ = 689)

Preparation Example 2-5

In a nitrogen atmosphere, compound H (15 g, 51.4 mmol) and compound sub10 (21.6 g, 52 mmol) were added to THF (300 ml) and stirred and refluxed. Thereafter, potassium carbonate (14.2 g, 102.9 mmol) was dissolved in water (43 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 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 18.2 g of compound subH-4. (Yield 61%, MS: [M+H] ⁺ = 582)

In a nitrogen atmosphere, compound subH-4 (10 g, 17.2 mmol), compound amine 4 (4.4 g, 18 mmol), and sodium tert-butoxide (2.1 g, 22.3 mmol) were added to xylene (200 ml), stirred and refluxed. did. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. When the reaction was completed after 5 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.1 g of compound 2-5. (Yield 52%, MS: [M+H] ⁺ = 791)

Production Example 2-6

In a nitrogen atmosphere, compound H (15 g, 51.4 mmol) and compound sub11 (15 g, 52 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (14.2 g, 102.9 mmol) was dissolved in water (43 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 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 14.5 g of compound subH-5. (Yield 62%, MS: [M+H] ⁺ = 456)

In a nitrogen atmosphere, compound subH-5 (10 g, 21.9 mmol), compound amine 5 (6 g, 23 mmol), and sodium tert-butoxide (2.7 g, 28.5 mmol) were added to xylene (200 ml), stirred and refluxed. did. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. When the reaction was completed after 5 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 8 g of compound 2-6. (Yield 54%, MS: [M+H] ⁺ = 679)

Production Example 2-7

In a nitrogen atmosphere, compound subH-5 (10 g, 21.9 mmol), compound amine 6 (8.1 g, 23 mmol), and sodium tert-butoxide (2.7 g, 28.5 mmol) were added to xylene (200 ml), stirred and refluxed. did. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. When the reaction was completed after 5 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.6 g of Compound 2-7. (Yield 63%, MS: [M+H] ⁺ = 772)

Production Example 2-8

In a nitrogen atmosphere, compound subH-5 (10 g, 21.9 mmol), compound amine 7 (7.7 g, 23 mmol), and sodium tert-butoxide (2.7 g, 28.5 mmol) were added to xylene (200 ml), stirred and refluxed. did. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. When the reaction was completed after 5 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 8.3 g of compound 2-8. (Yield 50%, MS: [M+H] ⁺ = 755)

Production Example 2-9

In a nitrogen atmosphere, compound subH-1 (10 g, 18.8 mmol), compound amine 8 (5.1 g, 19.7 mmol), and sodium tert-butoxide (2.3 g, 24.4 mmol) were added to xylene (200 ml), stirred and refluxed. did. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. When the reaction was completed after 5 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.7 g of compound 2-9. (Yield 54%, MS: [M+H] ⁺ = 755)

Preparation Example 2-10

In a nitrogen atmosphere, compound H (15 g, 51.4 mmol) and compound sub12 (19 g, 52 mmol) were added to THF (300 ml) and stirred and refluxed. Thereafter, potassium carbonate (14.2 g, 102.9 mmol) was dissolved in water (43 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 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 20.8 g of compound subH-6. (Yield 76%, MS: [M+H] ⁺ = 532)

In a nitrogen atmosphere, compound subH-6 (10 g, 18.8 mmol), compound amine 9 (6.6 g, 19.7 mmol), and sodium tert-butoxide (2.3 g, 24.4 mmol) were added to xylene (200 ml), stirred and refluxed. did. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. When the reaction was completed after 5 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.8 g of Compound 2-10. (Yield 69%, MS: [M+H] ⁺ = 830)

Preparation Example 2-11

In a nitrogen atmosphere, compound subH-5 (10 g, 21.9 mmol), compound amine 10 (7.7 g, 23 mmol), and sodium tert-butoxide (2.7 g, 28.5 mmol) were added to xylene (200 ml), stirred and refluxed. did. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. When the reaction was completed after 5 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.1 g of Compound 2-11. (Yield 61%, MS: [M+H] ⁺ = 754)

Preparation Example 2-12

In a nitrogen atmosphere, compound H (15 g, 51.4 mmol) and compound sub13 (41.3 g, 113.2 mmol) were added to THF (300 ml) and stirred and refluxed. After dissolving potassium carbonate (35.6 g, 257.2 mmol) in water (107 ml), it was added, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1 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 31.5 g of compound 2-12. (Yield 75%, MS: [M+H] ⁺ = 817)

Preparation Example 2-13

In a nitrogen atmosphere, compound subH-5 (15 g, 28.2 mmol) and compound sub9 (10.5 g, 31 mmol) were added to THF (300 ml) and stirred and refluxed. Thereafter, potassium carbonate (11.7 g, 84.6 mmol) was dissolved in water (35 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.3 g of compound 2-13. (Yield 73%, MS: [M+H] ⁺ = 791)

Production Example 2-14

In a nitrogen atmosphere, compound H (15 g, 51.4 mmol) and compound sub11 (32.7 g, 113.2 mmol) were added to THF (300 ml) and stirred and refluxed. After dissolving potassium carbonate (35.6 g, 257.2 mmol) in water (107 ml), it was added, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1 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 24.3 g of compound 2-14. (Yield 71%, MS: [M+H] ⁺ = 665)

Preparation Example 2-15

In a nitrogen atmosphere, compound H (15 g, 51.4 mmol) and compound sub14 (42.9 g, 113.2 mmol) were added to THF (300 ml) and stirred and refluxed. After dissolving potassium carbonate (35.6 g, 257.2 mmol) in water (107 ml), it was added, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1 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 34.7 g of compound 2-15. (Yield 80%, MS: [M+H] ⁺ = 845)

Preparation Example 2-16

In a nitrogen atmosphere, compound H (15 g, 51.4 mmol) and compound sub14 (19.7 g, 52 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (14.2 g, 102.9 mmol) was dissolved in water (43 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 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 21.6 g of compound subH-7. (Yield 77%, MS: [M+H] ⁺ = 546)

In a nitrogen atmosphere, compound subH-7 (15 g, 27.5 mmol) and compound sub15 (11.9 g, 30.2 mmol) were added to THF (300 ml), stirred and refluxed. After dissolving potassium carbonate (11.4 g, 82.4 mmol) in water (34 ml), it was added, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.4 g of compound 2-16. (Yield 65%, MS: [M+H] ⁺ = 861)

Preparation Example 2-17

In a nitrogen atmosphere, compound H (10 g, 34.3 mmol), compound amine 2 (17.7 g, 72 mmol), and sodium tert-butoxide (8.2 g, 85.7 mmol) were added to xylene (200 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added. When the reaction was completed after 5 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.9 g of compound 2-17. (Yield 70%, MS: [M+H] ⁺ = 665)

Preparation Example 2-18

In a nitrogen atmosphere, compound H (10 g, 34.3 mmol), compound amine 1 (5.8 g, 34.3 mmol), and sodium tert-butoxide (3.6 g, 37.7 mmol) were added to xylene (200 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. When the reaction was completed after 5 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 8.3 g of compound subH-8. (Yield 64%, MS: [M+H] ⁺ = 380)

In a nitrogen atmosphere, compound subH-8 (10 g, 26.3 mmol), compound amine 11 (8.2 g, 27.6 mmol), and sodium tert-butoxide (3.3 g, 34.2 mmol) were added to xylene (200 ml), stirred and refluxed. did. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. When the reaction was completed after 5 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9.4 g of compound 2-18. (Yield 56%, MS: [M+H] ⁺ = 639)

Preparation Example 2-19

In a nitrogen atmosphere, compound subH-8 (10 g, 26.3 mmol), compound amine 12 (9.5 g, 27.6 mmol), and sodium tert-butoxide (3.3 g, 34.2 mmol) were added to xylene (200 ml), stirred and refluxed. did. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. When the reaction was completed after 5 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9.1 g of compound 2-19. (Yield 50%, MS: [M+H] ⁺ = 689)

Preparation Example 2-20

In a nitrogen atmosphere, compound H (10 g, 34.3 mmol), compound amine 2 (8.4 g, 34.3 mmol), and sodium tert-butoxide (3.6 g, 37.7 mmol) were added to xylene (200 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. When the reaction was completed after 5 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9.5 g of compound subH-9. (Yield 61%, MS: [M+H] ⁺ = 456)

In a nitrogen atmosphere, compound subH-9 (10 g, 22 mmol), compound amine 13 (6.4 g, 23.1 mmol), and sodium tert-butoxide (2.7 g, 28.6 mmol) were added to xylene (200 ml), stirred and refluxed. did. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. When the reaction was completed after 5 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.6 g of compound 2-20. (Yield 50%, MS: [M+H] ⁺ = 695)

Preparation Example 2-21

In a nitrogen atmosphere, compound H (10 g, 34.3 mmol), compound amine 14 (18.7 g, 72 mmol), and sodium tert-butoxide (8.2 g, 85.7 mmol) were added to xylene (200 ml), stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added. When the reaction was completed after 5 hours, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.2 g of compound 2-21. (Yield 60%, MS: [M+H] ⁺ = 693)

[Example]

Example 1

A glass substrate coated with indium tin oxide (ITO) to a thickness of 1,000 Å was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, a 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, it was repeated twice with distilled water and ultrasonic cleaning was performed 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 on the hole injection layer by vacuum depositing the following HT-1 compound. Subsequently, an electron blocking layer was formed by vacuum depositing the following EB-1 compound to a film thickness of 150 Å on the hole transport layer. Then, on the EB-1 deposited film, the previously prepared compound 1-2, compound 2-2 (above, host) and the following Dp-7 compound (red dopant) were vacuum co-evaporated at a weight ratio of 49:49:2 A red light emitting layer having a thickness of 400 Å was formed. A hole blocking layer was formed on the light emitting layer by vacuum depositing the following HB-1 compound to a film 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. 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 negative electrode was 0.3 Å/sec, and the deposition rate of aluminum was 2 Å/sec, and the vacuum level during deposition was 2×10 Maintaining ^-7 to 5×10 ^-6 torr, an organic light emitting device was fabricated.

Examples 2 to 102

An organic light emitting device was manufactured in the same manner as in Example 1, but using the compounds listed in Tables 1 to 4 instead of Compounds 1-2 and 2-2.

Comparative Examples 1 to 124

An organic light emitting device was prepared in the same manner as in Example 1, but using the compounds listed in Tables 5 to 8 instead of Compounds 1-2 and 2-2. The compounds listed in Tables 5 to 8 are as follows.

When current was applied to the organic light emitting devices prepared in Examples 1 to 102 and Comparative Examples 1 to 124, voltage and efficiency were measured (15 mA/cm ² standard), and the results are shown in Tables 1 to 8 below. The lifetime T95 means the time required for the luminance to decrease from the initial luminance (6,000 nit) to 95%.

1st host 2nd host Driving voltage (V) Efficiency (cd/A) Lifetime T95(hr) luminescent color Example 1 compound 1-2 compound 2-2 3.58 20.7 247 Red Example 2 Compounds 2-5 3.64 21.3 250 Red Example 3 compounds 2-9 3.60 21.0 218 Red Example 4 compound 2-11 3.63 20.8 223 Red Example 5 Compounds 2-14 3.65 20.6 235 Red Example 6 compounds 2-19 3.61 21.5 229 Red Example 7 Compounds 1-3 compound 2-3 3.76 20.5 208 Red Example 8 Compounds 2-4 3.82 19.4 211 Red Example 9 Compounds 2-7 3.79 19.6 203 Red Example 10 Compounds 2-10 3.78 19.1 216 Red Example 11 Compounds 2-16 3.82 20.3 220 Red Example 12 compound 2-21 3.74 20.0 205 Red Example 13 Compounds 1-4 compound 2-2 3.53 19.3 253 Red Example 14 Compounds 2-5 3.60 19.7 240 Red Example 15 compounds 2-9 3.54 19.0 257 Red Example 16 compound 2-11 3.69 18.6 241 Red Example 17 Compounds 2-14 3.56 19.2 235 Red Example 18 compounds 2-19 3.55 19.5 254 Red Example 19 Compounds 1-8 compound 2-3 3.79 19.3 198 Red Example 20 Compounds 2-4 3.72 20.2 191 Red Example 21 Compounds 2-7 3.84 20.7 202 Red Example 22 Compounds 2-10 3.80 19.8 207 Red Example 23 Compounds 2-16 3.77 20.6 195 Red Example 24 compound 2-21 3.81 20.2 204 Red Example 25 compounds 1-9 compound 2-2 3.56 22.2 263 Red Example 26 Compounds 2-5 3.60 21.9 251 Red Example 27 compounds 2-9 3.64 22.0 277 Red Example 28 compound 2-11 3.59 21.8 258 Red Example 29 Compounds 2-14 3.54 21.5 270 Red Example 30 compounds 2-19 3.51 21.4 262 Red

1st host 2nd host Driving voltage (V) Efficiency (cd/A) Lifetime T95(hr) luminescent color Example 31 compounds 1-10 compound 2-3 3.75 18.4 183 Red Example 32 Compounds 2-4 3.81 18.6 195 Red Example 33 Compounds 2-7 3.82 18.7 199 Red Example 34 Compounds 2-10 3.88 19.0 204 Red Example 35 Compounds 2-16 3.83 18.9 192 Red Example 36 compound 2-21 3.87 18.3 202 Red Example 37 Compounds 1-13 compound 2-2 3.68 20.3 251 Red Example 38 Compounds 2-5 3.62 20.0 245 Red Example 39 compounds 2-9 3.55 20.5 253 Red Example 40 compound 2-11 3.50 20.1 257 Red Example 41 Compounds 2-14 3.53 19.8 245 Red Example 42 compounds 2-19 3.51 20.7 261 Red Example 43 compounds 1-15 compound 2-3 3.68 22.3 231 Red Example 44 Compounds 2-4 3.65 22.0 227 Red Example 45 Compounds 2-7 3.60 21.3 218 Red Example 46 Compounds 2-10 3.59 22.7 240 Red Example 47 Compounds 2-16 3.61 21.8 224 Red Example 48 compound 2-21 3.59 22.4 235 Red Example 49 compounds 1-16 compound 2-2 3.78 19.7 197 Red Example 50 Compounds 2-5 3.74 20.8 188 Red Example 51 compounds 2-9 3.78 19.3 205 Red Example 52 compound 2-11 3.82 19.5 190 Red Example 53 Compounds 2-14 3.76 20.2 198 Red Example 54 compounds 2-19 3.73 19.7 201 Red Example 55 Compounds 1-17 compound 2-3 3.66 19.3 223 Red Example 56 compound 2-4 3.62 19.8 232 Red Example 57 Compounds 2-7 3.66 18.1 217 Red Example 58 Compounds 2-10 3.73 19.5 208 Red Example 59 Compounds 2-16 3.61 18.7 225 Red Example 60 compound 2-21 3.62 18.9 214 Red

1st host 2nd host Driving voltage (V) Efficiency (cd/A) Lifetime T95(hr) luminescent color Example 61 Compounds 1-20 compound 2-2 3.89 20.1 173 Red Example 62 Compounds 2-5 3.87 20.3 185 Red Example 63 compounds 2-9 3.88 20.2 191 Red Example 64 compound 2-11 3.86 19.5 187 Red Example 65 Compounds 2-14 3.86 20.4 170 Red Example 66 compounds 2-19 3.92 19.8 183 Red Example 67 compound 1-21 compound 2-3 3.90 20.9 194 Red Example 68 Compounds 2-4 3.91 20.5 181 Red Example 69 Compounds 2-7 3.97 19.9 176 Red Example 70 Compounds 2-10 3.96 20.6 184 Red Example 71 Compounds 2-16 3.93 20.4 175 Red Example 72 compound 2-21 3.91 19.7 190 Red Example 73 Compounds 1-23 compound 2-2 3.86 19.9 191 Red Example 74 Compounds 2-5 3.88 20.3 206 Red Example 75 compounds 2-9 3.84 20.1 200 Red Example 76 compound 2-11 3.89 20.6 198 Red Example 77 Compounds 2-14 3.82 20.4 185 Red Example 78 compounds 2-19 3.79 19.7 199 Red Example 79 Compound 1-25 compound 2-3 3.82 20.1 203 Red Example 80 Compounds 2-4 3.85 20.3 214 Red Example 81 Compounds 2-7 3.83 20.8 219 Red Example 82 Compounds 2-10 3.81 20.5 195 Red Example 83 Compounds 2-16 3.86 21.0 215 Red Example 84 compound 2-21 3.80 20.6 207 Red Example 85 compound 1-27 compound 2-2 3.96 19.6 213 Red Example 86 Compounds 2-5 3.93 19.3 203 Red Example 87 compounds 2-9 3.96 19.8 218 Red Example 88 compound 2-11 3.88 20.4 209 Red Example 89 Compounds 2-14 3.93 19.1 203 Red Example 90 compounds 2-19 3.91 19.5 214 Red

1st host 2nd host Driving voltage (V) Efficiency (cd/A) Lifetime T95(hr) luminescent color Example 91 compound 1-28 compound 2-3 3.73 19.3 188 Red Example 92 Compounds 2-4 3.70 20.0 207 Red Example 93 Compounds 2-7 3.82 20.6 203 Red Example 94 Compounds 2-10 3.78 19.7 184 Red Example 95 Compounds 2-16 3.76 20.0 197 Red Example 96 compound 2-21 3.81 19.5 202 Red Example 97 compound 1-30 compound 2-2 3.92 18.9 181 Red Example 98 Compounds 2-5 3.85 19.2 207 Red Example 99 compounds 2-9 3.91 19.6 192 Red Example 100 compound 2-11 3.87 18.7 193 Red Example 101 Compounds 2-14 3.93 18.5 201 Red Example 102 compounds 2-19 3.90 18.4 194 Red

1st host 2nd host Driving voltage (V) Efficiency (cd/A) Lifetime T95(hr) luminescent color Comparative Example 1 compound B-1 compound 2-1 4.25 14.5 84 Red Comparative Example 2 Compounds 2-5 4.24 14.7 82 Red Comparative Example 3 compound 2-11 4.39 14.0 86 Red Comparative Example 4 Compounds 2-13 4.31 14.8 71 Red Comparative Example 5 Compounds 2-17 4.32 15.1 84 Red Comparative Example 6 compound B-2 compound 2-3 4.17 16.0 137 Red Comparative Example 7 Compounds 2-7 4.13 15.5 122 Red Comparative Example 8 Compounds 2-12 4.02 16.3 134 Red Comparative Example 9 Compounds 2-16 4.10 15.7 130 Red Comparative Example 10 compound 2-20 4.12 15.4 13 Red Comparative Example 11 compound B-3 compound 2-1 4.43 14.4 73 Red Comparative Example 12 Compounds 2-5 4.41 13.7 78 Red Comparative Example 13 compound 2-11 4.36 13.9 84 Red Comparative Example 14 Compounds 2-13 4.39 13.4 80 Red Comparative Example 15 Compounds 2-17 4.40 13.6 79 Red Comparative Example 16 compound B-4 compound 2-3 4.14 16.6 122 Red Comparative Example 17 Compounds 2-7 4.27 15.3 14 Red Comparative Example 18 Compounds 2-12 4.23 15.1 118 Red Comparative Example 19 Compounds 2-16 4.30 13.5 122 Red Comparative Example 20 compound 2-20 4.24 14.2 118 Red Comparative Example 21 Compound B-5 compound 2-1 4.30 13.7 104 Red Comparative Example 22 Compounds 2-5 4.32 14.2 121 Red Comparative Example 23 compound 2-11 4.35 14.4 114 Red Comparative Example 24 Compounds 2-13 4.29 14.5 120 Red Comparative Example 25 Compounds 2-17 4.27 13.8 108 Red Comparative Example 26 Compound B-6 compound 2-3 4.25 14.3 131 Red Comparative Example 27 Compounds 2-7 4.32 14.2 133 Red Comparative Example 28 Compounds 2-12 4.33 14.5 118 Red Comparative Example 29 Compounds 2-16 4.37 15.1 125 Red Comparative Example 30 compound 2-20 4.35 14.9 139 Red

1st host 2nd host Driving voltage (V) Efficiency (cd/A) Lifetime T95(hr) luminescent color Comparative Example 31 Compound B-7 compound 2-1 4.24 15.2 141 Red Comparative Example 32 Compounds 2-5 4.26 15.5 146 Red Comparative Example 33 compound 2-11 4.23 15.3 140 Red Comparative Example 34 Compounds 2-13 4.19 16.2 138 Red Comparative Example 35 Compounds 2-17 4.20 16.1 145 Red Comparative Example 36 Compound B-8 compound 2-3 4.30 15.0 105 Red Comparative Example 37 Compounds 2-7 4.34 14.3 114 Red Comparative Example 38 Compounds 2-12 4.39 14.5 108 Red Comparative Example 39 Compounds 2-16 4.41 13.9 112 Red Comparative Example 40 compound 2-20 4.38 14.7 101 Red Comparative Example 41 Compound B-9 compound 2-1 4.10 15.3 116 Red Comparative Example 42 Compounds 2-5 4.23 15.8 108 Red Comparative Example 43 compound 2-11 4.20 15.1 112 Red Comparative Example 44 Compounds 2-13 4.17 15.6 117 Red Comparative Example 45 Compounds 2-17 4.24 14.9 122 Red Comparative Example 46 Compound B-10 compound 2-3 4.14 14.4 121 Red Comparative Example 47 Compounds 2-7 4.17 14.7 124 Red Comparative Example 48 Compounds 2-12 4.19 14.5 118 Red Comparative Example 49 Compounds 2-16 4.14 15.3 113 Red Comparative Example 50 compound 2-20 4.22 15.8 120 Red Comparative Example 51 compound B-11 compound 2-1 4.24 14.9 110 Red Comparative Example 52 Compounds 2-5 4.23 14.6 115 Red Comparative Example 53 compound 2-11 4.30 15.1 119 Red Comparative Example 54 Compounds 2-13 4.21 15.0 101 Red Comparative Example 55 Compounds 2-17 4.20 15.3 118 Red Comparative Example 56 compound B-12 compound 2-3 4.28 14.1 100 Red Comparative Example 57 Compounds 2-7 4.31 13.9 97 Red Comparative Example 58 Compounds 2-12 4.26 14.5 101 Red Comparative Example 59 Compounds 2-16 4.32 14.2 94 Red Comparative Example 60 compound 2-20 4.24 13.7 105 Red

1st host 2nd host Driving voltage (V) Efficiency (cd/A) Lifetime T95(hr) luminescent color Comparative Example 61 compound 1-2 compound C-1 4.18 14.3 145 Red Comparative Example 62 Compounds 1-4 4.26 15.1 134 Red Comparative Example 63 Compounds 1-8 4.20 14.7 150 Red Comparative Example 64 Compounds 1-13 4.12 14.0 145 Red Comparative Example 65 compounds 1-16 4.17 16.9 134 Red Comparative Example 66 compound 1-21 4.24 15.1 142 Red Comparative Example 67 compound 1-25 4.22 15.8 137 Red Comparative Example 68 compound 1-28 4.22 15.6 138 Red Comparative Example 69 Compounds 1-3 compound C-2 4.31 15.0 105 Red Comparative Example 70 Compounds 1-8 4.36 16.8 94 Red Comparative Example 71 compounds 1-9 4.27 15.3 100 Red Comparative Example 72 compounds 1-15 4.35 16.9 89 Red Comparative Example 73 compounds 1-19 4.26 14.7 95 Red Comparative Example 74 Compounds 1-20 4.33 16.3 72 Red Comparative Example 75 compound 1-27 4.30 15.8 98 Red Comparative Example 76 compound 1-30 4.38 14.6 96 Red Comparative Example 77 compound 1-2 compound C-3 4.30 14.0 114 Red Comparative Example 78 Compounds 1-4 4.36 14.8 115 Red Comparative Example 79 Compounds 1-8 4.30 16.3 123 Red Comparative Example 80 Compounds 1-13 4.23 14.9 110 Red Comparative Example 81 Compounds 1-17 4.31 14.7 121 Red Comparative Example 82 compound 1-21 4.29 16.0 113 Red Comparative Example 83 compound 1-25 4.32 15.4 109 Red Comparative Example 84 compound 1-28 4.41 14.1 111 Red Comparative Example 85 Compounds 1-3 compound C-4 4.37 13.0 89 Red Comparative Example 86 Compounds 1-8 4.34 13.9 72 Red Comparative Example 87 compounds 1-9 4.38 13.1 81 Red Comparative Example 88 compounds 1-15 4.41 12.8 93 Red Comparative Example 89 compounds 1-19 4.39 14.3 101 Red Comparative Example 90 Compounds 1-23 4.31 13.8 84 Red Comparative Example 91 compound 1-27 4.33 14.2 95 Red Comparative Example 92 compound 1-30 4.34 13.0 98 Red

1st host 2nd host Driving voltage (V) Efficiency (cd/A) Lifetime T95(hr) luminescent color Comparative Example 93 compound 1-2 compound C-5 4.21 14.1 104 Red Comparative Example 94 Compounds 1-4 4.10 14.4 109 Red Comparative Example 95 Compounds 1-8 4.25 15.5 111 Red Comparative Example 96 Compounds 1-13 4.13 14.7 104 Red Comparative Example 97 compounds 1-16 4.11 14.6 105 Red Comparative Example 98 compound 1-21 4.19 15.5 111 Red Comparative Example 99 compound 1-25 4.12 14.8 107 Red Comparative Example 100 compound 1-28 4.20 15.3 113 Red Comparative Example 101 Compounds 1-3 compound C-6 4.15 19.2 122 Red Comparative Example 102 Compounds 1-8 4.13 18.4 119 Red Comparative Example 103 compounds 1-9 4.21 16.9 124 Red Comparative Example 104 compounds 1-15 4.18 15.2 127 Red Comparative Example 105 compounds 1-19 4.12 14.1 119 Red Comparative Example 106 Compounds 1-20 4.17 15.7 130 Red Comparative Example 107 compound 1-27 4.20 16.2 124 Red Comparative Example 108 compound 1-30 4.19 14.5 132 Red Comparative Example 109 compound 1-2 compound C-7 4.29 15.6 129 Red Comparative Example 110 Compounds 1-4 4.23 15.1 111 Red Comparative Example 111 Compounds 1-8 4.27 17.5 124 Red Comparative Example 112 Compounds 1-13 4.28 16.8 130 Red Comparative Example 113 Compounds 1-17 4.20 14.9 127 Red Comparative Example 114 compound 1-21 4.29 15.3 123 Red Comparative Example 115 compound 1-25 4.30 16.8 129 Red Comparative Example 116 compound 1-28 4.27 16.2 113 Red Comparative Example 117 Compounds 1-3 compound C-8 4.59 13.0 61 Red Comparative Example 118 Compounds 1-8 4.60 12.8 45 Red Comparative Example 119 compounds 1-9 4.51 13.7 59 Red Comparative Example 120 compounds 1-15 4.46 12.9 36 Red Comparative Example 121 compounds 1-19 4.51 11.3 48 Red Comparative Example 122 Compounds 1-23 4.47 12.4 32 Red Comparative Example 123 compound 1-27 4.59 13.8 44 Red Comparative Example 124 compound 1-30 4.55 15.6 61 Red

According to the present invention, when the compound of Formula 1 and the compound of Formula 2 were co-deposited and used as a red light emitting layer, it was confirmed that the driving voltage decreased and the efficiency and lifespan increased compared to the comparative examples as shown in Tables 1 to 4. In addition, as shown in Tables 5 and 6, when the compounds B-1 to B-12 as comparative examples and the compound of Formula 2 of the present invention are co-deposited and used as a red light emitting layer, the driving voltage is generally higher than that of the combination according to the present invention. and the efficiency and lifespan decreased. In addition, as shown in Tables 7 and 8, when the compounds C-1 to C-12, which are comparative examples, and the compound of Formula 1 of the present invention are co-deposited and used as a red light emitting layer, the driving voltage is higher and the efficiency is higher than that of the combination according to the present invention. and decreased lifespan.

From this, the combination of the compound of Formula 1 as the first host and the compound of Formula 2 as the second host of the present invention achieves good energy transfer to the red dopant in the red light emitting layer, thereby improving voltage and improving efficiency and lifetime. rise can be seen. This confirms that the combination of the compound of Formula 1 and the compound of Formula 2 of the present invention, rather than the combination with the comparative compound, increases efficiency and lifespan by forming excitons by combining electrons and holes through a more stable balance in the light emitting layer. could Therefore, it can be seen that the driving voltage, luminous efficiency and lifetime characteristics of the organic light emitting device can be improved when the compound of Formula 1 and the compound of Formula 2 of the present invention are combined and co-evaporated and 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: electron transport layer 8: electron injection layer

Claims (10)

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

In Formula 1,
L ₁ is a single bond; or a substituted or unsubstituted C _6-60 arylene;
L ₂ and L ₃ are single bonds;
Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, triphenylenyl, naphthylphenyl, phenylnaphthyl, dimethylfluorenyl, dibenzofuranyl, dibenzo thiophenyl, carbazol-9-yl, or 9-phenyl-9H-carbazolyl;
Ar ₁ and Ar ₂ are each independently unsubstituted or substituted with one or more deuterium groups;
R is hydrogen, deuterium, dibenzofuranyl, dibenzothiophenyl, or substituted or unsubstituted C _6-60 aryl;
[Formula 2]

In Formula 2,
L ₄ and L ₅ are each independently a single bond; or a substituted or unsubstituted C _6-60 arylene;
Ar ₃ to Ar ₆ are each independently substituted or unsubstituted C _6-60 aryl; Or a C _5-60 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O and S.
According to claim 1,
L ₁ is a single bond, phenylene, or naphthylene;
organic light emitting device.
According to claim 1,
L ₁ is a single bond; , or person,
organic light emitting device.
delete delete According to claim 1,
R is hydrogen, deuterium, phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, dibenzofuranyl, or dibenzothiophenyl;
organic light emitting device.
According to claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of
Organic Light-Emitting Elements:

According to claim 1,
L ₄ and L ₅ are each independently a single bond; or phenylene,
organic light emitting device.
According to claim 1,
Ar ₃ to Ar ₆ are each independently phenyl, biphenylyl, naphthyl, phenylnaphthyl, naphthylphenyl, dimethylfluorenyl, dibenzofuranyl, (dibenzofuranyl)phenyl, dibenzothiophenyl, or (dibenzothiophenyl)phenylin,
organic light emitting device.
According to claim 1,
The compound represented by Formula 2 is any one selected from the group consisting of
Organic Light-Emitting Elements: