KR20230069848A - Novel compound and organic light emitting device comprising the same - Google Patents

Abstract

The present invention provides a novel compound and an organic light emitting device using the same. The present invention provides a compound represented by chemical formula 1. The compound represented by chemical formula 1 can be used as a material for an organic layer of the organic light emitting device, and thus can improve efficiency, lower driving voltage, and/or improve lifespan characteristics of the organic light emitting device.

Description

Novel compound and organic light emitting device using the same

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

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

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

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

Korean Patent Publication No. 10-2000-0051826

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

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

[Formula 1]

In Formula 1,

One of X ₁ to X ₁₀ is N, the other is C substituted with a substituent represented by Formula 2 below, and the others are CR ₁ ;

R ₁ is each independently hydrogen or deuterium;

[Formula 2]

In Formula 2,

Y is each independently N or CR ₂ , provided that at least one of Y is N;

R ₂ are each independently hydrogen or deuterium;

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

L ₁ and L ₂ 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 substituted or unsubstituted C _2-60 heteroaryl containing at least one selected from the group consisting of N, O and S; ego,

However, when X ₅ or X ₆ is N, one of X ₁ to X ₄ and X ₇ to X ₁₀ is C substituted with the substituent of Formula 2,

When one of X ₇ to X ₁₀ is N, one of X ₁ to X ₆ is C substituted with the substituent of Formula 2 above.

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

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

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

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

또는

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

or

means a bond connected to another substituent.

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

In the present specification, the number of carbon atoms of the carbonyl group is not particularly limited, but is preferably 1 to 40 carbon atoms. Specifically, it may be a substituent 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 substituent 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 substituent 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 this specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.

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

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

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

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

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

etc. However, it is not limited thereto.

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

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

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

Preferably, Y is all N.

Preferably, Formula 1 is represented by any one of Formulas 1-1 to 1-10 below:

In Formula 1-1, one of X ₂ to X ₁₀ is C substituted with a substituent of Formula 2, and the others are each independently CH or CD,

In Formula 1-2, one of X ₁ and X ₃ to X ₁₀ is C substituted with a substituent of Formula 2, and the others are each independently CH or CD,

In Formula 1-3, one of X ₁ , X ₂ and X ₄ to X ₁₀ is C substituted with a substituent of Formula 2, and the others are each independently CH or CD,

In Formula 1-4, one of X ₁ to X ₃ and X ₅ to X ₁₀ is C substituted with a substituent of Formula 2, and the others are each independently CH or CD,

In Formula 1-5, one of X ₁ to X ₄ and X ₇ to X ₁₀ is C substituted with a substituent of Formula 2, the others are each independently CH or CD, X ₆ is CH or CD,

In Formula 1-6, one of X ₁ to X ₄ and X ₇ to X ₁₀ is C substituted with a substituent of Formula 2, the others are each independently CH or CD, X ₅ is CH or CD,

In Formula 1-7, one of X ₁ to X ₆ is C substituted with a substituent of Formula 2, the others are each independently CH or CD, and X ₈ to X ₁₀ are each independently CH or CD,

In Formula 1-8, one of X ₁ to X ₆ is C substituted with a substituent of Formula 2, the others are each independently CH or CD, and X ₇ , X ₉ and X ₁₀ are each independently CH or is a CD,

In Formula 1-9, one of X ₁ to X ₆ is C substituted with a substituent of Formula 2, the others are each independently CH or CD, and X ₇ , X ₈ and X ₁₀ are each independently CH or is a CD,

In Formula 1-10, one of X ₁ to X ₆ is C substituted with a substituent of Formula 2, the others are each independently CH or CD, and X ₇ to X ₉ are each independently CH or CD.

Preferably, L is a single bond, unsubstituted or substituted with one or more deuterium phenylene, or unsubstituted or substituted with one or more deuterium naphthylene. More preferably, L is a single bond, 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, 1,4-naphthylene, 1,3-naphthylene, 1,5-naphthylene ethylene, or 1,6-naphthylene, where L may be substituted with at least one deuterium.

Preferably, L ₁ and L ₂ are each independently a single bond, unsubstituted or substituted with one or more deuterium phenylene, or unsubstituted or one or more deuterium substituted naphthylene. More preferably, L ₁ and L ₂ are each independently a single bond, 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, 1,4-naphthylene, 1,3-naphthylene ethylene, 1,5-naphthylene, or 1,6-naphthylene, wherein L may be substituted with at least one deuterium.

Preferably, Ar ₁ and Ar ₂ are each independently selected from phenyl, biphenylyl, terphenylyl, naphthyl, (phenyl)naphthyl, (naphthyl)phenyl, phenanthrenyl, benzophenanthrenyl, dibenzofuran Ranyl, dibenzothiophenyl, carbazol-9-yl, or 9-phenyl-carbazolyl, wherein Ar ₁ and Ar ₂ are each independently unsubstituted or substituted with at least one deuterium. Meanwhile, the benzophenanthrenyl includes benzo[a]phenanthrenyl, benzo[b]phenanthrenyl, or benzo[c]phenanthrenyl.

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

Among the compounds represented by Formula 1, when X ₁ is N, X ₂ is C substituted with a substituent represented by Formula 2, and the others are CR ₁ , for example, it can be prepared by a manufacturing method as shown in Scheme 1 below. and other compounds can be similarly prepared.

[Scheme 1]

In Scheme 1, everything except Z is as defined above, and Z is halogen, preferably bromo or chloro.

The reaction is preferably carried out in the presence of a palladium catalyst and a base, and the reactor for the reaction can be changed as known in the art. The manufacturing method may be more specific in Preparation Examples to be described later.

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

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

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

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

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

In addition, the organic material layer may include a light emitting layer and an electron transport layer, and the electron transport layer may include the compound represented by Chemical Formula 1.

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

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

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

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

For example, the organic light emitting device according to the present invention may be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate. At this time, by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation, depositing a metal or a metal oxide having conductivity or an alloy thereof on the substrate to form an anode After forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer thereon, and depositing a material that can be used as a cathode thereon, it can be prepared. In addition to this method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

In addition, the compound represented by Chemical Formula 1 may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light emitting device. Here, the solution coating method means spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, etc., but is not limited to these.

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

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

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

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

The hole injection layer is a layer for injecting holes from the electrode, and the hole injection material has the ability to transport holes and has a hole injection effect at the anode, an excellent hole injection effect for the light emitting layer or the light emitting material, and generated in the light emitting layer A compound that prevents migration of excitons to the electron injecting layer or electron injecting material and has excellent thin film formation ability is preferred. It is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injection material include metal porphyrins, oligothiophenes, arylamine-based organic materials, hexanitrilehexaazatriphenylene-based organic materials, quinacridone-based organic materials, and perylene-based organic materials. of organic materials, anthraquinone, polyaniline, and polythiophene-based conductive polymers, but are not limited thereto.

The hole transport layer is a layer that receives holes from the hole injection layer and transports the holes to the light emitting layer. As a hole transport material, a material capable of receiving holes from the anode or the hole injection layer and transferring them to the light emitting layer is a material having high hole mobility. this is suitable Specific examples include, but are not limited to, arylamine-based organic materials, conductive polymers, and block copolymers having both conjugated and non-conjugated parts.

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

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

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

The electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer. As the electron transport material, a material capable of receiving electrons from the cathode and transferring them to the light emitting layer is suitable. do. Specific examples include Al complexes of 8-hydroxyquinoline; complexes including Alq ₃ ; organic radical compounds; hydroxyflavone-metal complexes and the like, but are not limited thereto. The electron transport layer can be used with any desired cathode material as used according to the prior art. In particular, examples of suitable cathode materials are conventional materials having a low work function followed by a layer of aluminum or silver. Specifically cesium, barium, calcium, ytterbium and samarium, followed in each case by a layer of aluminum or silver.

The electron injection layer is a layer for injecting electrons from an electrode, has the ability to transport electrons, has an excellent electron injection effect from a cathode, an excellent electron injection effect for a light emitting layer or a light emitting material, and injects holes of excitons generated in the light emitting layer. A compound that prevents migration to a layer and has excellent thin film forming ability is preferred. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preonylidene methane, anthrone, etc. and their derivatives, metals complex compounds and nitrogen-containing 5-membered ring derivatives, but are not limited thereto.

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

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

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

[Example]

Preparation Example 1

5-bromo-2-chloropyridin-4-amine (15g, 72.3mmol) and (2-methoxynaphthalen-1-yl)boronic acid (15.3g, 75.9mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (30g, 216.9mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.4g, 0.7mmol) was added. After reacting for 5 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 A-1-1_P1. (Yield 68%, MS: [M+H] ⁺ = 285)

Compound A-1-1_P1 (15g, 52.7mmol) and HBF ₄ (9.3g, 105.4mmol) were added to 150ml of Acetonitrile and stirred. After that, NaNO ₂ (14.6g, 105.4mmol) was dissolved in 30ml of water and added slowly at 0 ^o C. After reacting for 8 hours, the temperature was raised to room temperature, and diluted with 300 ml of water. After dissolving in chloroform and washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 6.9 g of compound A-1-1_P2. (Yield 52%, MS: [M+H] ⁺ = 254)

Compound A-1-1_P2 (15g, 59.1mmol) and bis(pinacolato)diboron (16.5g, 65mmol) were stirred while refluxing in 300ml of 1,4-dioxane. After that, potassium acetate (8.7g, 88.7mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (1g, 1.8mmol) and tricyclohexylphosphine (1g, 3.5mmol) were added. After reacting for 10 hours, cooling to room temperature and separating the organic layer using chloroform and water, 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 12.9 g of Compound A-1-1. (Yield 63%, MS: [M+H] ⁺ = 346)

Preparation Example 2

3-bromopyridin-4-amine (15g, 86.7mmol) and (6-chloro-2-methoxynaphthalen-1-yl)boronic acid (21.3g, 91mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (35.9g, 260.1mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.4g, 0.9mmol) was added. After reacting for 4 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 17.5 g of compound A-1-6_P1. (Yield 71%, MS: [M+H] ⁺ = 285)

Compound A-1-6_P1 (15g, 52.7mmol) and HBF ₄ (9.3g, 105.4mmol) were added to 150ml of Acetonitrile and stirred. After that, NaNO ₂ (14.6g, 105.4mmol) was dissolved in 30ml of water and added slowly at 0 ^o C. After reacting for 10 hours, the temperature was raised to room temperature, and diluted with 300 ml of water. After dissolving in chloroform and washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 7.3 g of compound A-1-6_P2. (Yield 55%, MS: [M+H] ⁺ = 254)

Compound A-1-6_P2 (15g, 59.1mmol) and bis(pinacolato)diboron (16.5g, 65mmol) were stirred while refluxing in 300ml of 1,4-dioxane. After that, potassium acetate (8.7g, 88.7mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (1g, 1.8mmol) and tricyclohexylphosphine (1g, 3.5mmol) were added. After reacting for 8 hours, cooling to room temperature and separating the organic layer using chloroform and water, 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 A-1-6. (Yield 71%, MS: [M+H] ⁺ = 346)

Preparation Example 3

4-bromopyridin-3-amine (15g, 86.7mmol) and (7-chloro-2-methoxynaphthalen-1-yl)boronic acid (21.3g, 91mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (35.9g, 260.1mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.4g, 0.9mmol) was added. After reacting for 4 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 16.3 g of compound A-2-7_P1. (Yield 66%, MS: [M+H] ⁺ = 285)

Compound A-2-7_P1 (15g, 52.7mmol) and HBF ₄ (9.3g, 105.4mmol) were added to 150ml of Acetonitrile and stirred. After that, NaNO ₂ (14.6g, 105.4mmol) was dissolved in 30ml of water and added slowly at 0 ^o C. After reacting for 9 hours, the temperature was raised to room temperature, and diluted with 300 ml of water. After dissolving in chloroform and washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 7.3 g of compound A-2-7_P2. (Yield 55%, MS: [M+H] ⁺ = 254)

Compound A-2-7_P2 (15g, 59.1mmol) and bis(pinacolato)diboron (16.5g, 65mmol) were stirred while refluxing in 300ml of 1,4-dioxane. After that, potassium acetate (8.7g, 88.7mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (1g, 1.8mmol) and tricyclohexylphosphine (1g, 3.5mmol) were added. After reacting for 9 hours, cooling to room temperature and separating the organic layer using chloroform and water, 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 12.2 g of compound A-2-7. (Yield 60%, MS: [M+H] ⁺ = 346)

Production Example 4

3-bromo-5-chloropyridin-2-amine (15g, 73.7mmol) and (2-methoxynaphthalen-1-yl)boronic acid (15.6g, 77.4mmol) were added to 300ml of THF and stirred and refluxed. After that, potassium carbonate (30.6g, 221.2mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.4g, 0.7mmol) was added. After reacting for 3 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 15.5 g of compound A-3-1_P1. (Yield 74%, MS: [M+H] ⁺ = 285)

Compound A-3-1_P1 (15g, 52.7mmol) and HBF ₄ (9.3g, 105.4mmol) were added to 150ml of Acetonitrile and stirred. After that, NaNO ₂ (14.6g, 105.4mmol) was dissolved in 30ml of water and added slowly at 0 ^o C. After reacting for 8 hours, the temperature was raised to room temperature, and diluted with 300 ml of water. After dissolving in chloroform and washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 7.9 g of compound A-3-1_P2. (Yield 59%, MS: [M+H] ⁺ = 254)

Compound A-3-1_P2 (15g, 59.1mmol) and bis(pinacolato)diboron (16.5g, 65mmol) were stirred while refluxing in 300ml of 1,4-dioxane. After that, potassium acetate (8.7g, 88.7mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (1g, 1.8mmol) and tricyclohexylphosphine (1g, 3.5mmol) were added. After reacting for 6 hours, cooling to room temperature and separating the organic layer using chloroform and water, 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 13.3 g of Compound A-3-1. (Yield 65%, MS: [M+H] ⁺ = 346)

Preparation Example 5

3-bromopyridin-2-amine (15g, 86.7mmol) and (5-chloro-2-methoxynaphthalen-1-yl)boronic acid (21.5g, 91mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (35.9g, 260.1mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.4g, 0.9mmol) was added. After reacting for 4 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 17.7 g of compound A-3-5_P1. (Yield 72%, MS: [M+H] ⁺ = 285)

Compound A-3-5_P1 (15g, 52.7mmol) and HBF ₄ (9.3g, 105.4mmol) were added to 150ml of Acetonitrile and stirred. After that, NaNO ₂ (14.6g, 105.4mmol) was dissolved in 30ml of water and added slowly at 0 ^o C. After reacting for 9 hours, the temperature was raised to room temperature, and diluted with 300 ml of water. After dissolving in chloroform and washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 7.1 g of compound A-3-5_P2. (Yield 53%, MS: [M+H] ⁺ = 254)

Compound A-3-5_P2 (15g, 59.1mmol) and bis(pinacolato)diboron (16.5g, 65mmol) were stirred while refluxing in 300ml of 1,4-dioxane. After that, potassium acetate (8.7g, 88.7mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (1g, 1.8mmol) and tricyclohexylphosphine (1g, 3.5mmol) were added. After reacting for 7 hours, cooling to room temperature and separating the organic layer using chloroform and water, 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 A-3-5. (Yield 75%, MS: [M+H] ⁺ = 346)

Preparation Example 6

2-bromo-4-chloropyridin-3-amine (15g, 73.7mmol) and (2-methoxynaphthalen-1-yl)boronic acid (15.6g, 77.4mmol) were added to 300ml of THF and stirred and refluxed. After that, potassium carbonate (30.6g, 221.2mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.4g, 0.7mmol) was added. After reacting for 4 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 14.5 g of compound A-4-3_P1. (Yield 69%, MS: [M+H] ⁺ = 285)

Compound A-4-3_P1 (15g, 52.7mmol) and HBF ₄ (9.3g, 105.4mmol) were added to 150ml of Acetonitrile and stirred. After that, NaNO ₂ (14.6g, 105.4mmol) was dissolved in 30ml of water and added slowly at 0 ^o C. After reacting for 8 hours, the temperature was raised to room temperature, and diluted with 300 ml of water. After dissolving in chloroform and washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.2 g of compound A-4-3_P2. (Yield 69%, MS: [M+H] ⁺ = 254)

Compound A-4-3_P2 (15g, 59.1mmol) and bis(pinacolato)diboron (16.5g, 65mmol) were stirred while refluxing in 300ml of 1,4-dioxane. After that, potassium acetate (8.7g, 88.7mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (1g, 1.8mmol) and tricyclohexylphosphine (1g, 3.5mmol) were added. After reacting for 5 hours, cooling to room temperature and separating the organic layer using chloroform and water, 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 13.1 g of compound A-4-3. (Yield 64%, MS: [M+H] ⁺ = 346)

Preparation Example 7

2-bromo-6-chloroaniline (15g, 72.6mmol) and (3-methoxyisoquinolin-4-yl)boronic acid (15.5g, 76.3mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (30.1g, 217.9mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.4g, 0.7mmol) was added. After reacting for 3 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 13.8 g of compound A-5-3_P1. (Yield 67%, MS: [M+H] ⁺ = 285)

Compound A-5-3_P1 (15g, 52.7mmol) and HBF ₄ (9.3g, 105.4mmol) were added to 150ml of Acetonitrile and stirred. After that, NaNO ₂ (14.6g, 105.4mmol) was dissolved in 30ml of water and added slowly at 0 ^o C. After reacting for 10 hours, the temperature was raised to room temperature, and diluted with 300 ml of water. After dissolving in chloroform and washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.3 g of compound A-5-3_P2. (Yield 62%, MS: [M+H] ⁺ = 254)

Compound A-5-3_P2 (15g, 59.1mmol) and bis(pinacolato)diboron (16.5g, 65mmol) were stirred while refluxing in 300ml of 1,4-dioxane. After that, potassium acetate (8.7g, 88.7mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (1g, 1.8mmol) and tricyclohexylphosphine (1g, 3.5mmol) were added. After reacting for 7 hours, cooling to room temperature and separating the organic layer using chloroform and water, 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 14.9 g of compound A-5-3. (Yield 73%, MS: [M+H] ⁺ = 346)

Preparation Example 8

2-bromoaniline (15g, 87.2mmol) and (7-chloro-3-methoxyquinolin-4-yl)boronic acid (21.7g, 91.5mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (36.2g, 261.6mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.4g, 0.9mmol) was added. After reacting for 3 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 18.6 g of compound A-6-6_P1. (Yield 75%, MS: [M+H] ⁺ = 285)

Compound A-6-6_P1 (15g, 52.7mmol) and HBF ₄ (9.3g, 105.4mmol) were added to 150ml of Acetonitrile and stirred. After that, NaNO ₂ (14.6g, 105.4mmol) was dissolved in 30ml of water and added slowly at 0 ^o C. After reacting for 8 hours, the temperature was raised to room temperature, and diluted with 300 ml of water. After dissolving in chloroform and washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 7.7 g of compound A-6-6_P2. (Yield 58%, MS: [M+H] ⁺ = 254)

Compound A-6-6_P2 (15g, 59.1mmol) and bis(pinacolato)diboron (16.5g, 65mmol) were stirred while refluxing in 300ml of 1,4-dioxane. After that, potassium acetate (8.7g, 88.7mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (1g, 1.8mmol) and tricyclohexylphosphine (1g, 3.5mmol) were added. After reacting for 7 hours, cooling to room temperature and separating the organic layer using chloroform and water, 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 A-6-6. (Yield 75%, MS: [M+H] ⁺ = 346)

Preparation Example 9

2-bromoaniline (15g, 87.2mmol) and (7-chloro-6-methoxyquinolin-5-yl)boronic acid (21.7g, 91.5mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (36.2g, 261.6mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.4g, 0.9mmol) was added. After reacting for 5 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 18.1 g of compound A-7-4_P1. (Yield 73%, MS: [M+H] ⁺ = 285)

Compound A-7-4_P1 (15g, 52.7mmol) and HBF ₄ (9.3g, 105.4mmol) were added to 150ml of Acetonitrile and stirred. After that, NaNO ₂ (14.6g, 105.4mmol) was dissolved in 30ml of water and added slowly at 0 ^o C. After reacting for 10 hours, the temperature was raised to room temperature, and diluted with 300 ml of water. After dissolving in chloroform and washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 7.9 g of compound A-7-4_P2. (Yield 59%, MS: [M+H] ⁺ = 254)

Compound A-7-4_P2 (15g, 59.1mmol) and bis(pinacolato)diboron (16.5g, 65mmol) were stirred while refluxing in 300ml of 1,4-dioxane. After that, potassium acetate (8.7g, 88.7mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (1g, 1.8mmol) and tricyclohexylphosphine (1g, 3.5mmol) were added. After reacting for 8 hours, cooling to room temperature and separating the organic layer using chloroform and water, 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 13.1 g of Compound A-7-4. (Yield 64%, MS: [M+H] ⁺ = 346)

Preparation Example 10

2-bromo-5-chloroaniline (15g, 72.6mmol) and (6-methoxyisoquinolin-5-yl)boronic acid (15.5g, 76.3mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (30.1g, 217.9mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.4g, 0.7mmol) was added. After reacting for 2 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 13.6 g of compound A-8-2_P1. (Yield 66%, MS: [M+H] ⁺ = 285)

Compound A-8-2_P1 (15g, 52.7mmol) and HBF ₄ (9.3g, 105.4mmol) were added to 150ml of Acetonitrile and stirred. After that, NaNO ₂ (14.6g, 105.4mmol) was dissolved in 30ml of water and added slowly at 0 ^o C. After reacting for 8 hours, the temperature was raised to room temperature, and diluted with 300 ml of water. After dissolving in chloroform and washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.2 g of compound A-8-2_P2. (Yield 69%, MS: [M+H] ⁺ = 254)

Compound A-8-2_P2 (15g, 59.1mmol) and bis(pinacolato)diboron (16.5g, 65mmol) were stirred while refluxing in 300ml of 1,4-dioxane. After that, potassium acetate (8.7g, 88.7mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (1g, 1.8mmol) and tricyclohexylphosphine (1g, 3.5mmol) were added. After reacting for 6 hours, cooling to room temperature and separating the organic layer using chloroform and water, 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 A-8-2. (Yield 68%, MS: [M+H] ⁺ = 346)

Preparation Example 11

2-bromo-4-chloroaniline (15g, 72.6mmol) and (7-methoxyisoquinolin-8-yl)boronic acid (15.5g, 76.3mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (30.1g, 217.9mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.4g, 0.7mmol) was added. After reacting for 5 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 14.2 g of compound A-9-1_P1. (Yield 69%, MS: [M+H] ⁺ = 285)

Compound A-9-1_P1 (15g, 52.7mmol) and HBF ₄ (9.3g, 105.4mmol) were added to 150ml of Acetonitrile and stirred. After that, NaNO ₂ (14.6g, 105.4mmol) was dissolved in 30ml of water and added slowly at 0 ^o C. After reacting for 10 hours, the temperature was raised to room temperature, and diluted with 300 ml of water. After dissolving in chloroform and washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.9 g of compound A-9-1_P2. (Yield 74%, MS: [M+H] ⁺ = 254)

Compound A-9-1_P2 (15g, 59.1mmol) and bis(pinacolato)diboron (16.5g, 65mmol) were stirred while refluxing in 300ml of 1,4-dioxane. After that, potassium acetate (8.7g, 88.7mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (1g, 1.8mmol) and tricyclohexylphosphine (1g, 3.5mmol) were added. After reacting for 8 hours, cooling to room temperature and separating the organic layer using chloroform and water, 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 A-9-1. (Yield 71%, MS: [M+H] ⁺ = 346)

Preparation Example 12

2-bromoaniline (15g, 87.2mmol) and (5-chloro-7-methoxyquinolin-8-yl)boronic acid (21.7g, 91.5mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (36.2g, 261.6mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.4g, 0.9mmol) was added. After reacting for 4 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 18.1 g of compound A-10-5_P1. (Yield 73%, MS: [M+H] ⁺ = 285)

Compound A-10-5_P1 (15g, 52.7mmol) and HBF ₄ (9.3g, 105.4mmol) were added to 150ml of Acetonitrile and stirred. After that, NaNO ₂ (14.6g, 105.4mmol) was dissolved in 30ml of water and added slowly at 0 ^o C. After reacting for 8 hours, the temperature was raised to room temperature, and diluted with 300 ml of water. After dissolving in chloroform and washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.4 g of compound A-10-5_P2. (Yield 63%, MS: [M+H] ⁺ = 254)

Compound A-10-5_P2 (15g, 59.1mmol) and bis(pinacolato)diboron (16.5g, 65mmol) were stirred while refluxing in 300ml of 1,4-dioxane. After that, potassium acetate (8.7g, 88.7mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (1g, 1.8mmol) and tricyclohexylphosphine (1g, 3.5mmol) were added. After reacting for 9 hours, cooling to room temperature and separating the organic layer using chloroform and water, 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 14.1 g of compound A-10-5. (Yield 69%, MS: [M+H] ⁺ = 346)

Synthesis Example 1

Trz1 (15g, 41.9mmol) and compound A-3-2 (15.2g, 44mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (17.4g, 125.8mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 3 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 16.3 g of Compound 1. (Yield 72%, MS: [M+H] ⁺ = 541)

Synthesis Example 2

Trz2 (15g, 33.3mmol) and Compound A-3-1 (12.1g, 35mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (13.8g, 100mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 2 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 15.6 g of Compound 2. (Yield 74%, MS: [M+H] ⁺ = 633)

Synthesis Example 3

Trz3 (15g, 34.6mmol) and Compound A-3-1 (12.6g, 36.4mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.4g, 103.9mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 2 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 17.1 g of Compound 3. (Yield 80%, MS: [M+H] ⁺ = 616)

Synthesis Example 4

Trz4 (15g, 38.1mmol) and Compound A-3-1 (13.8g, 40mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (15.8g, 114.3mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 5 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 17.3 g of Compound 4. (Yield 79%, MS: [M+H] ⁺ = 577)

Synthesis Example 5

Trz5 (15g, 38.1mmol) and compound A-3-3 (13.8g, 40mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (15.8g, 114.3mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 4 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 15.8 g of Compound 5. (Yield 72%, MS: [M+H] ⁺ = 577)

Synthesis Example 6

Trz6 (15g, 43.6mmol) and compound A-3-3 (15.8g, 45.8mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (18.1g, 130.9mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 4 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 17.9 g of Compound 6. (Yield 78%, MS: [M+H] ⁺ = 527)

Synthesis Example 7

Trz7 (15g, 34.6mmol) and compound A-3-4 (12.6g, 36.4mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.4g, 103.9mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 4 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 17.1 g of Compound 7. (Yield 80%, MS: [M+H] ⁺ = 616)

Synthesis Example 8

Trz8 (15g, 35.9mmol) and compound A-3-4 (13g, 37.7mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.9g, 107.7mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 2 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 14.9 g of Compound 8. (Yield 69%, MS: [M+H] ⁺ = 601)

Synthesis Example 9

Trz9 (15g, 36.8mmol) and Compound A-3-5 (13.3g, 38.6mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (15.2g, 110.3mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 5 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 13.5 g of Compound 9. (Yield 62%, MS: [M+H] ⁺ = 591)

Synthesis Example 10

Trz10 (15g, 43.6mmol) and Compound A-3-5 (15.8g, 45.8mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.1g, 130.9mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 4 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 13.8 g of Compound 10. (Yield 60%, MS: [M+H] ⁺ = 527)

Synthesis Example 11

Trz11 (15g, 56mmol) and compound A-3-7 (20.3g, 58.8mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (23.2g, 168.1mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.3g, 0.6mmol) was added. After reacting for 4 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 17.7 g of Compound 11. (Yield 70%, MS: [M+H] ⁺ = 451)

Synthesis Example 12

Trz12 (15g, 38.1mmol) and compound A-3-7 (13.8g, 40mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (15.8g, 114.3mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 2 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 13.2 g of Compound 12. (Yield 60%, MS: [M+H] ⁺ = 577)

Synthesis Example 13

Trz13 (15g, 38.1mmol) and compound A-2-2 (13.8g, 40mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (15.8g, 114.3mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 3 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 17.3 g of Compound 13. (Yield 79%, MS: [M+H] ⁺ = 577)

Synthesis Example 14

Trz14 (15g, 40.1mmol) and compound A-2-2 (14.5g, 42.1mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (16.6g, 120.4mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 4 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 13.8 g of Compound 14. (Yield 62%, MS: [M+H] ⁺ = 557)

Synthesis Example 15

Trz15 (15g, 33.8mmol) and Compound A-2-1 (12.2g, 35.5mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14g, 101.4mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 3 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 15. (Yield 74%, MS: [M+H] ⁺ = 627)

Synthesis Example 16

Trz16 (15g, 40.8mmol) and compound A-2-3 (14.8g, 42.8mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (16.9g, 122.3mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 5 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 17.1 g of Compound 16. (Yield 76%, MS: [M+H] ⁺ = 551)

Synthesis Example 17

Trz17 (15g, 35.9mmol) and Compound A-2-4 (13g, 37.7mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.9g, 107.7mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 3 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 17.2 g of compound 17. (Yield 80%, MS: [M+H] ⁺ = 601)

Synthesis Example 18

Trz18 (15g, 35.9mmol) and compound A-2-6 (13g, 37.7mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.9g, 107.7mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 4 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 15.3 g of Compound 18. (Yield 71%, MS: [M+H] ⁺ = 601)

Synthesis Example 19

Trz1 (15g, 41.9mmol) and compound A-2-6 (15.2g, 44mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (17.4g, 125.8mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 5 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 14.5 g of Compound 19. (Yield 64%, MS: [M+H] ⁺ = 541)

Synthesis Example 20

Trz19 (15g, 34.6mmol) and compound A-2-7 (12.6g, 36.4mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.4g, 103.9mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.8 g of Compound 20. (Yield 60%, MS: [M+H] ⁺ = 616)

Synthesis Example 21

Trz20 (15g, 41.9mmol) and Compound A-2-7 (15.2g, 44mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (17.4g, 125.8mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 3 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 21. (Yield 63%, MS: [M+H] ⁺ = 541)

Synthesis Example 22

Trz21 (15g, 31mmol) and Compound A-1-2 (11.2g, 32.5mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (12.9g, 93mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 5 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 15.1 g of Compound 22. (Yield 73%, MS: [M+H] ⁺ = 667)

Synthesis Example 23

Trz22 (15g, 41.9mmol) and compound A-1-2 (15.2g, 44mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (17.4g, 125.8mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 4 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 13.8 g of Compound 23. (Yield 61%, MS: [M+H] ⁺ = 541)

Synthesis Example 24

Trz17 (15g, 31mmol) and compound A-1-1 (11.2g, 32.5mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (12.9g, 93mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 5 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 11.3 g of Compound 24. (Yield 61%, MS: [M+H] ⁺ = 601)

Synthesis Example 25

Trz23 (15g, 34.6mmol) and compound A-1-4 (12.6g, 36.4mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.4g, 103.9mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 5 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 17.1 g of Compound 25. (Yield 80%, MS: [M+H] ⁺ = 616)

Synthesis Example 26

Trz18 (15g, 35.9mmol) and Compound A-1-4 (13g, 37.7mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.9g, 107.7mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 3 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 14.2 g of Compound 26. (Yield 66%, MS: [M+H] ⁺ = 601)

Synthesis Example 27

Trz8 (15g, 35.9mmol) and Compound A-1-7 (13g, 37.7mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.9g, 107.7mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 5 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 14.2 g of Compound 27. (Yield 66%, MS: [M+H] ⁺ = 601)

Synthesis Example 28

Trz24 (15g, 33.8mmol) and Compound A-1-7 (12.2g, 35.5mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14g, 101.4mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 3 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 28. (Yield 62%, MS: [M+H] ⁺ = 627)

Synthesis Example 29

Trz25 (15g, 31mmol) and compound A-1-7 (11.2g, 32.5mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (12.9g, 93mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.4 g of Compound 29. (Yield 60%, MS: [M+H] ⁺ = 667)

Synthesis Example 30

Trz26 (15g, 42mmol) and compound A-4-3 (15.2g, 44.1mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (17.4g, 126.1mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 4 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 15.9 g of Compound 30. (Yield 70%, MS: [M+H] ⁺ = 540)

Synthesis Example 31

Trz27 (15g, 35.9mmol) and compound A-4-3 (13g, 37.7mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (14.9g, 107.7mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 4 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 14.6 g of Compound 31. (Yield 68%, MS: [M+H] ⁺ = 601)

Synthesis Example 32

Trz28 (15g, 30.4mmol) and compound A-4-3 (11g, 31.9mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (12.6g, 91.1mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 5 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 14.8 g of Compound 32. (Yield 72%, MS: [M+H] ⁺ = 677)

Synthesis Example 33

Trz29 (15g, 41.9mmol) and compound A-4-2 (15.2g, 44mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (17.4g, 125.8mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 2 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 15.9 g of Compound 33. (Yield 70%, MS: [M+H] ⁺ = 541)

Synthesis Example 34

Trz30 (15g, 40.8mmol) and compound A-4-2 (14.8g, 42.8mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (16.9g, 122.3mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 4 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 14.6 g of Compound 34. (Yield 65%, MS: [M+H] ⁺ = 551)

Synthesis Example 35

Trz31 (15g, 40.8mmol) and compound A-4-1 (14.8g, 42.8mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (16.9g, 122.3mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 4 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 13.7 g of Compound 35. (Yield 61%, MS: [M+H] ⁺ = 551)

Synthesis Example 36

Trz32 (15g, 40.1mmol) and compound A-4-5 (14.5g, 42.1mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (16.6g, 120.4mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 2 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 18.8 g of Compound 36. (Yield 78%, MS: [M+H] ⁺ = 603)

Synthesis Example 37

Trz9 (15g, 36.8mmol) and compound A-4-5 (13.3g, 38.6mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (15.2g, 110.3mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 2 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 16.3 g of Compound 37. (Yield 75%, MS: [M+H] ⁺ = 591)

Synthesis Example 38

Trz8 (15g, 35.9mmol) and compound A-4-5 (13g, 37.7mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.9g, 107.7mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 4 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 38. (Yield 75%, MS: [M+H] ⁺ = 601)

Synthesis Example 39

Trz33 (15g, 35.7mmol) and compound A-5-3 (12.9g, 37.5mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (14.8g, 107.2mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 5 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 15.5 g of Compound 39. (Yield 72%, MS: [M+H] ⁺ = 603)

Synthesis Example 40

Trz34 (15g, 35.9mmol) and compound A-5-3 (13g, 37.7mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (14.9g, 107.7mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 5 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 40. (Yield 65%, MS: [M+H] ⁺ = 601)

Synthesis Example 41

Trz35 (15g, 38.1mmol) and compound A-5-3 (13.8g, 40mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (15.8g, 114.3mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 5 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 g of Compound 41. (Yield 73%, MS: [M+H] ⁺ = 577)

Synthesis Example 42

Trz36 (15g, 35.9mmol) and compound A-5-2 (13g, 37.7mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (14.9g, 107.7mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 3 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 15.3 g of Compound 42. (Yield 71%, MS: [M+H] ⁺ = 601)

Synthesis Example 43

Trz31 (15g, 40.8mmol) and compound A-5-4 (14.8g, 42.8mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (16.9g, 122.3mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 3 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 14.6 g of Compound 43. (Yield 65%, MS: [M+H] ⁺ = 551)

Synthesis Example 44

Trz37 (15g, 35.4mmol) and compound A-5-5 (12.8g, 37.2mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.7g, 106.2mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 3 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 15.4 g of Compound 44. (Yield 72%, MS: [M+H] ⁺ = 607)

Synthesis Example 45

Trz38 (15g, 38.1mmol) and compound A-5-6 (13.8g, 40mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (15.8g, 114.3mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 5 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 16.2 g of Compound 45. (Yield 74%, MS: [M+H] ⁺ = 577)

Synthesis Example 46

Trz9 (15g, 36.8mmol) and compound A-5-6 (13.3g, 38.6mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (15.2g, 110.3mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 4 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 14.3 g of Compound 46. (Yield 66%, MS: [M+H] ⁺ = 591)

Synthesis Example 47

Trz39 (15g, 33.8mmol) and compound A-5-6 (12.2g, 35.5mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14g, 101.4mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 5 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 47. (Yield 79%, MS: [M+H] ⁺ = 627)

Synthesis Example 48

Trz40 (15g, 31mmol) and compound A-6-3 (11.2g, 32.5mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (12.9g, 93mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 5 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 16.1 g of Compound 48. (Yield 78%, MS: [M+H] ⁺ = 667)

Synthesis Example 49

Trz41 (15g, 32.1mmol) and Compound A-6-1 (11.6g, 33.7mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (13.3g, 96.2mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.5 g of Compound 49. (Yield 60%, MS: [M+H] ⁺ = 651)

Synthesis Example 50

Trz42 (15g, 38.1mmol) and compound A-6-4 (13.8g, 40mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (15.8g, 114.3mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 2 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 17.3 g of Compound 50. (Yield 79%, MS: [M+H] ⁺ = 577)

Synthesis Example 51

Trz43 (15g, 35.9mmol) and compound A-6-4 (13g, 37.7mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (14.9g, 107.7mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 3 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 14.2 g of Compound 51. (Yield 66%, MS: [M+H] ⁺ = 601)

Synthesis Example 52

Trz18 (15g, 35.9mmol) and compound A-6-5 (13g, 37.7mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (14.9g, 107.7mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 4 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 52. (Yield 65%, MS: [M+H] ⁺ = 601)

Synthesis Example 53

Trz18 (15g, 41.9mmol) and compound A-6-5 (15.2g, 44mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (17.4g, 125.8mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 5 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 13.8 g of compound 53. (Yield 61%, MS: [M+H] ⁺ = 541)

Synthesis Example 54

Trz17 (15g, 35.9mmol) and compound A-6-6 (13g, 37.7mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (14.9g, 107.7mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 4 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 54. (Yield 75%, MS: [M+H] ⁺ = 601)

Synthesis Example 55

Trz44 (15g, 38.1mmol) and compound A-6-6 (13.8g, 40mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (15.8g, 114.3mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 5 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 15.1 g of compound 55. (Yield 69%, MS: [M+H] ⁺ = 577)

Synthesis Example 56

Trz32 (15g, 35.7mmol) and compound A-7-3 (12.9g, 37.5mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (14.8g, 107.2mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 2 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 14.8 g of compound 56. (Yield 69%, MS: [M+H] ⁺ = 603)

Synthesis Example 57

Trz18 (15g, 35.9mmol) and compound A-7-3 (13g, 37.7mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (14.9g, 107.7mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 3 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 16.2 g of Compound 57. (Yield 75%, MS: [M+H] ⁺ = 601)

Synthesis Example 58

Trz45 (15g, 29.5mmol) and Compound A-7-1 (10.7g, 30.9mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (12.2g, 88.4mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 2 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 16.3 g of compound 58. (Yield 80%, MS: [M+H] ⁺ = 692)

Synthesis Example 59

Trz46 (15g, 35.9mmol) and compound A-7-4 (13g, 37.7mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (14.9g, 107.7mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 2 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 13.1 g of compound 59. (Yield 61%, MS: [M+H] ⁺ = 601)

Synthesis Example 60

Trz47 (15g, 33.8mmol) and compound A-7-4 (12.2g, 35.5mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (14g, 101.4mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 2 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 12.9 g of compound 60. (Yield 61%, MS: [M+H] ⁺ = 627)

Synthesis Example 61

Trz48 (15g, 32.1mmol) and compound A-7-5 (11.6g, 33.7mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (13.3g, 96.2mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 2 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 13.5 g of compound 61. (Yield 65%, MS: [M+H] ⁺ = 651)

Synthesis Example 62

Trz42 (15g, 38.1mmol) and compound A-7-5 (13.8g, 40mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (15.8g, 114.3mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 3 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 15.4 g of Compound 62. (Yield 70%, MS: [M+H] ⁺ = 577)

Synthesis Example 63

Trz42 (15g, 38.1mmol) and compound A-8-3 (13.8g, 40mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (15.8g, 114.3mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 5 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 13.8 g of compound 63. (Yield 63%, MS: [M+H] ⁺ = 577)

Synthesis Example 64

Trz49 (15g, 31.1mmol) and compound A-8-3 (11.3g, 32.6mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (12.9g, 93.2mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 2 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 13.2 g of Compound 64. (Yield 64%, MS: [M+H] ⁺ = 666)

Synthesis Example 65

Trz9 (15g, 36.8mmol) and compound A-8-2 (13.3g, 38.6mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (15.2g, 110.3mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 4 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 g of compound 65. (Yield 60%, MS: [M+H] ⁺ = 591)

Synthesis Example 66

Trz50 (15g, 35.4mmol) and compound A-8-1 (12.8g, 37.2mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (14.7g, 106.2mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 3 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 17.9 g of compound 66. (Yield 75%, MS: [M+H] ⁺ = 677)

Synthesis Example 67

Trz51 (15g, 35.4mmol) and compound A-8-4 (12.8g, 37.2mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.7g, 106.2mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 5 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 13.7 g of compound 67. (Yield 64%, MS: [M+H] ⁺ = 607)

Synthesis Example 68

Trz52 (15g, 43.6mmol) and compound A-8-5 (15.8g, 45.8mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (18.1g, 130.9mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 3 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 17.4 g of compound 68. (Yield 76%, MS: [M+H] ⁺ = 527)

Synthesis Example 69

Trz53 (15g, 30.4mmol) and compound A-8-5 (11g, 31.9mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (12.6g, 91.1mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 3 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 13.8 g of Compound 69. (Yield 67%, MS: [M+H] ⁺ = 677)

Synthesis Example 70

Trz54 (15g, 35.7mmol) and compound A-9-3 (12.9g, 37.5mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.8g, 107.2mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 3 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 14.4 g of Compound 70. (Yield 67%, MS: [M+H] ⁺ = 603)

Synthesis Example 71

Trz55 (15g, 30.4mmol) and compound A-9-3 (11g, 31.9mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (12.6g, 91.1mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 4 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 13.6 g of compound 71. (Yield 66%, MS: [M+H] ⁺ = 677)

Synthesis Example 72

Trz56 (15g, 30.4mmol) and compound A-9-1 (11g, 31.9mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (12.6g, 91.1mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 5 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 13.3 g of Compound 72. (Yield 65%, MS: [M+H] ⁺ = 677)

Synthesis Example 73

Trz57 (15g, 30.4mmol) and compound A-9-4 (11g, 31.9mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (12.6g, 91.1mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 3 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 73. (Yield 74%, MS: [M+H] ⁺ = 677)

Synthesis Example 74

Trz58 (15g, 29.5mmol) and compound A-9-5 (10.7g, 30.9mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (12.2g, 88.4mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 2 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 15.1 g of Compound 74. (Yield 74%, MS: [M+H] ⁺ = 692)

Synthesis Example 75

Trz18 (15g, 35.9mmol) and compound A-9-5 (13g, 37.7mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.9g, 107.7mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 2 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 15.5 g of Compound 75. (Yield 72%, MS: [M+H] ⁺ = 601)

Synthesis Example 76

Trz59 (15g, 38.1mmol) and compound A-10-3 (13.8g, 40mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (15.8g, 114.3mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 5 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 17.6 g of compound 76. (Yield 80%, MS: [M+H] ⁺ = 577)

Synthesis Example 77

Trz60 (15g, 38.1mmol) and compound A-10-3 (13.8g, 40mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (15.8g, 114.3mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 4 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 13.6 g of Compound 77. (Yield 62%, MS: [M+H] ⁺ = 577)

Synthesis Example 78

Trz61 (15g, 35.4mmol) and compound A-10-2 (12.8g, 37.2mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (14.7g, 106.2mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 2 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 15.4 g of Compound 78. (Yield 72%, MS: [M+H] ⁺ = 607)

Synthesis Example 79

Trz63 (15g, 43.6mmol) and compound A-10-1 (15.8g, 45.8mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.1g, 130.9mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 4 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 14.9 g of compound 79. (Yield 65%, MS: [M+H] ⁺ = 527)

Synthesis Example 80

Trz32 (15g, 35.7mmol) and compound A-10-4 (12.9g, 37.5mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (14.8g, 107.2mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 4 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 14.4 g of Compound 80. (Yield 67%, MS: [M+H] ⁺ = 603)

Synthesis Example 81

Trz64 (15g, 35.9mmol) and compound A-10-4 (13g, 37.7mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (14.9g, 107.7mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.9 g of compound 81. (Yield 60%, MS: [M+H] ⁺ = 601)

Synthesis Example 82

Trz65 (15g, 31.1mmol) and compound A-10-4 (11.3g, 32.6mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (12.9g, 93.2mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 3 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 14.9 g of compound 82. (Yield 72%, MS: [M+H] ⁺ = 666)

Synthesis Example 83

Trz6 (15g, 43.6mmol) and compound A-10-5 (15.8g, 45.8mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.1g, 130.9mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 5 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 18.1 g of compound 83. (Yield 79%, MS: [M+H] ⁺ = 527)

Example 1

A glass substrate coated with ITO (indium tin oxide) to a thickness of 1,000 Å was put in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, a Fischer Co. product was used as the detergent, and distilled water filtered through a second filter of a Millipore Co. product was used as the distilled water. After washing the ITO for 30 minutes, 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%. On the hole injection layer, the following HT-1 compound was vacuum deposited to form a hole transport layer having a thickness of 800 Å. 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, Compound 1 as a host and Compound Dp-7 as a dopant were vacuum deposited at a weight ratio of 98:2 to form a red light emitting layer having a thickness of 400 Å. 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 ~ 0.7Å / sec, the deposition rate of lithium fluoride on the cathode was 0.3Å / sec, and the deposition rate of aluminum was 2Å / sec, and the vacuum level during deposition was 2ⅹ10 ^-7 ~ Maintaining 5x10 ^-6 torr, an organic light emitting device was manufactured.

Examples 2 to 83

An organic light emitting device was manufactured in the same manner as in Example 1, except for using the compounds listed in Table 1 below in Example 1.

Comparative Examples 1 to 12

An organic light emitting device was manufactured in the same manner as in Example 1, except for using the compounds listed in Table 1 below in Example 1. Compounds B-1 to B-12 in Table 1 are as follows.

When current was applied to the organic light emitting devices prepared in Examples 1 to 83 and Comparative Examples 1 to 12, voltage and efficiency were measured (based on 15 mA/cm ² ) and the results are shown in Tables 1 to 12 below. shown in 2. The lifetime T95 means the time required for the luminance to decrease from the initial luminance (6,000 nit) to 95%.

division host Driving voltage (V) Efficiency (cd/A) Lifetime T95(hr) luminescent color Example 1 compound 1 3.58 21.31 158 Red Example 2 compound 2 3.57 20.23 168 Red Example 3 compound 3 3.55 20.76 172 Red Example 4 compound 4 3.59 20.92 173 Red Example 5 compound 5 3.56 20.70 157 Red Example 6 compound 6 3.56 20.83 153 Red Example 7 compound 7 3.56 20.22 155 Red Example 8 compound 8 3.58 21.41 163 Red Example 9 compound 9 3.57 21.40 159 Red Example 10 compound 10 3.60 20.21 160 Red Example 11 compound 11 3.61 21.44 172 Red Example 12 compound 12 3.55 21.19 158 Red Example 13 compound 13 3.51 22.09 189 Red Example 14 compound 14 3.41 21.80 176 Red Example 15 compound 15 3.53 22.11 184 Red Example 16 compound 16 3.43 22.19 191 Red Example 17 compound 17 3.55 21.78 184 Red Example 18 compound 18 3.53 21.35 179 Red Example 19 compound 19 3.53 21.25 193 Red Example 20 compound 20 3.47 22.15 184 Red Example 21 compound 21 3.43 21.97 187 Red Example 22 compound 22 3.40 22.41 212 Red Example 23 compound 23 3.33 23.35 216 Red Example 24 compound 24 3.37 22.57 222 Red Example 25 compound 25 3.32 22.34 199 Red Example 26 compound 26 3.29 22.91 212 Red Example 27 compound 27 3.32 22.65 188 Red Example 28 compound 28 3.42 22.95 228 Red Example 29 compound 29 3.33 23.32 191 Red Example 30 compound 30 3.60 20.34 161 Red Example 31 compound 31 3.60 20.68 152 Red Example 32 compound 32 3.54 20.81 152 Red Example 33 compound 33 3.60 21.19 171 Red Example 34 compound 34 3.53 20.86 153 Red Example 35 compound 35 3.56 20.70 162 Red Example 36 compound 36 3.55 20.71 172 Red Example 37 compound 37 3.55 20.86 156 Red Example 38 compound 38 3.60 20.45 152 Red Example 39 compound 39 3.67 19.87 155 Red Example 40 compound 40 3.68 20.07 153 Red Example 41 compound 41 3.64 20.08 153 Red Example 42 compound 42 3.62 20.06 167 Red Example 43 compound 43 3.60 20.37 157 Red Example 44 compound 44 3.61 20.49 168 Red Example 45 compound 45 3.67 19.90 159 Red Example 46 compound 46 3.63 19.44 170 Red Example 47 compound 47 3.65 19.83 166 Red Example 48 compound 48 3.56 20.86 169 Red Example 49 compound 49 3.58 20.90 170 Red Example 50 compound 50 3.56 21.04 180 Red Example 51 compound 51 3.58 21.45 176 Red Example 52 compound 52 3.57 20.61 168 Red Example 53 compound 53 3.60 20.43 177 Red Example 54 compound 54 3.60 21.50 176 Red Example 55 compound 55 3.55 20.24 177 Red Example 56 compound 56 3.35 20.40 210 Red Example 57 compound 57 3.33 21.37 225 Red Example 58 compound 58 3.30 21.19 227 Red Example 59 compound 59 3.43 20.80 194 Red Example 60 compound 60 3.41 20.44 194 Red Example 61 compound 61 3.37 21.13 212 Red Example 62 compound 62 3.31 20.78 191 Red Example 63 compound 63 3.60 20.38 152 Red Example 64 compound 64 3.60 19.98 166 Red Example 65 compound 65 3.65 19.41 158 Red Example 66 compound 66 3.69 20.10 163 Red Example 67 compound 67 3.61 19.48 170 Red Example 68 compound 68 3.60 20.19 170 Red Example 69 compound 69 3.68 20.10 153 Red Example 70 compound 70 3.35 22.88 212 Red Example 71 compound 71 3.28 22.98 225 Red Example 72 compound 72 3.36 22.73 208 Red Example 73 compound 73 3.41 22.54 211 Red Example 74 compound 74 3.35 23.19 206 Red Example 75 compound 75 3.31 23.31 208 Red Example 76 compound 76 3.61 21.47 154 Red Example 77 compound 77 3.56 20.69 153 Red Example 78 compound 78 3.56 21.33 152 Red Example 79 compound 79 3.55 21.08 165 Red Example 80 compound 80 3.56 20.82 169 Red Example 81 compound 81 3.61 21.26 173 Red Example 82 compound 82 3.57 20.84 157 Red Example 83 compound 83 3.58 21.22 165 Red Comparative Example 1 compound B-1 4.09 18.20 91 Red Comparative Example 2 compound B-2 4.26 17.90 79 Red Comparative Example 3 compound B-3 3.89 18.83 124 Red Comparative Example 4 compound B-4 3.75 18.48 119 Red Comparative Example 5 Compound B-5 4.12 17.10 103 Red Comparative Example 6 Compound B-6 4.07 18.29 78 Red Comparative Example 7 Compound B-7 4.05 18.17 94 Red Comparative Example 8 Compound B-8 4.04 17.95 89 Red Comparative Example 9 Compound B-9 4.06 18.22 79 Red Comparative Example 10 Compound B-10 4.11 18.18 86 Red Comparative Example 11 compound B-11 4.02 16.76 103 Red Comparative Example 12 compound B-12 4.12 16.98 92 Red

When current was applied to the organic light emitting devices manufactured in Examples 1 to 83 and Comparative Examples 1 to 12, the results of Tables 1 to 2 were obtained. The red organic light emitting device of Example 1 used materials widely used in the prior art, and had a structure using compound [EB-1] as an electron blocking layer and Dp-7 as a red dopant.

When the compound of the present invention was used as a red light emitting layer, as shown in Table 1, the driving voltage decreased and the efficiency and lifespan increased compared to the comparative examples in Table 2. It was found that the energy transfer to the red dopant in the light emitting layer was well achieved. It can be determined that this is because electrons and holes combine to form excitons through a more stable balance in the light emitting layer compared to the comparative compound.

In conclusion, it can be confirmed that the driving voltage, luminous efficiency and lifetime characteristics of the organic light emitting device can be improved when the compound of the present invention is used as a host of the red light emitting layer.

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

Claims (9)

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

In Formula 1,
One of X ₁ to X ₁₀ is N, the other is C substituted with a substituent represented by Formula 2 below, and the others are CR ₁ ;
R ₁ is each independently hydrogen or deuterium;
[Formula 2]

In Formula 2,
Y is each independently N or CR ₂ , provided that at least one of Y is N;
R ₂ are each independently hydrogen or deuterium;
L is a single bond or a substituted or unsubstituted C _6-60 arylene;
L ₁ and L ₂ 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 substituted or unsubstituted C _2-60 heteroaryl containing at least one selected from the group consisting of N, O and S; ego,
However, when X ₅ or X ₆ is N, one of X ₁ to X ₄ and X ₇ to X ₁₀ is C substituted with the substituent of Formula 2,
When one of X ₇ to X ₁₀ is N, one of X ₁ to X ₆ is C substituted with the substituent of Formula 2 above.
According to claim 1,
Y is all N,
compound.
According to claim 1,
Formula 1 is represented by any one of Formulas 1-1 to 1-10,
compound:

In Formula 1-1, one of X ₂ to X ₁₀ is C substituted with a substituent of Formula 2, and the others are each independently CH or CD,
In Formula 1-2, one of X ₁ and X ₃ to X ₁₀ is C substituted with a substituent of Formula 2, and the others are each independently CH or CD,
In Formula 1-3, one of X ₁ , X ₂ and X ₄ to X ₁₀ is C substituted with a substituent of Formula 2, and the others are each independently CH or CD,
In Formula 1-4, one of X ₁ to X ₃ and X ₅ to X ₁₀ is C substituted with a substituent of Formula 2, and the others are each independently CH or CD,
In Formula 1-5, one of X ₁ to X ₄ and X ₇ to X ₁₀ is C substituted with a substituent of Formula 2, the others are each independently CH or CD, X ₆ is CH or CD,
In Formula 1-6, one of X ₁ to X ₄ and X ₇ to X ₁₀ is C substituted with a substituent of Formula 2, the others are each independently CH or CD, X ₅ is CH or CD,
In Formula 1-7, one of X ₁ to X ₆ is C substituted with a substituent of Formula 2, the others are each independently CH or CD, and X ₈ to X ₁₀ are each independently CH or CD,
In Formula 1-8, one of X ₁ to X ₆ is C substituted with a substituent of Formula 2, the others are each independently CH or CD, and X ₇ , X ₉ and X ₁₀ are each independently CH or is a CD,
In Formula 1-9, one of X ₁ to X ₆ is C substituted with a substituent of Formula 2, the others are each independently CH or CD, and X ₇ , X ₈ and X ₁₀ are each independently CH or is a CD,
In Formula 1-10, one of X ₁ to X ₆ is C substituted with a substituent of Formula 2, the others are each independently CH or CD, and X ₇ to X ₉ are each independently CH or CD.
According to claim 1,
L is a single bond, unsubstituted or substituted with one or more deuterium phenylene, or unsubstituted or substituted with one or more deuterium naphthylene;
compound.
According to claim 1,
L ₁ and L ₂ are each independently a single bond, unsubstituted or substituted with one or more deuterium phenylene, or unsubstituted or substituted with one or more deuterium naphthylene;
compound.
According to claim 1,
Ar ₁ and Ar ₂ are each independently selected from phenyl, biphenylyl, terphenylyl, naphthyl, (phenyl)naphthyl, (naphthyl)phenyl, phenanthrenyl, benzophenanthrenyl, dibenzofuranyl, dibenzo thiophenyl, carbazol-9-yl, or 9-phenyl-carbazolyl;
Ar ₁ and Ar ₂ are each independently unsubstituted or substituted with at least one deuterium,
compound.
According to claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of
compound:

a first electrode; a second electrode provided to face the first electrode; and one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the compound according to any one of claims 1 to 6. That is, an organic light emitting device.
According to claim 8,
The organic material layer containing the compound is a light emitting layer,
organic light emitting device.

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