KR102568928B1 - 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 including the same.

Description

Novel compound and organic light emitting device comprising the same {Novel compound and organic light emitting device comprising 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 organic light emitting material 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,

A is a thiazole ring or an oxazole ring fused with an adjacent ring,

L ₁ is a single bond; Substituted or unsubstituted C _6-60 arylene; Or a C _2-60 heteroarylene containing at least one selected from the group consisting of substituted or unsubstituted N, O and S,

또는

이고,R ₁ is

or

ego,

Ar ₁ to Ar ₄ are each independently a substituted or unsubstituted C _6-60 aryl; Or a C _2-60 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O and S,

The L ₂ to L ₅ are each independently a single bond; Substituted or unsubstituted C _6-60 arylene; Or a C _2-60 heteroarylene containing at least one selected from the group consisting of substituted or unsubstituted N, O and S,

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

D is deuterium;

n is an integer of 0 or more and 5 or less.

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 at least one compound represented by Chemical Formula 1. to provide.

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

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.

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

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 heteroaryl group containing one or more 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 the present specification, the boron group specifically includes a trimethyl boron group, a triethyl boron group, a t-butyldimethyl boron group, a triphenyl boron group, a phenyl boron group, but is not limited thereto.

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

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

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

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

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

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

In the present specification, the heteroaryl group is a heteroaryl group containing one or more 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. According to one embodiment, the heteroaryl group has 6 to 30 carbon atoms. According to one embodiment, the carbon number of the heteroaryl group is 6 to 20. Examples of the heteroaryl 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 heteroaryl 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 heteroaryl group described above may be applied except that 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, heteroaryl is not a monovalent group, and the description of the above-described heteroaryl group may be applied, except that it is formed by combining two substituents.

Preferably, Chemical Formula 1 may be represented by any one of the following Chemical Formulas 1-1 to 1-4:

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Formula 1-1 to Formula 1-4,

Descriptions of R ₁ , R ₂ , L ₁ , D and n are as defined in Formula 1 above.

Preferably, L ₁ is a single bond; Substituted or unsubstituted C _6-20 arylene; Or a C _2-20 heteroarylene containing at least one selected from the group consisting of substituted or unsubstituted N, O and S,

More preferably, L ₁ may be a single bond, phenylene, biphenyldiyl, or naphthalenediyl.

Most preferably, L ₁ may be a single bond or any one selected from the group consisting of:

.

.

Preferably, Ar ₁ and Ar ₂ are each independently substituted or unsubstituted C _6-20 aryl; Or a substituted or unsubstituted C _2-20 heteroaryl containing at least one selected from the group consisting of N, O and S,

More preferably, Ar ₁ and Ar ₂ may each independently be phenyl, biphenylyl, naphthyl, phenanthrenyl, dibenzofuranyl, or dibenzothiophenyl.

Most preferably, Ar ₁ and Ar ₂ may each independently be any one selected from the group consisting of:

.

.

Preferably, Ar ₃ and Ar ₄ are each independently substituted or unsubstituted C _6-20 aryl; Or a substituted or unsubstituted C _2-20 heteroaryl containing at least one selected from the group consisting of N, O and S,

More preferably, Ar ₃ and Ar ₄ are each independently phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, dibenzofuranyl, dibenzothiophenyl, phenyl carbazolyl, or phenyl naphthylyl. can

Most preferably, Ar ₃ and Ar ₄ may each independently be any one selected from the group consisting of:

.

.

Preferably, L ₂ and L ₃ are each independently a single bond; It may be a substituted or unsubstituted C _6-20 arylene,

More preferably, L ₂ and L ₃ may each independently represent a single bond, phenylene, or naphthalenediyl.

Most preferably, L ₂ and L ₃ may each independently be a single bond or any one selected from the group consisting of:

.

.

Preferably, L ₄ and L ₅ are each independently a single bond; Substituted or unsubstituted C _6-20 arylene; Or a C _2-20 heteroarylene containing at least one selected from the group consisting of substituted or unsubstituted N, O and S,

More preferably, L ₄ and L ₅ may each independently represent a single bond, phenylene, biphenyldiyl, naphthalenediyl, or carbazolediyl.

Most preferably, L ₄ and L ₅ may each independently be a single bond or any one selected from the group consisting of:

.

.

Preferably, at least one of Ar ₁ and Ar ₂ may be a substituted or unsubstituted C _6-60 aryl, more preferably, at least one of Ar ₁ and Ar ₂ is a substituted or unsubstituted C _6-20 aryl, more preferably, at least one of Ar ₁ and Ar ₂ can be an unsubstituted C _6-20 aryl, and most preferably, at least one of Ar ₁ and Ar ₂ is phenyl, or naphthylyl can

Preferably, at least one of Ar ₃ and Ar ₄ may be a substituted or unsubstituted C _6-60 aryl, more preferably, at least one of Ar ₃ and Ar ₄ is a substituted or unsubstituted C _6-20 aryl, more preferably, at least one of Ar ₃ and Ar ₄ may be an unsubstituted C _6-20 aryl, and most preferably, at least one of Ar ₃ and Ar ₄ is phenyl, biphenylyl , or naphthyl.

Meanwhile, R ₂ is a substituent of Ring A.

Preferably, R ₂ is a substituted or unsubstituted C _6-20 aryl; Or it may be a C _2-20 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O and S.

More preferably, R ₂ can be phenyl, biphenylyl, naphthyl, dibenzofuranyl, or dibenzothiophenyl.

Most preferably, R ₂ can be any one selected from the group consisting of:

.

.

Preferably, n may be 0.

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

.

.

인 경우, 하기 반응식 1과 같은 제조 방법으로 제조할 수 있으며, 일부 화합물의 경우 하기 반응식 2와 같은 제조 방법으로 제조할 수 있고, 그 외 나머지 화합물도 유사하게 제조할 수 있다.In the compound represented by Formula 1, for example, L ₁ is a single bond, and R ₁ is

In the case of, it can be prepared by a manufacturing method such as the following Reaction Scheme 1, and in the case of some compounds, it can be prepared by a manufacturing method such as the following Reaction Scheme 2, and other compounds can be prepared similarly.

[Scheme 1]

[Scheme 2]

In Reaction Schemes 1 and 2, R ₁ , R ₂ , L ₁ , L ₄ , L ₅ , Ar ₃ and Ar ₄ are as defined in Formula 1, X ₁ and X ₂ are each independently a halogen, Preferably X ₁ and X ₂ are each independently chloro or bromo.

Reaction Scheme 1 is an amine substitution reaction, which is preferably carried out in the presence of a palladium catalyst and a base, and the reactor for the amine substitution reaction can be changed as known in the art. In addition, Reaction Scheme 2 is a Suzuki coupling reaction, which is preferably carried out in the presence of a palladium catalyst and a base, and the reactor for the Suzuki coupling reaction can be changed as known in the art. The manufacturing method may be more specific in Preparation Examples to be described later.

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

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 diode is not limited thereto and may include a smaller number of organic material layers.

In addition, the organic material layer may include an electron blocking layer or a light emitting layer, and the electron blocking layer or light emitting 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. 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 such a structure, the compound represented by Chemical Formula 1 may be included in the light emitting layer or the electron blocking 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 And, after forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer thereon, it can be prepared by depositing a material that can be used as a cathode thereon. In addition to this method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

In addition, the compound represented by 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 electron blocking layer is a layer placed between the hole transport layer and the light emitting layer to prevent electrons injected from the cathode from passing to the hole transport layer without recombination in the light emitting layer, and is also called an electron blocking layer or an electron blocking layer. A material having a smaller electron affinity than the electron transport layer is preferable for the electron blocking layer. Preferably, a material represented by Chemical Formula 1 of the present invention may be used as an electron blocking layer material.

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. Preferably, a material represented by Formula 1 of the present invention may be used as a host material, and one or more materials represented by Formula 1 may be included as a host material. Preferably, when two types of compounds represented by Formula 1 are used in the light emitting layer, the weight ratio is 10:90 to 90:10, more preferably 20:80 to 80:20, 30:70 to 70 :30 or 40:60 to 60:40.

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.

For example, as a dopant material, one or more selected from the group consisting of the following may be used, but is not limited thereto:

.

.

The hole blocking layer is a layer placed between the electron transport layer and the light emitting layer to prevent holes injected from the anode from being recombinated in the light emitting layer and passing to the electron transport layer, and is also called a hole blocking layer. A material having high ionization energy is preferred for the hole-blocking layer.

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

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

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

On the other hand, in the present invention, the "electron injection and transport layer" is a layer that performs both the roles of the electron injection layer and the electron transport layer, and materials that play the role of each layer may be used alone or in combination, but are limited thereto. It doesn't work.

The organic light emitting device according to the present invention may be a bottom emission device, a top emission device, or a double-sided light emitting device, and in particular, may be a bottom emission device requiring relatively high light emitting efficiency.

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

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

[Production Example]

Preparation Example 1-1

In a nitrogen atmosphere, compound AA (15 g, 53.9 mmol) and [1,1'-biphenyl]-4-ylboronic acid (10.7 g, 53.9 mmol) were put in 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (22.4 g, 161.8 mmol) was dissolved in 67 ml of water, and after sufficiently stirred, Tetrakis (triphenylphosphine) palladium (0) (0.6 g, 0.5 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.4 g of compound subAA-1. (Yield 63%, MS: [M+H]+= 396)

Compound subAA-1 (15 g, 37.9 mmol) and bis(pinacolato)diboron (10.6 g, 41.7 mmol) were stirred while refluxing in 300 ml of 1,4-dioxane in a nitrogen atmosphere. Then, potassium acetate (5.6 g, 56.8 mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.7 g, 1.1 mmol) and tricyclohexylphosphine (0.6 g, 2.3 mmol) 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 obtain 12.4 g of compound subAA-2. (Yield 67%, MS: [M+H]+= 488)

In a nitrogen atmosphere, the compound subAA-2 (15 g, 30.8 mmol) and Trz1 (9.8 g, 30.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (12.8 g, 92.3 mmol) was dissolved in 38 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 12 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.9 g of Compound 1-1. (Yield 60%, MS: [M+H]+= 643)

Preparation Example 1-2

In a nitrogen atmosphere, compound AB (15 g, 53.9 mmol) and phenylboronic acid (6.6 g, 53.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (22.4 g, 161.8 mmol) was dissolved in 67 ml of water, and after sufficiently stirred, Tetrakis (triphenylphosphine) palladium (0) (0.6 g, 0.5 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.4 g of compound subAB-1. (Yield 78%, MS: [M+H]+= 320)

Compound subAB-1 (15 g, 46.9 mmol) and bis(pinacolato)diboron (13.1 g, 51.6 mmol) were stirred while refluxing in 300 ml of 1,4-dioxane in a nitrogen atmosphere. Then, potassium acetate (6.9 g, 70.4 mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.8 g, 1.4 mmol) and tricyclohexylphosphine (0.8 g, 2.8 mmol) 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 obtain 14.3 g of compound subAB-2. (Yield 74%, MS: [M+H]+= 412)

In a nitrogen atmosphere, the compounds subAB-2 (15 g, 36.5 mmol) and Trz2 (9.8 g, 36.5 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (15.1 g, 109.4 mmol) was dissolved in 45 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer 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 12.4 g of Compound 1-2. (Yield 66%, MS: [M+H]+= 517)

Preparation Example 1-3

Compound AE (15 g, 53.9 mmol) and phenylboronic acid (6.6 g, 53.9 mmol) were added to 300 ml of THF under a nitrogen atmosphere, followed by stirring and reflux. Thereafter, potassium carbonate (22.4 g, 161.8 mmol) was dissolved in 67 ml of water, and after sufficiently stirred, Tetrakis (triphenylphosphine) palladium (0) (0.6 g, 0.5 mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.7 g of compound subAE-1. (Yield 62%, MS: [M+H]+= 320)

In a nitrogen atmosphere, the compound subAE-1 (15 g, 46.9 mmol) and Trz3 (22.5 g, 46.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (19.5 g, 140.7 mmol) was dissolved in 58 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 9 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 25.3 g of Compound 1-3. (Yield 75%, MS: [M+H]+= 719)

Preparation Example 1-4

In a nitrogen atmosphere, the compound subAE-1 (15 g, 46.9 mmol) and Trz4 (20.8 g, 46.9 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (19.5 g, 140.7 mmol) was dissolved in 58 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 22.1 g of compound 1-4. (Yield 69%, MS: [M+H]+= 683)

Preparation Example 1-5

Compound AF (15 g, 53.9 mmol) and naphthalen-2-ylboronic acid (9.3 g, 53.9 mmol) were added to 300 ml of THF under a nitrogen atmosphere, followed by stirring and reflux. Thereafter, potassium carbonate (22.4 g, 161.8 mmol) was dissolved in 67 ml of water, and after sufficiently stirred, Tetrakis (triphenylphosphine) palladium (0) (0.6 g, 0.5 mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.1 g of compound subAF-1. (Yield 66%, MS: [M+H]+= 370)

In a nitrogen atmosphere, the compounds subAF-1 (15 g, 40.6 mmol) and Trz5 (16.4 g, 40.6 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (16.8 g, 121.7 mmol) was dissolved in 50 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 12 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 17.4 g of compound 1-5. (Yield 62%, MS: [M+H]+= 693)

Preparation Example 1-6

Compound BA (15 g, 53.9 mmol) and phenylboronic acid (6.6 g, 53.9 mmol) were added to 300 ml of THF under a nitrogen atmosphere, followed by stirring and reflux. Thereafter, potassium carbonate (22.4 g, 161.8 mmol) was dissolved in 67 ml of water, and after sufficiently stirred, Tetrakis (triphenylphosphine) palladium (0) (0.6 g, 0.5 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.6 g of compound subBA-1. (Yield 79%, MS: [M+H]+= 320)

Compound subBA-1 (15 g, 46.9 mmol) and bis(pinacolato)diboron (13.1 g, 51.6 mmol) were stirred while refluxing in 300 ml of 1,4-dioxane in a nitrogen atmosphere. Then, potassium acetate (6.9 g, 70.4 mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.8 g, 1.4 mmol) and tricyclohexylphosphine (0.8 g, 2.8 mmol) 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 obtain 13.1 g of compound subBA-2. (Yield 68%, MS: [M+H]+= 412)

In a nitrogen atmosphere, the compound subBA-2 (15 g, 36.5 mmol) and Trz7 (14.4 g, 36.5 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (15.1 g, 109.4 mmol) was dissolved in 45 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.5 g of Compound 1-6. (Yield 66%, MS: [M+H]+= 643)

Production Example 1-7

Compound BB (15 g, 53.9 mmol) and phenylboronic acid (6.6 g, 53.9 mmol) were added to 300 ml of THF under a nitrogen atmosphere, followed by stirring and reflux. Thereafter, potassium carbonate (22.4 g, 161.8 mmol) was dissolved in 67 ml of water, and after sufficiently stirred, Tetrakis (triphenylphosphine) palladium (0) (0.6 g, 0.5 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.2 g of compound subBB-1. (Yield 65%, MS: [M+H]+= 320)

Compound subBB-1 (15 g, 46.9 mmol) and Trz8 (18.9 g, 46.9 mmol) were added to 300 ml of THF under a nitrogen atmosphere, followed by stirring and reflux. Thereafter, potassium carbonate (19.5 g, 140.7 mmol) was dissolved in 58 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 18.1 g of compound 1-7. (Yield 60%, MS: [M+H]+= 643)

Production Example 1-8

In a nitrogen atmosphere, compound BE (15 g, 53.9 mmol) and dibenzo[b,d]thiophen-1-ylboronic acid (12.3 g, 53.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (22.4 g, 161.8 mmol) was dissolved in 67 ml of water, and after sufficiently stirred, Tetrakis (triphenylphosphine) palladium (0) (0.6 g, 0.5 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 16.7 g of compound subBE-1. (Yield 73%, MS: [M+H]+= 426)

In a nitrogen atmosphere, the compound subBE-1 (15 g, 35.2 mmol) and Trz9 (14.2 g, 35.2 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.6 g, 105.7 mmol) was dissolved in 44 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 18.2 g of Compound 1-8. (Yield 69%, MS: [M+H]+= 749)

Production Example 1-9

In a nitrogen atmosphere, the compound BF (15 g, 53.9 mmol) and phenylboronic acid (6.6 g, 53.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (22.4 g, 161.8 mmol) was dissolved in 67 ml of water, and after sufficiently stirred, Tetrakis (triphenylphosphine) palladium (0) (0.6 g, 0.5 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.5 g of compound subBF-1. (Yield 61%, MS: [M+H]+= 320)

Compound subBF-1 (15 g, 46.9 mmol) and Trz10 (22.5 g, 46.9 mmol) were added to 300 ml of THF under a nitrogen atmosphere, followed by stirring and reflux. Thereafter, potassium carbonate (19.5 g, 140.7 mmol) was dissolved in 58 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.2 g of Compound 1-9. (Yield 60%, MS: [M+H]+= 719)

Production Example 1-10

In a nitrogen atmosphere, compound CA (15 g, 51 mmol) and phenylboronic acid (6.2 g, 51 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 153 mmol) was dissolved in 63 ml of water, and after stirring sufficiently, Tetrakis (triphenylphosphine) palladium (0) (0.6 g, 0.5 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.4 g of compound subCA-1. (Yield 61%, MS: [M+H]+= 336)

Compound subCA-1 (15 g, 44.7 mmol) and Trz12 (19.2 g, 44.7 mmol) were added to 300 ml of THF under nitrogen atmosphere, followed by stirring and reflux. Thereafter, potassium carbonate (18.5 g, 134 mmol) was dissolved in 56 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.5 g of compound 1-10. (Yield 67%, MS: [M+H]+= 685)

Preparation Example 1-11

In a nitrogen atmosphere, compound CB (15 g, 51 mmol) and phenylboronic acid (6.2 g, 51 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 153 mmol) was dissolved in 63 ml of water, and after stirring sufficiently, Tetrakis (triphenylphosphine) palladium (0) (0.6 g, 0.5 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.2 g of compound subCB-1. (Yield 77%, MS: [M+H]+= 336)

In a nitrogen atmosphere, the compound subCB-1 (15 g, 44.7 mmol) and bis(pinacolato)diboron (12.5 g, 49.1 mmol) were stirred while refluxing in 300 ml of 1,4-dioxane. Then, potassium acetate (6.6 g, 67 mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.8 g, 1.3 mmol) and tricyclohexylphosphine (0.8 g, 2.7 mmol) 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 obtain 13.9 g of compound subCB-2. (Yield 73%, MS: [M+H]+= 428)

In a nitrogen atmosphere, the compound subCB-2 (15 g, 35.1 mmol) and Trz13 (13.8 g, 35.1 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.6 g, 105.3 mmol) was dissolved in 44 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 16.6 g of Compound 1-11. (Yield 72%, MS: [M+H]+= 659)

Production Example 1-12

In a nitrogen atmosphere, the compound subCB-1 (15 g, 36.5 mmol) and Trz14 (14.7 g, 36.5 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (15.1 g, 109.4 mmol) was dissolved in 45 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 12 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 g of Compound 1-12. (Yield 71%, MS: [M+H]+= 659)

Production Example 1-13

In a nitrogen atmosphere, compound CE (15 g, 51 mmol) and dibenzo[b,d]furan-1-ylboronic acid (10.8 g, 51 mmol) were put into 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 153 mmol) was dissolved in 63 ml of water, and after stirring sufficiently, Tetrakis (triphenylphosphine) palladium (0) (0.6 g, 0.5 mmol) was added. After reacting for 12 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.7 g of compound subCE-1. (Yield 63%, MS: [M+H]+= 426)

In a nitrogen atmosphere, the compound subCE-1 (15 g, 35.2 mmol) and Trz15 (12.4 g, 35.2 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.6 g, 105.7 mmol) was dissolved in 44 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.2 g of compound 1-13. (Yield 62%, MS: [M+H]+= 699)

Production Example 1-14

In a nitrogen atmosphere, compound CF (15 g, 51 mmol) and naphthalen-2-ylboronic acid (8.8 g, 51 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 153 mmol) was dissolved in 63 ml of water, and after stirring sufficiently, Tetrakis (triphenylphosphine) palladium (0) (0.6 g, 0.5 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.9 g of compound subCF-1. (Yield 76%, MS: [M+H]+= 386)

In a nitrogen atmosphere, the compounds subCF-1 (15 g, 38.9 mmol) and Trz5 (15.7 g, 38.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (16.1 g, 116.6 mmol) was dissolved in 48 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 12 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 18.2 g of Compound 1-14. (Yield 66%, MS: [M+H]+= 709)

Production Example 1-15

In a nitrogen atmosphere, compound DA (15 g, 51 mmol) and phenylboronic acid (6.2 g, 51 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 153 mmol) was dissolved in 63 ml of water, and after stirring sufficiently, Tetrakis (triphenylphosphine) palladium (0) (0.6 g, 0.5 mmol) was added. After reacting for 12 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.6 g of compound subDA-1. (Yield 68%, MS: [M+H]+= 336)

In a nitrogen atmosphere, the compound subDA-1 (15 g, 44.7 mmol) and bis(pinacolato)diboron (12.5 g, 49.1 mmol) were stirred while refluxing in 300 ml of 1,4-dioxane. Then, potassium acetate (6.6 g, 67 mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.8 g, 1.3 mmol) and tricyclohexylphosphine (0.8 g, 2.7 mmol) 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 obtain 13.4 g of compound subDA-2. (Yield 70%, MS: [M+H]+= 428)

In a nitrogen atmosphere, the compound subDA-2 (15 g, 35.1 mmol) and Trz17 (13.8 g, 35.1 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.6 g, 105.3 mmol) was dissolved in 44 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.6 g of compound 1-15. (Yield 63%, MS: [M+H]+= 659)

Production Example 1-16

In a nitrogen atmosphere, compound DB (15 g, 51 mmol) and naphthalen-2-ylboronic acid (8.8 g, 51 mmol) were put into 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 153 mmol) was dissolved in 63 ml of water, and after stirring sufficiently, Tetrakis (triphenylphosphine) palladium (0) (0.6 g, 0.5 mmol) was added. After reacting for 12 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.4 g of compound subDB-1. (Yield 68%, MS: [M+H]+= 386)

In a nitrogen atmosphere, the compound subDB-1 (15 g, 39 mmol) and bis(pinacolato)diboron (10.9 g, 42.9 mmol) were stirred while refluxing in 300 ml of 1,4-dioxane. Then, potassium acetate (5.7 g, 58.5 mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.7 g, 1.2 mmol) and tricyclohexylphosphine (0.7 g, 2.3 mmol) 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 obtain 13.9 g of compound subDB-2. (Yield 75%, MS: [M+H]+= 478)

In a nitrogen atmosphere, the compounds subDB-2 (15 g, 31.4 mmol) and Trz2 (8.4 g, 31.4 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (13 g, 94.3 mmol) was dissolved in 39 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous 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 1-16. (Yield 71%, MS: [M+H]+= 583)

Production Example 1-17

Compound DF (15 g, 51 mmol) and phenylboronic acid (6.2 g, 51 mmol) were added to 300 ml of THF under a nitrogen atmosphere, followed by stirring and reflux. Thereafter, potassium carbonate (21.1 g, 153 mmol) was dissolved in 63 ml of water, and after stirring sufficiently, Tetrakis (triphenylphosphine) palladium (0) (0.6 g, 0.5 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.1 g of compound subDF-1. (Yield 65%, MS: [M+H]+= 336)

In a nitrogen atmosphere, the compound subDF-1 (15 g, 44.7 mmol) and Trz18 (18 g, 44.7 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.5 g, 134 mmol) was dissolved in 56 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 12 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 18.2 g of Compound 1-17. (Yield 62%, MS: [M+H]+= 659)

Preparation Example 2-1

In a nitrogen atmosphere, compound AA (15 g, 53.9 mmol) and naphthalen-2-ylboronic acid (9.3 g, 53.9 mmol) were put in 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (22.4 g, 161.8 mmol) was dissolved in 67 ml of water, and after sufficiently stirred, Tetrakis (triphenylphosphine) palladium (0) (0.6 g, 0.5 mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.3 g of compound subAA-3. (Yield 77%, MS: [M+H]+= 370)

In a nitrogen atmosphere, compound subAA-3 (10 g, 27 mmol), compound amine1 (9.1 g, 27 mmol), and sodium tert-butoxide (8.6 g, 40.6 mmol) were added to 200 ml of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.8 g of Compound 2-1. (Yield 60%, MS: [M+H]+= 669)

Preparation Example 2-2

In a nitrogen atmosphere, compound subAB-1 (10 g, 31.3 mmol), compound amine2 (9.2 g, 31.3 mmol), and sodium tert-butoxide (10 g, 46.9 mmol) were added to 200 ml of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.9 g of Compound 2-2. (Yield 66%, MS: [M+H]+= 579)

Preparation Example 2-3

In a nitrogen atmosphere, compound AC (15 g, 53.9 mmol) and phenylboronic acid (6.6 g, 53.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (22.4 g, 161.8 mmol) was dissolved in 67 ml of water, and after sufficiently stirred, Tetrakis (triphenylphosphine) palladium (0) (0.6 g, 0.5 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.1 g of compound subAC-1. (Yield 76%, MS: [M+H]+= 320)

In a nitrogen atmosphere, compound subAC-1 (10 g, 31.3 mmol), compound amine3 (12.8 g, 31.3 mmol), and sodium tert-butoxide (10 g, 46.9 mmol) were added to 200 ml of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15 g of Compound 2-3. (Yield: 69%, MS: [M+H] + = 694)

Preparation Example 2-4

In a nitrogen atmosphere, compound subAC-1 (15 g, 46.9 mmol) and compound amine4 (22.8 g, 46.9 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (19.5 g, 140.7 mmol) was dissolved in 58 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 23.1 g of Compound 2-4. (Yield 68%, MS: [M+H]+= 725)

Preparation Example 2-5

Compound AE (15 g, 53.9 mmol) and [1,1'-biphenyl] -4-ylboronic acid (10.7 g, 53.9 mmol) were added to 300 ml of THF under a nitrogen atmosphere, followed by stirring and reflux. Thereafter, potassium carbonate (22.4 g, 161.8 mmol) was dissolved in 67 ml of water, and after sufficiently stirred, Tetrakis (triphenylphosphine) palladium (0) (0.6 g, 0.5 mmol) was added. After reacting for 12 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 17 g of compound subAE-2. (Yield 80%, MS: [M+H]+= 396)

In a nitrogen atmosphere, compound subAE-2 (10 g, 25.3 mmol), compound amine5 (7.5 g, 25.3 mmol), and sodium tert-butoxide (8 g, 37.9 mmol) were added to 200 ml of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 8.3 g of Compound 2-5. (Yield 50%, MS: [M+H]+= 655)

Production Example 2-6

In a nitrogen atmosphere, compound AF (15 g, 53.9 mmol) and phenylboronic acid (6.6 g, 53.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (22.4 g, 161.8 mmol) was dissolved in 67 ml of water, and after sufficiently stirred, Tetrakis (triphenylphosphine) palladium (0) (0.6 g, 0.5 mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.7 g of compound subAF-2. (Yield 74%, MS: [M+H]+= 320)

In a nitrogen atmosphere, compound subAF-2 (15 g, 46.9 mmol) and compound amine6 (20.7 g, 46.9 mmol) were added to 300 ml of THF, followed by stirring and reflux. Thereafter, potassium carbonate (19.5 g, 140.7 mmol) was dissolved in 58 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 20.1 g of compound 2-6. (Yield 63%, MS: [M+H]+= 681)

Production Example 2-7

In a nitrogen atmosphere, compound subBA-1 (15 g, 46.9 mmol) and compound amine10 (18.5 g, 46.9 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (19.5 g, 140.7 mmol) was dissolved in 58 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 23.2 g of compound 2-7. (Yield 78%, MS: [M+H]+= 635)

Production Example 2-8

In a nitrogen atmosphere, compound subBB-1 (15 g, 46.9 mmol) and compound amine11 (23.1 g, 46.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (19.5 g, 140.7 mmol) was dissolved in 58 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 12 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 26.7 g of Compound 2-8. (Yield 78%, MS: [M+H]+= 731)

Production Example 2-9

In a nitrogen atmosphere, compound subBB-1 (10 g, 31.3 mmol), compound amine12 (13.3 g, 31.3 mmol), and sodium tert-butoxide (10 g, 46.9 mmol) were added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.2 g of Compound 2-9. (Yield 60%, MS: [M+H]+= 703)

Preparation Example 2-10

In a nitrogen atmosphere, compound BC (15 g, 53.9 mmol) and naphthalen-2-ylboronic acid (9.3 g, 53.9 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (22.4 g, 161.8 mmol) was dissolved in 67 ml of water, and after sufficiently stirred, Tetrakis (triphenylphosphine) palladium (0) (0.6 g, 0.5 mmol) was added. After reacting for 11 hours, it was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.1 g of compound subBC-1. (Yield 76%, MS: [M+H]+= 370)

In a nitrogen atmosphere, compound subBC-1 (10 g, 27 mmol), compound amine13 (8.7 g, 27 mmol), and sodium tert-butoxide (8.6 g, 40.6 mmol) were added to 200 ml of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9 g of compound 2-10. (Yield 51%, MS: [M+H] + = 655)

Preparation Example 2-11

In a nitrogen atmosphere, compound BC (15 g, 53.9 mmol) and phenylboronic acid (6.6 g, 53.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (22.4 g, 161.8 mmol) was dissolved in 67 ml of water, and after sufficiently stirred, Tetrakis (triphenylphosphine) palladium (0) (0.6 g, 0.5 mmol) was added. After reacting for 11 hours, it was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.4 g of compound subBC-2. (Yield 78%, MS: [M+H]+= 320)

In a nitrogen atmosphere, compound subBC-2 (15 g, 46.9 mmol) and compound amine14 (17.8 g, 46.9 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (19.5 g, 140.7 mmol) was dissolved in 58 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 21.5 g of Compound 2-11. (Yield 74%, MS: [M+H]+= 619)

Preparation Example 2-12

In a nitrogen atmosphere, compound BC (15 g, 53.9 mmol) and dibenzo[b,d]furan-1-ylboronic acid (11.4 g, 53.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (22.4 g, 161.8 mmol) was dissolved in 67 ml of water, and after sufficiently stirred, Tetrakis (triphenylphosphine) palladium (0) (0.6 g, 0.5 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.9 g of compound subBC-3. (Yield 63%, MS: [M+H]+= 410)

In a nitrogen atmosphere, compound subBC-3 (15 g, 36.6 mmol) and compound amine15 (16.2 g, 36.6 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (15.2 g, 109.8 mmol) was dissolved in 46 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 18.3 g of Compound 2-12. (Yield 65%, MS: [M+H]+= 771)

Preparation Example 2-13

In a nitrogen atmosphere, compound BE (15 g, 53.9 mmol) and phenylboronic acid (6.6 g, 53.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (22.4 g, 161.8 mmol) was dissolved in 67 ml of water, and after sufficiently stirred, Tetrakis (triphenylphosphine) palladium (0) (0.6 g, 0.5 mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.1 g of compound subBE-2. (Yield 76%, MS: [M+H]+= 320)

In a nitrogen atmosphere, compound subBE-2 (10 g, 31.3 mmol), compound amine16 (10.8 g, 31.3 mmol), and sodium tert-butoxide (10 g, 46.9 mmol) were added to 200 ml of Xylene, followed by stirring and reflux. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13 g of compound 2-13. (Yield 66%, MS: [M+H]+ = 629)

Production Example 2-14

In a nitrogen atmosphere, compound subBE-2 (15 g, 46.9 mmol) and compound amine17 (21.4 g, 46.9 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (19.5 g, 140.7 mmol) was dissolved in 58 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 23.4 g of Compound 2-14. (Yield 72%, MS: [M+H]+= 695)

Preparation Example 2-15

In a nitrogen atmosphere, compound subBF-1 (15 g, 46.9 mmol) and compound amine18 (22.1 g, 46.9 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (19.5 g, 140.7 mmol) was dissolved in 58 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 23.3 g of compound 2-15. (Yield 70%, MS: [M+H]+= 711)

Preparation Example 2-16

In a nitrogen atmosphere, compound CA (15 g, 51 mmol) and dibenzo[b,d]thiophen-3-ylboronic acid (11.6 g, 51 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 153 mmol) was dissolved in 63 ml of water, and after stirring sufficiently, Tetrakis (triphenylphosphine) palladium (0) (0.6 g, 0.5 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.4 g of compound subCA-2. (Yield 64%, MS: [M+H]+= 442)

In a nitrogen atmosphere, compound subCA-2 (15 g, 33.9 mmol) and compound amine22 (14.1 g, 33.9 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (14.1 g, 101.8 mmol) was dissolved in 42 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 20.8 g of compound 2-16. (Yield 79%, MS: [M+H]+= 777)

Preparation Example 2-17

In a nitrogen atmosphere, compound subCB-1 (10 g, 29.8 mmol), compound amine23 (12.6 g, 29.8 mmol), and sodium tert-butoxide (9.5 g, 44.7 mmol) were added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.5 g of compound 2-17. (Yield 58%, MS: [M+H]+= 722)

Preparation Example 2-18

In a nitrogen atmosphere, compound subCB-1 (15 g, 44.7 mmol) and compound amine24 (21.1 g, 44.7 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (18.5 g, 134 mmol) was dissolved in 56 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 20.1 g of Compound 2-18. (Yield 62%, MS: [M+H]+= 727)

Preparation Example 2-19

In a nitrogen atmosphere, compound CC (15 g, 51 mmol) and phenylboronic acid (6.2 g, 51 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 153 mmol) was dissolved in 63 ml of water, and after stirring sufficiently, Tetrakis (triphenylphosphine) palladium (0) (0.6 g, 0.5 mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.9 g of compound subCC-1. (Yield 64%, MS: [M+H]+= 336)

In a nitrogen atmosphere, compound subCC-1 (10 g, 29.8 mmol), compound amine25 (12.3 g, 29.8 mmol), and sodium tert-butoxide (9.5 g, 44.7 mmol) were added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14 g of compound 2-19. (Yield: 66%, MS: [M+H] + = 711)

Preparation Example 2-20

In a nitrogen atmosphere, compound subCC-1 (10 g, 29.8 mmol), compound amine26 (11.1 g, 29.8 mmol), and sodium tert-butoxide (9.5 g, 44.7 mmol) were added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12 g of compound 2-20. (Yield: 60%, MS: [M+H] + = 671)

Preparation Example 2-21

In a nitrogen atmosphere, compound subCC-1 (10 g, 29.8 mmol), compound amine27 (14.6 g, 29.8 mmol), and sodium tert-butoxide (9.5 g, 44.7 mmol) were added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.8 g of compound 2-21. (Yield 53%, MS: [M+H]+= 747)

Preparation Example 2-22

In a nitrogen atmosphere, compound CD (15 g, 51 mmol) and phenylboronic acid (6.2 g, 51 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 153 mmol) was dissolved in 63 ml of water, and after stirring sufficiently, Tetrakis (triphenylphosphine) palladium (0) (0.6 g, 0.5 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.8 g of compound subCD-1. (Yield 75%, MS: [M+H]+= 336)

In a nitrogen atmosphere, compound subCD-1 (15 g, 44.7 mmol) and compound amine28 (19.7 g, 44.7 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (18.5 g, 134 mmol) was dissolved in 56 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 11 hours, it was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 20.2 g of Compound 2-22. (Yield 65%, MS: [M+H]+= 697)

Preparation Example 2-23

In a nitrogen atmosphere, compound CE (15 g, 51 mmol) and phenylboronic acid (6.2 g, 51 mmol) were put into 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 153 mmol) was dissolved in 63 ml of water, and after stirring sufficiently, Tetrakis (triphenylphosphine) palladium (0) (0.6 g, 0.5 mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.5 g of compound subCE-2. (Yield 79%, MS: [M+H]+= 336)

In a nitrogen atmosphere, compound subCE-2 (10 g, 29.8 mmol), compound amine29 (10.3 g, 29.8 mmol), and sodium tert-butoxide (9.5 g, 44.7 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.9 g of compound 2-23. (Yield 62%, MS: [M+H]+= 645)

Preparation Example 2-24

In a nitrogen atmosphere, compound CF (15 g, 51 mmol) and phenylboronic acid (6.2 g, 51 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 153 mmol) was dissolved in 63 ml of water, and after stirring sufficiently, Tetrakis (triphenylphosphine) palladium (0) (0.6 g, 0.5 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.6 g of compound subCF-2. (Yield 68%, MS: [M+H]+= 336)

In a nitrogen atmosphere, compound subCF-2 (10 g, 29.8 mmol), compound amine30 (10.5 g, 29.8 mmol), and sodium tert-butoxide (9.5 g, 44.7 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.4 g of compound 2-24. (Yield 64%, MS: [M+H]+= 651)

Preparation Example 2-25

In a nitrogen atmosphere, compound subDB-1 (15 g, 38.9 mmol) and compound amine33 (17.2 g, 38.9 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (16.1 g, 116.6 mmol) was dissolved in 48 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 21.2 g of Compound 2-25. (Yield 73%, MS: [M+H]+= 747)

Preparation Example 2-26

In a nitrogen atmosphere, compound DB (15 g, 51 mmol) and phenylboronic acid (6.2 g, 51 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 153 mmol) was dissolved in 63 ml of water, and after stirring sufficiently, Tetrakis (triphenylphosphine) palladium (0) (0.6 g, 0.5 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.2 g of compound subDB-2. (Yield 77%, MS: [M+H]+= 336)

In a nitrogen atmosphere, compound subDB-2 (10 g, 31.3 mmol), compound amine34 (12.9 g, 31.3 mmol), and sodium tert-butoxide (10 g, 46.9 mmol) were added to 200 ml of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15 g of compound 2-26. (Yield 69%, MS: [M+H] + = 695)

Preparation Example 2-27

Compound DC (15 g, 51 mmol) and naphthalen-2-ylboronic acid (8.8 g, 51 mmol) were added to 300 ml of THF under nitrogen atmosphere and stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 153 mmol) was dissolved in 63 ml of water, and after stirring sufficiently, Tetrakis (triphenylphosphine) palladium (0) (0.6 g, 0.5 mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.8 g of compound subDC-1. (Yield 65%, MS: [M+H]+= 386)

In a nitrogen atmosphere, compound subDC-1 (10 g, 25.9 mmol), compound amine13 (8.3 g, 25.9 mmol), and sodium tert-butoxide (8.3 g, 38.9 mmol) were added to 200 ml of Xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.9 g of compound 2-27. (Yield 63%, MS: [M+H]+= 671)

Preparation Example 2-28

Compound DC (15 g, 51 mmol) and phenylboronic acid (6.2 g, 51 mmol) were added to 300 ml of THF under a nitrogen atmosphere, followed by stirring and reflux. Thereafter, potassium carbonate (21.1 g, 153 mmol) was dissolved in 63 ml of water, and after stirring sufficiently, Tetrakis (triphenylphosphine) palladium (0) (0.6 g, 0.5 mmol) was added. After reacting for 12 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.1 g of compound subDC-2. (Yield 65%, MS: [M+H]+= 336)

In a nitrogen atmosphere, compound subDC-2 (15 g, 44.7 mmol) and compound amine7 (21 g, 44.7 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (18.5 g, 134 mmol) was dissolved in 56 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 21 g of compound 2-28. (Yield 65%, MS: [M+H]+= 725)

Preparation Example 2-29

In a nitrogen atmosphere, compound DE (15 g, 51 mmol) and dibenzo[b,d]furan-2-ylboronic acid (10.8 g, 51 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 153 mmol) was dissolved in 63 ml of water, and after stirring sufficiently, Tetrakis (triphenylphosphine) palladium (0) (0.6 g, 0.5 mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16 g of compound subDE-1. (Yield 74%, MS: [M+H]+= 426)

In a nitrogen atmosphere, compound subDE-1 (15 g, 35.2 mmol) and compound amine35 (17.3 g, 35.2 mmol) were added to 300 ml of THF, followed by stirring and reflux. Thereafter, potassium carbonate (14.6 g, 105.7 mmol) was dissolved in 44 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 19.7 g of Compound 2-29. (Yield 67%, MS: [M+H]+= 837)

Preparation Example 2-30

Compound DF (15 g, 51 mmol) and [1,1'-biphenyl] -4-ylboronic acid (10.1 g, 51 mmol) were added to 300 ml of THF under a nitrogen atmosphere, followed by stirring and reflux. Thereafter, potassium carbonate (21.1 g, 153 mmol) was dissolved in 63 ml of water, and after stirring sufficiently, Tetrakis (triphenylphosphine) palladium (0) (0.6 g, 0.5 mmol) was added. After reacting for 12 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.5 g of compound subDF-2. (Yield 74%, MS: [M+H]+= 412)

In a nitrogen atmosphere, the compound subDF-2 (15 g, 57.8 mmol) and the compound amine35 (28.4 g, 57.8 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (23.9 g, 173.3 mmol) was dissolved in 72 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 29.4 g of Compound 2-30. (Yield 62%, MS: [M+H]+= 823)

[Example]

Comparative Example A

A glass substrate coated with ITO (indium tin oxide) to a thickness of 1000 Å was put in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, a Fischer Co. product was used as the detergent, and distilled water filtered through a second filter of a Millipore Co. product was used as the distilled water. After washing the ITO for 30 minutes, ultrasonic cleaning was performed twice with distilled water for 10 minutes. After washing with distilled water, ultrasonic cleaning was performed with solvents such as isopropyl alcohol, acetone, and methanol, dried, and transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transferred to a vacuum deposition machine.

The following compound HI-1 was formed to a thickness of 1150 Å as a hole injection layer on the prepared ITO transparent electrode, but the following compound A-1 was p-doped at a concentration of 1.5 wt%. The following compound HT-1 was vacuum deposited on the hole injection layer to form a hole transport layer having a thickness of 800 Å. Subsequently, an electron blocking layer was formed by vacuum depositing the following compound EB-1 to a film thickness of 150 Å on the hole transport layer. Subsequently, the following compound RH-1 and compound Dp-7 were vacuum deposited on the EB-1 deposited film in 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 compound HB-1 to a film thickness of 30 Å. Subsequently, the following compound ET-1 and the following compound LiQ 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 1000 Å on the electron injection and transport layer.

In the above process, the deposition rate of the organic material was maintained at 0.4 ~ 0.7 Å/sec, the deposition rate of lithium fluoride on the cathode was 0.3 Å/sec, and the deposition rate of aluminum was 2 Å/sec, and the vacuum level during deposition was 2×10 ^-7 While maintaining ~ 5ⅹ10 ^-6 torr, an organic light emitting device was fabricated.

Examples 1 to 17

An organic light emitting device was manufactured in the same manner as in Comparative Example A, except that the compound shown in Table 1 was used instead of compound RH-1 as a host in the organic light emitting device of Comparative Example A.

Comparative Examples 1 to 7

An organic light emitting device was manufactured in the same manner as in Comparative Example A, except that the compound shown in Table 1 was used instead of compound RH-1 as a host in the organic light emitting device of Comparative Example A. The structures of compounds B-8 to B-14 in Table 1 are as follows.

Examples 18 to 47

An organic light emitting device of Comparative Example A was manufactured in the same manner as in Comparative Example A, except that the compound shown in Table 2 was used as an electron blocking layer material instead of compound EB-1 in the organic light emitting device of Comparative Example A.

Comparative Examples 8 to 14

An organic light emitting device of Comparative Example A was manufactured in the same manner as in Comparative Example A, except that the compound shown in Table 2 was used as an electron blocking layer material instead of compound EB-1 in the organic light emitting device of Comparative Example A. The structures of compounds B-1 to B-7 in Table 2 below are as follows.

Examples 48 to 115

In the organic light emitting device of Comparative Example A, in the same manner as in Comparative Example A, except that the compounds of the first host and the second host described in Table 3 were used in a weight ratio of 1: 1 instead of compound RH-1. An organic light emitting device was manufactured.

[Experimental Example]

When current was applied to the organic light emitting devices prepared in Examples 1 to 161 and Comparative Examples A and Comparative Examples 1 to 88, voltage and efficiency were measured (15 mA/cm ² standard) and the results It was shown in Tables 1 to 3 below. The lifetime T95 means the time required for the luminance to decrease to 95% from the initial luminance of 7,000 nit.

division host driving voltage
(V) Efficiency (cd/A) life span
T95 (hr) luminescent color Comparative Example A Compound RH-1 3.91 16.54 113 Red Example 1 compound 1-1 3.63 19.35 178 Red Example 2 compound 1-2 3.65 19.89 187 Red Example 3 compound 1-3 3.61 20.14 196 Red Example 4 compound 1-4 3.54 20.86 217 Red Example 5 compound 1-5 3.59 20.35 203 Red Example 6 compound 1-6 3.63 19.67 186 Red Example 7 compound 1-7 3.72 19.03 173 Red Example 8 compound 1-8 3.69 20.27 193 Red Example 9 compound 1-9 3.73 19.38 182 Red Example 10 compound 1-10 3.76 18.86 186 Red Example 11 compound 1-11 3.81 18.51 179 Red Example 12 compound 1-12 3.83 18.30 167 Red Example 13 compound 1-13 3.72 19.34 193 Red Example 14 compound 1-14 3.75 19.02 190 Red Example 15 compound 1-15 3.80 18.45 172 Red Example 16 compound 1-16 3.84 18.26 169 Red Example 17 compound 1-17 3.76 18.93 184 Red Comparative Example 1 Compound B-8 4.05 16.92 98 Red Comparative Example 2 Compound B-9 3.98 17.39 125 Red Comparative Example 3 Compound B-10 3.95 17.64 133 Red Comparative Example 4 compound B-11 4.03 17.03 117 Red Comparative Example 5 compound B-12 3.97 16.85 102 Red Comparative Example 6 compound B-13 4.09 16.31 94 Red Comparative Example 7 Compound B-14 4.11 12.76 76 Red

division electron blocking layer driving voltage
(V) Efficiency (cd/A) life span
T95 (hr) luminescent color Example 18 compound 2-1 3.71 18.72 159 Red Example 19 compound 2-2 3.78 18.75 167 Red Example 20 compound 2-3 3.75 18.22 172 Red Example 21 compound 2-4 3.82 19.19 161 Red Example 22 compound 2-5 3.79 18.64 164 Red Example 23 compound 2-6 3.73 18.36 166 Red Example 24 compound 2-7 3.71 18.67 179 Red Example 25 compound 2-8 3.84 18.76 185 Red Example 26 compound 2-9 3.67 18.96 165 Red Example 27 compound 2-10 3.69 19.37 186 Red Example 28 compound 2-11 3.77 19.82 183 Red Example 29 compound 2-12 3.67 20.51 178 Red Example 30 compound 2-13 3.71 19.12 184 Red Example 31 compound 2-14 3.78 20.61 171 Red Example 32 compound 2-15 3.72 19.26 169 Red Example 33 compound 2-16 3.84 21.63 183 Red Example 34 compound 2-17 3.75 21.97 180 Red Example 35 compound 2-18 3.78 20.55 174 Red Example 36 compound 2-19 3.76 19.49 186 Red Example 37 compound 2-20 3.67 20.45 187 Red Example 38 compound 2-21 3.80 20.10 180 Red Example 39 compound 2-22 3.81 19.44 175 Red Example 40 compound 2-23 3.78 21.76 164 Red Example 41 compound 2-24 3.74 18.84 193 Red Example 42 compound 2-25 3.81 20.37 179 Red Example 43 compound 2-26 3.71 18.69 183 Red Example 44 compound 2-27 3.72 19.46 176 Red Example 45 compound 2-28 3.83 20.97 168 Red Example 46 compound 2-29 3.82 18.93 179 Red Example 47 compound 2-30 3.80 20.08 175 Red Comparative Example 8 Compound B-1 3.96 16.36 104 Red Comparative Example 9 Compound B-2 4.03 17.09 127 Red Comparative Example 10 Compound B-3 3.92 17.12 138 Red Comparative Example 11 Compound B-4 3.96 16.23 106 Red Comparative Example 12 Compound B-5 3.94 16.18 93 Red Comparative Example 13 Compound B-6 4.13 15.60 71 Red Comparative Example 14 Compound B-7 4.27 12.21 84 Red

division 1st host 2nd host driving voltage
(V) efficiency
(cd/A) life span
T95 (hr) luminescent color Example 48 compound 1-1 compound 2-1 3.49 21.52 218 Red Example 49 compound 1-1 Compounds 2-4 3.50 21.87 223 Red Example 50 compound 1-1 Compounds 2-10 3.41 20.19 216 Red Example 51 compound 1-1 Compounds 2-15 3.57 21.10 221 Red Example 52 compound 1-1 compound 2-22 3.45 19.82 207 Red Example 53 compound 1-1 compound 2-26 3.49 19.84 208 Red Example 56 Compounds 1-3 compound 2-2 3.65 23.65 229 Red Example 57 Compounds 1-3 Compounds 2-5 3.63 23.18 220 Red Example 58 Compounds 1-3 compound 2-11 3.65 21.54 230 Red Example 59 Compounds 1-3 Compounds 2-16 3.48 23.31 233 Red Example 60 Compounds 1-3 compound 2-23 3.62 22.16 212 Red Example 61 Compounds 1-3 compound 2-27 3.46 23.65 212 Red Example 62 Compounds 1-4 compound 2-3 3.49 23.86 237 Red Example 63 Compounds 1-4 compound 2-6 3.47 23.17 217 Red Example 64 Compounds 1-4 Compounds 2-12 3.44 23.77 232 Red Example 65 Compounds 1-4 Compounds 2-17 3.51 22.92 232 Red Example 66 Compounds 1-4 compound 2-24 3.56 24.00 229 Red Example 67 Compounds 1-4 compound 2-28 3.49 22.88 232 Red Example 68 Compounds 1-5 compound 2-1 3.42 19.68 216 Red Example 69 Compounds 1-5 Compounds 2-4 3.40 20.99 221 Red Example 70 Compounds 1-5 Compounds 2-13 3.56 19.58 214 Red Example 71 Compounds 1-5 Compounds 2-18 3.40 20.84 206 Red Example 72 Compounds 1-5 compound 2-25 3.50 21.32 218 Red Example 73 Compounds 1-5 compound 2-29 3.40 19.56 222 Red Example 74 Compounds 1-8 compound 2-1 3.51 23.01 215 Red Example 75 Compounds 1-8 Compounds 2-4 3.62 23.29 221 Red Example 76 Compounds 1-8 Compounds 2-10 3.64 23.17 216 Red Example 77 Compounds 1-8 Compounds 2-15 3.63 21.39 233 Red Example 78 Compounds 1-8 compound 2-22 3.63 22.22 238 Red Example 79 Compounds 1-8 compound 2-26 3.61 22.77 234 Red Example 80 compounds 1-9 compound 2-2 3.45 22.43 210 Red Example 81 compounds 1-9 Compounds 2-5 3.63 22.06 218 Red Example 82 compounds 1-9 compound 2-11 3.60 21.97 214 Red Example 83 compounds 1-9 Compounds 2-16 3.58 19.40 214 Red Example 84 compounds 1-9 compound 2-23 3.59 21.49 209 Red Example 85 compounds 1-9 compound 2-27 3.58 21.86 224 Red Example 86 compounds 1-10 compound 2-3 3.45 23.54 224 Red Example 87 compounds 1-10 compound 2-6 3.46 22.53 214 Red Example 88 compounds 1-10 Compounds 2-12 3.50 23.21 217 Red Example 89 compounds 1-10 Compounds 2-17 3.48 23.16 226 Red Example 90 compounds 1-10 compound 2-24 3.65 21.57 206 Red Example 91 compounds 1-10 compound 2-28 3.59 22.68 206 Red Example 92 Compounds 1-13 compound 2-1 3.46 21.32 223 Red Example 93 Compounds 1-13 Compounds 2-4 3.60 20.86 212 Red Example 94 Compounds 1-13 Compounds 2-13 3.41 20.17 211 Red Example 95 Compounds 1-13 Compounds 2-18 3.42 21.64 221 Red Example 96 Compounds 1-13 compound 2-25 3.52 20.87 209 Red Example 97 Compounds 1-13 compound 2-29 3.50 21.27 216 Red Example 98 Compounds 1-14 compound 2-1 3.55 24.25 217 Red Example 99 Compounds 1-14 Compounds 2-4 3.36 24.03 219 Red Example 100 Compounds 1-14 Compounds 2-10 3.57 23.66 240 Red Example 101 Compounds 1-14 Compounds 2-15 3.35 23.52 240 Red Example 102 Compounds 1-14 compound 2-22 3.41 23.56 223 Red Example 103 Compounds 1-14 compound 2-26 3.56 23.66 219 Red Example 104 compounds 1-15 compound 2-2 3.49 21.05 226 Red Example 105 compounds 1-15 Compounds 2-5 3.60 21.68 211 Red Example 106 compounds 1-15 compound 2-11 3.48 21.49 210 Red Example 107 compounds 1-15 Compounds 2-16 3.60 22.04 215 Red Example 108 compounds 1-15 compound 2-23 3.56 22.26 235 Red Example 109 compounds 1-15 compound 2-27 3.65 22.87 228 Red Example 110 compounds 1-16 compound 2-3 3.41 19.24 215 Red Example 111 compounds 1-16 compound 2-6 3.45 20.36 215 Red Example 112 compounds 1-16 Compounds 2-12 3.47 19.91 215 Red Example 113 compounds 1-16 Compounds 2-17 3.44 21.52 224 Red Example 114 compounds 1-16 compound 2-24 3.58 21.40 216 Red Example 115 compounds 1-16 compound 2-28 3.42 21.17 220 Red

When current was applied to the organic light emitting devices manufactured in Examples 1 to 115 and Comparative Examples 1 to 14, the results of Tables 1 to 3 were obtained.

When the compounds 1-1 to 1-17 of the present invention were used as red hosts, it was confirmed that the driving voltage decreased and the efficiency and lifetime increased compared to the compounds of Comparative Examples, as shown in Table 1. Compounds 2-1 to 2 of the present invention Even when -40 was used as an electron blocking layer, as shown in Table 2, the driving voltage decreased and the efficiency and lifespan increased compared to the comparative compounds.

Additionally, in Table 3, a single material was used as a red host by co-deposition using one of compounds 1-1 to 1-17 as a first host and one of compounds 2-1 to 2-40 as a second host. It was confirmed that the driving voltage decreased and the efficiency and lifetime increased compared to when using the host of .

That is, from the results of Tables 1 to 3, when the compound of one embodiment is used as a host of a red light emitting layer or an electron blocking layer in a device expressing red color, the driving voltage, luminous efficiency and lifetime characteristics of the organic light emitting device can be improved. I was able to confirm that there is

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 (13)

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

In Formula 1,
A is a thiazole ring or an oxazole ring fused with an adjacent ring,
L ₁ is a single bond; Substituted or unsubstituted C _6-60 arylene; Or a C _2-60 heteroarylene containing at least one selected from the group consisting of substituted or unsubstituted N, O and S,
R ₁ is

or

ego,
Ar ₁ to Ar ₄ are each independently a substituted or unsubstituted C _6-60 aryl; Or a C _2-60 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O and S,
The L ₂ to L ₅ are each independently a single bond; Substituted or unsubstituted C _6-60 arylene; Or a C _2-60 heteroarylene containing at least one selected from the group consisting of substituted or unsubstituted N, O and S,
R ₂ is unsubstituted C _6-60 aryl; Or a C _2-60 heteroaryl containing at least one selected from the group consisting of unsubstituted N, O and S,
D is deuterium;
n is an integer of 0 or more and 5 or less;
However, the following compounds are excluded from the compounds represented by Formula 1:
.
According to claim 1,
Formula 1 is represented by any one of the following Formulas 1-1 to 1-4,
compound:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Formula 1-1 to Formula 1-4,
Descriptions of R ₁ , R ₂ , L ₁ , D and n are as defined in claim 1.
According to claim 1,
L ₁ is a single bond, phenylene, biphenyldiyl, or naphthalenediyl;
compound.
According to claim 1,
Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, naphthyl, phenanthrenyl, dibenzofuranyl, or dibenzothiophenyl;
compound.
According to claim 1,
Ar ₃ and Ar ₄ are each independently phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, dibenzofuranyl, dibenzothiophenyl, phenyl carbazolyl, or phenyl naphthyl;
compound.
According to claim 1,
L ₂ and L ₃ are each independently a single bond, phenylene, or naphthalenediyl;
compound.
According to claim 1,
L ₄ and L ₅ are each independently a single bond, phenylene, biphenyldiyl, naphthalenediyl, or carbazoldiyl;
compound.
According to claim 1,
At least one of Ar ₁ and Ar ₂ is a substituted or unsubstituted C _6-60 aryl;
compound.
According to claim 1,
At least one of Ar ₃ and Ar ₄ is a substituted or unsubstituted C _6-60 aryl;
compound.
According to claim 1,
R ₂ is phenyl, biphenylyl, naphthyl, dibenzofuranyl, or dibenzothiophenyl;
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 contains one compound according to any one of claims 1 to 11. including more than
organic light emitting device.
According to claim 12,
The organic material layer is a light emitting layer or an electron blocking layer,
organic light emitting device.