KR102576738B1 - 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 containing the same.

Description

Novel compound and organic light emitting device comprising the same}

The present invention relates to novel compounds and organic light-emitting devices containing them.

In general, organic luminescence refers to a phenomenon that converts electrical energy into light energy using organic materials. Organic light-emitting devices using the organic light-emitting phenomenon have a wide viewing angle, excellent contrast, fast response time, and excellent luminance, driving voltage, and response speed characteristics, so much research is being conducted.

Organic light emitting devices generally have a structure including an anode, a cathode, and an organic layer between the anode and the cathode. The organic material layer is often composed of a multi-layer structure made of different materials to increase the efficiency and stability of the organic light-emitting device, and may be composed of, 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 into the organic material layer. When the injected holes and electrons meet, an exciton is formed, and this exciton is When it falls back to the ground state, it glows.

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

Korean Patent Publication No. 10-2000-0051826

The present invention relates to novel organic light-emitting materials and organic light-emitting devices containing the same.

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

[Formula 1]

In Formula 1,

A is a thiazole ring or oxazole ring fused to 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 substituted or unsubstituted C _6-60 aryl; or C _2-60 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O and S,

Wherein 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 substituted or unsubstituted C _6-60 aryl; or 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 between 0 and 5.

In addition, the present invention includes a first electrode; a second electrode provided opposite to the first electrode; and an organic light-emitting device comprising at least one organic material layer provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes at least one compound represented by Formula 1. to provide.

The compound represented by the above-described formula 1 can be used as a material for the organic layer of an organic light-emitting device, and can improve efficiency, low driving voltage, and/or lifespan characteristics of the organic light-emitting device. In particular, the compound represented by the above-mentioned formula 1 can be used as a hole injection, hole transport, light emitting, electron transport, or electron injection material.

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

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

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

In this specification, or means a bond connected to another substituent.

As used herein, the term “substituted or unsubstituted” refers to deuterium; halogen group; Nitrile group; nitro group; hydroxyl group; carbonyl group; ester group; imide group; amino group; Phosphine oxide group; Alkoxy group; Aryloxy group; Alkylthioxy group; Arylthioxy group; Alkyl sulphoxy group; Aryl sulfoxy group; silyl group; boron group; Alkyl group; Cycloalkyl group; alkenyl group; Aryl group; Aralkyl group; Aralkenyl group; Alkylaryl group; Alkylamine group; Aralkylamine group; heteroarylamine group; Arylamine group; Arylphosphine group; or 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 of the above-exemplified substituents linked. . For example, “a substituent group in which two or more substituents are connected” may be a biphenyl group. That is, the biphenyl group may be an aryl group, or it may be interpreted as a substituent in which two phenyl groups are connected.

In this specification, the carbon number of the carbonyl group is not particularly limited, but is preferably 1 to 40 carbon atoms. Specifically, the substituent may have the following structure, but is not limited thereto.

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

In this specification, the carbon number of the imide group is not particularly limited, but is preferably 1 to 25 carbon atoms. Specifically, the substituent may have the following structure, but is not limited thereto.

In the present specification, the silyl group specifically includes trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, etc. However, it is not limited to this.

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

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

In the present specification, the alkyl group may be straight chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the carbon number of the alkyl group is 1 to 20. According to another embodiment, the carbon number of the alkyl group is 1 to 10. According to another embodiment, the carbon number of the alkyl group is 1 to 6. Specific examples of alkyl groups 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 to these.

In the present specification, the alkenyl group may be straight chain 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 embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another 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 are not limited to these.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another embodiment, the carbon number of the cycloalkyl group is 3 to 20. According to another embodiment, the carbon number 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, Examples include, but are not limited to, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, and cyclooctyl.

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 aryl group has 6 to 30 carbon atoms. According to one embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a monocyclic aryl group, such as a phenyl group, biphenyl group, or terphenyl 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, etc., but is not limited thereto.

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

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 it is preferably 2 to 60 carbon atoms. According to one embodiment, the heteroaryl group has 6 to 30 carbon atoms. According to one embodiment, the heteroaryl group has 6 to 20 carbon atoms. Examples of heteroaryl groups include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, and acridyl group. , pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group , carbazole group, benzooxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, isoxazolyl group, thiadia These include, but are not limited to, a zolyl group, a phenothiazinyl group, and a dibenzofuranyl group.

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

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

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Formulas 1-1 to 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 it may be 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, naphthalenediyl, or dibenzofurandiyl.

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 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, Ar ₁ and Ar ₂ may each independently be phenyl, biphenylyl, terphenylyl, 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 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, Ar ₃ and Ar ₄ are each independently selected from phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, dimethylfluorenyl, dibenzofuranyl, dibenzothiophenyl, phenyl carbazolyl. , or phenyl naphthyl.

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 be a single bond, phenylene, biphenyldiyl, 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 it may be 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 be a single bond, phenylene, biphenyldiyl, naphthalenediyl, or carbazoldiyl.

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 substituted or unsubstituted C _6-60 aryl, and more preferably, at least one of Ar ₁ and Ar ₂ may be substituted or unsubstituted C _6-20 It may be aryl, more preferably, at least one of Ar ₁ and Ar ₂ may be unsubstituted C _6-20 aryl, and most preferably, at least one of Ar ₁ and Ar ₂ may be phenyl, biphenylyl. , terphenylyl, or naphthyl.

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

Meanwhile, R ₂ is a substituent of ring A.

Preferably, R ₂ is substituted or unsubstituted C _6-20 aryl; Alternatively, 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 may be phenyl, biphenylyl, naphthyl, dibenzofuranyl, or dibenzothiophenyl.

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

.

.

Preferably, n is an integer equal to 0.

Representative examples of compounds 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.For example, in the compound represented by Formula 1, L ₁ is a single bond, and R ₁ is

In this case, it can be prepared by the preparation method shown in Scheme 1 below. For some compounds, it can be prepared by the preparation method shown in Scheme 2 below, and the remaining compounds can be prepared similarly.

[Scheme 1]

[Scheme 2]

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

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 according to what is known in the art. In addition, 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 according to what is known in the art. The manufacturing method may be further detailed in the manufacturing examples described later.

Additionally, the present invention provides an organic light-emitting device containing the compound represented by Formula 1 above. In one example, the present invention includes a first electrode; a second electrode provided opposite to the first electrode; And an organic light-emitting device comprising at least one organic material layer provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes at least one compound represented by 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 that includes a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, etc. as an organic material layer. However, the structure of the organic light emitting device is not limited to this and may include a smaller number of organic material layers.

Additionally, the organic layer may include a light-emitting layer, and the light-emitting layer may include the compound represented by Formula 1.

In addition, the organic material layer may include a hole transport layer, a hole injection layer, or a layer that simultaneously performs hole transport and hole injection, and the hole transport layer, the hole injection layer, or the layer that performs both hole transport and hole injection has the formula above: It may include a compound represented by 1.

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

Additionally, 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. Additionally, the organic light emitting device according to the present invention may be an inverted type organic light emitting device in which a cathode, one or more organic 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 FIG. 1.

Figure 1 shows an example of an organic light emitting device consisting of a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4. Figure 2 shows a substrate (1), anode (2), hole injection layer (5), hole transport layer (6), electron blocking layer (7), light emitting layer (3), hole blocking layer (8), electron injection and transport layer ( 9) and a cathode 4. An example of an organic light-emitting device is shown. In this structure, the compound represented by 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 can be manufactured using materials and methods known in the art, except that at least one of the organic layers includes the compound represented by Formula 1 above. Additionally, 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 can be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate. At this time, an anode is formed by depositing a metal or a conductive metal oxide or an alloy thereof on the substrate using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation. It can be manufactured by forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer thereon, and then depositing a material that can be used as a cathode thereon. In addition to this method, an organic light-emitting device can be made by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

In addition, the compound represented by Formula 1 may be formed as an organic layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light-emitting device. Here, the solution application method refers to 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 can be manufactured by sequentially depositing a cathode material, an organic layer, and an anode material on a substrate (WO 2003/012890). However, the manufacturing method is not limited to this.

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.

The anode material is generally preferably a material with a large work function to facilitate hole injection into the organic layer. Specific examples of the anode 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 are included, but are not limited to these.

The cathode material is generally preferably a material with a small work function to facilitate electron injection into the organic layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof; There are multi-layer structure materials such as LiF/Al or LiO ₂ /Al, but they are not limited to these.

The hole injection layer is a layer that injects holes from an electrode. The hole injection material has the ability to transport holes, has an excellent hole injection effect at the anode, a light-emitting layer or a light-emitting material, and has an excellent hole injection effect on the light-emitting layer or light-emitting material. A compound that prevents movement of excitons to the electron injection layer or electron injection material and has excellent thin film forming 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 material layer. Specific examples of hole injection materials include metal porphyrin, oligothiophene, arylamine-based organic substances, hexanitrilehexaazatriphenylene-based organic substances, quinacridone-based organic substances, and perylene-based organic substances. organic substances, anthraquinone, polyaniline, and polythiophene series conductive polymers, etc., but are not limited to these.

The hole transport layer is a layer that receives holes from the hole injection layer and transports holes to the light-emitting layer. It is a hole transport material that can receive holes from the anode or hole injection layer and transfer them to the light-emitting layer, and is a material with high mobility for holes. This is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers with both conjugated and non-conjugated portions, but are not limited to these.

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 being recombined in the light emitting layer, and is also called an electron suppressing layer or an electron blocking layer. A material with lower electron affinity than the electron transport layer is preferred for the electron blocking layer. Preferably, the material represented by Formula 1 of the present invention can be used as the electron blocking layer material.

The light-emitting material is a material that can emit light in the visible light range by receiving holes and electrons from the hole transport layer and the electron transport layer, respectively, and combining them, and is preferably a material with good quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compound; Compounds of the benzoxazole, benzthiazole and benzimidazole series; Poly(p-phenylenevinylene) (PPV) series polymer; Spiro compounds; Polyfluorene, rubrene, etc., but are not limited to these.

The light emitting layer may include a host material and a dopant material. Host materials include condensed aromatic ring derivatives or heterocyclic ring-containing compounds. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, and ladder-type compounds. These include, but are not limited to, furan compounds and pyrimidine derivatives. Preferably, the 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 the 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, and 30:70 to 70. :30 or 40:60 to 60:40.

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

For example, any one or more selected from the group consisting of the following may be used as the dopant material, but it 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 recombined in the light emitting layer and passing to the electron transport layer, and is also called a hole blocking layer. A material with 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. The electron transport material is a material that can easily inject electrons from the cathode and transfer them to the light-emitting layer, and a material with high electron mobility is suitable. do. Specific examples include Al complex of 8-hydroxyquinoline; Complex containing Alq ₃ ; organic radical compounds; Hydroxyflavone-metal complexes, etc., but are not limited to these. 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 with a low work function followed by an aluminum or silver layer. Specifically, cesium, barium, calcium, ytterbium and samarium, in each case followed by an aluminum layer or a silver layer.

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

Examples of the metal complex compounds include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato)aluminum, Tris(2-methyl-8-hydroxyquinolinato)aluminum, Tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h] Quinolinato)beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)( o-cresolato) gallium, bis(2-methyl-8-quinolinato)(1-naphtolato) aluminum, bis(2-methyl-8-quinolinato)(2-naphtolato) gallium, etc. It is not limited to this.

Meanwhile, in the present invention, the “electron injection and transport layer” is a layer that performs the functions of both the electron injection layer and the electron transport layer. The materials that play the role of each layer can be used singly 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-emitting device, a top-emitting device, or a double-sided light-emitting device. In particular, it may be a bottom-emitting device that requires relatively high luminous efficiency.

Additionally, the compound represented by Formula 1 may be included in organic solar cells or organic transistors in addition to organic light-emitting devices.

The preparation of the compound represented by Formula 1 and an organic light-emitting device containing the same will be described in detail in the following Examples. However, the following examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

[Manufacturing example]

Manufacturing Example 1-1

In a nitrogen atmosphere, compound AA (15 g, 56.2 mmol) and [1,1'-biphenyl]-4-ylboronic acid (11.1 g, 56.2 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (23.3 g, 168.5 mmol) was dissolved in 70 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.6 mmol) was added. After reacting for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.2 g of compound subAA-1 (yield 64%, MS: [M+H]+= 396).

In a nitrogen atmosphere, compounds subAA-1 (15 g, 37.9 mmol) and bis(pinacolato)diboron (10.6 g, 41.7 mmol) were refluxed and stirred in 300 ml of 1,4-dioxane. Afterwards, 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 6 hours, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.8 g of compound subAA-2 (yield 75%, MS: [M+H]+= 488).

In a nitrogen atmosphere, compound subAA-2 (15 g, 30.8 mmol) and compound Trz1 (12.1 g, 30.8 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (12.8 g, 92.3 mmol) was dissolved in 38 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.2 g of compound 1-1 (yield 78%, MS: [M+H]+= 719).

Manufacturing Example 1-2

In a nitrogen atmosphere, compound AA (15 g, 56.2 mmol) and phenylboronic acid (6.8 g, 56.2 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (23.3 g, 168.5 mmol) was dissolved in 70 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.6 mmol) was added. After reaction for 8 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12 g of compound subAA-3 (yield 67%, MS: [M+H]+= 320).

In a nitrogen atmosphere, compound subAA-3 (15 g, 46.9 mmol) and compound Trz2 (18.9 g, 46.9 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (19.5 g, 140.7 mmol) was dissolved in 58 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.8 g of compound 1-2 (yield 79%, MS: [M+H]+= 643).

Manufacturing Example 1-3

In a nitrogen atmosphere, compound AB (15 g, 56.2 mmol) and phenylboronic acid (6.8 g, 56.2 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (23.3 g, 168.5 mmol) was dissolved in 70 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.6 mmol) was added. After reacting for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.6 g of compound subAB-1 (yield 76%, MS: [M+H]+= 320).

In a nitrogen atmosphere, compound subAB-1 (15 g, 46.9 mmol) and compound Trz3 (18.9 g, 46.9 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (19.5 g, 140.7 mmol) was dissolved in 58 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.9 g of compound 1-3 (yield 66%, MS: [M+H]+= 643).

Manufacturing Example 1-4

In a nitrogen atmosphere, compounds subAB-1 (15 g, 46.9 mmol) and bis(pinacolato)diboron (13.1 g, 51.6 mmol) were refluxed in 300 ml of 1,4-dioxane and stirred. Afterwards, 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 5 hours, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.5 g of compound subAB-2 (yield 65%, MS: [M+H]+= 412).

In a nitrogen atmosphere, compound subAB-2 (15 g, 46.9 mmol) and compound Trz4 (17.3 g, 46.9 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (19.5 g, 140.7 mmol) was dissolved in 58 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.6 g of compound 1-4 (yield 61%, MS: [M+H]+= 617).

Manufacturing Example 1-5

In a nitrogen atmosphere, compound AC (15 g, 56.2 mmol) and naphthalen-2-ylboronic acid (9.7 g, 56.2 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (23.3 g, 168.5 mmol) was dissolved in 70 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.6 mmol) was added. After reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.5 g of compound subAC-1 (yield 70%, MS: [M+H]+= 370).

In a nitrogen atmosphere, compounds subAC-1 (15 g, 40.6 mmol) and bis(pinacolato)diboron (11.3 g, 44.6 mmol) were refluxed in 300 ml of 1,4-dioxane and stirred. Afterwards, potassium acetate (6 g, 60.8 mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.7 g, 1.2 mmol) and tricyclohexylphosphine (0.7 g, 2.4 mmol) were added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.2 g of compound subAC-2 (yield 60%, MS: [M+H]+= 462).

In a nitrogen atmosphere, compound subAC-2 (15 g, 40.6 mmol) and compound Trz1 (16 g, 40.6 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (16.8 g, 121.7 mmol) was dissolved in 50 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.8 g of compound 1-5 (yield 60%, MS: [M+H]+= 693).

Manufacturing Example 1-6

In a nitrogen atmosphere, compound AD (15 g, 56.2 mmol) and phenylboronic acid (6.8 g, 56.2 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (23.3 g, 168.5 mmol) was dissolved in 70 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.6 mmol) was added. After reacting for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.1 g of compound subAD-1 (yield 62%, MS: [M+H]+= 320).

In a nitrogen atmosphere, compounds subAD-1 (15 g, 46.9 mmol) and bis(pinacolato)diboron (13.1 g, 51.6 mmol) were refluxed in 300 ml of 1,4-dioxane and stirred. Afterwards, 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 5 hours, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.5 g of compound subAD-2 (yield 65%, MS: [M+H]+= 412).

In a nitrogen atmosphere, compound subAD-1 (15 g, 46.9 mmol) and compound Trz5 (12.6 g, 46.9 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (19.5 g, 140.7 mmol) was dissolved in 58 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.7 g of compound 1-6 (yield 73%, MS: [M+H]+= 517).

Manufacturing Example 1-7

In a nitrogen atmosphere, compound subAD-2 (15 g, 46.9 mmol) and compound Trz6 (16.8 g, 46.9 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (19.5 g, 140.7 mmol) was dissolved in 58 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.6 g of compound 1-7 (yield 76%, MS: [M+H]+= 607).

Manufacturing Example 1-8

In a nitrogen atmosphere, compound subAD-1 (15 g, 36.5 mmol) and compound Trz7 (18 g, 36.5 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (15.1 g, 109.4 mmol) was dissolved in 45 ml of water, stirred sufficiently, and then 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, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.8 g of compound 1-8 (yield 74%, MS: [M+H]+= 733).

Manufacturing Example 1-9

In a nitrogen atmosphere, compound subAD-1 (15 g, 46.9 mmol) and compound Trz8 (18.9 g, 46.9 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (19.5 g, 140.7 mmol) was dissolved in 58 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.3 g of compound 1-9 (yield 64%, MS: [M+H]+= 643).

Manufacturing Example 1-10

In a nitrogen atmosphere, compound subAD-2 (15 g, 36.5 mmol) and compound Trz9 (14.7 g, 36.5 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (15.1 g, 109.4 mmol) was dissolved in 45 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.1 g of compound 1-10 (yield 60%, MS: [M+H]+= 643).

Manufacturing Example 1-11

In a nitrogen atmosphere, compound AD (15 g, 56.2 mmol) and dibenzo[b,d]thiophen-4-ylboronic acid (12.8 g, 56.2 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (23.3 g, 168.5 mmol) was dissolved in 70 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.6 mmol) was added. After reacting for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.7 g of compound subAD-3 (yield 74%, MS: [M+H]+= 426).

In a nitrogen atmosphere, compounds subAD-3 (15 g, 35.2 mmol) and bis(pinacolato)diboron (9.8 g, 38.7 mmol) were refluxed and stirred in 300 ml of 1,4-dioxane. Afterwards, potassium acetate (5.2 g, 52.8 mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.6 g, 1.1 mmol) and tricyclohexylphosphine (0.6 g, 2.1 mmol) were added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then 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 subAD-4 (yield 68%, MS: [M+H]+= 519).

In a nitrogen atmosphere, compound subAD-4 (15 g, 35.2 mmol) and compound Trz5 (9.4 g, 35.2 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (14.6 g, 105.7 mmol) was dissolved in 44 ml of water, stirred sufficiently, and then 0 (0.4 g, 0.4 mmol) was added. After reacting for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.7 g of compound 1-11 (yield 76%, MS: [M+H]+= 623).

Manufacturing Example 1-12

In a nitrogen atmosphere, compound AE (15 g, 56.2 mmol) and phenylboronic acid (6.8 g, 56.2 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (23.3 g, 168.5 mmol) was dissolved in 70 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.6 mmol) was added. After reacting for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.9 g of compound subAE-1 (yield 72%, MS: [M+H]+= 320).

In a nitrogen atmosphere, compound subAE-1 (15 g, 46.9 mmol) and compound Trz10 (21.3 g, 46.9 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (19.5 g, 140.7 mmol) was dissolved in 58 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.1 g of compound 1-12 (yield 68%, MS: [M+H]+= 693).

Manufacturing Example 1-13

In a nitrogen atmosphere, compound AE (15 g, 56.2 mmol) and naphthalen-2-ylboronic acid (9.7 g, 56.2 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (23.3 g, 168.5 mmol) was dissolved in 70 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.6 mmol) was added. After reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.6 g of compound subAE-2 (yield 80%, MS: [M+H]+= 370).

In a nitrogen atmosphere, compounds subAE-2 (15 g, 40.6 mmol) and bis(pinacolato)diboron (11.3 g, 44.6 mmol) were refluxed and stirred in 300 ml of 1,4-dioxane. Afterwards, potassium acetate (6 g, 60.8 mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.7 g, 1.2 mmol) and tricyclohexylphosphine (0.7 g, 2.4 mmol) were added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.2 g of compound subAE-3 (yield 60%, MS: [M+H]+= 462).

In a nitrogen atmosphere, compound subAE-3 (15 g, 32.5 mmol) and compound Trz11 (15.6 g, 32.5 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (13.5 g, 97.6 mmol) was dissolved in 40 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.7 g of compound 1-13 (yield 79%, MS: [M+H]+= 769).

Manufacturing Example 1-14

In a nitrogen atmosphere, compound AF (15 g, 56.2 mmol) and phenylboronic acid (6.8 g, 56.2 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (23.3 g, 168.5 mmol) was dissolved in 70 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.6 mmol) was added. After reacting for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.7 g of compound subAF-1 (yield 71%, MS: [M+H]+= 320).

In a nitrogen atmosphere, compounds subAF-1 (15 g, 46.9 mmol) and bis(pinacolato)diboron (13.1 g, 51.6 mmol) were refluxed and stirred in 300 ml of 1,4-dioxane. Afterwards, 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 5 hours, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.5 g of compound subAF-2 (yield 65%, MS: [M+H]+= 412).

In a nitrogen atmosphere, compound subAF-2 (15 g, 46.9 mmol) and compound Trz12 (18.5 g, 46.9 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (19.5 g, 140.7 mmol) was dissolved in 58 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reaction for 8 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.6 g of compound 1-14 (yield 65%, MS: [M+H]+= 643).

Manufacturing Example 1-15

In a nitrogen atmosphere, compound AF (15 g, 56.2 mmol) and [1,1'-biphenyl]-4-ylboronic acid (11.1 g, 56.2 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (23.3 g, 168.5 mmol) was dissolved in 70 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.6 mmol) was added. After reacting for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.4 g of compound subAF-3 (yield 74%, MS: [M+H]+= 396).

In a nitrogen atmosphere, compounds subAF-3 (15 g, 37.9 mmol) and bis(pinacolato)diboron (10.6 g, 41.7 mmol) were refluxed in 300 ml of 1,4-dioxane and stirred. Afterwards, 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, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14 g of compound subAF-4 (yield 76%, MS: [M+H]+= 488).

In a nitrogen atmosphere, compound subAF-4 (15 g, 36.5 mmol) and compound Trz13 (14.4 g, 36.5 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (15.1 g, 109.4 mmol) was dissolved in 45 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.5 g of compound 1-15 (yield 63%, MS: [M+H]+= 719).

Manufacturing Example 1-16

In a nitrogen atmosphere, compound BA (15 g, 56.2 mmol) and dibenzo[b,d]furan-2-ylboronic acid (11.9 g, 56.2 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (23.3 g, 168.5 mmol) was dissolved in 70 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.6 mmol) was added. After reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.9 g of compound subBA-1 (yield 78%, MS: [M+H]+= 410).

In a nitrogen atmosphere, compounds subBA-1 (15 g, 36.6 mmol) and bis(pinacolato)diboron (10.2 g, 40.3 mmol) were refluxed in 300 ml of 1,4-dioxane and stirred. Afterwards, potassium acetate (5.4 g, 54.9 mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.6 g, 1.1 mmol) and tricyclohexylphosphine (0.6 g, 2.2 mmol) were added. After reacting for 9 hours, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.7 g of compound subBA-2 (yield 80%, MS: [M+H]+= 502).

In a nitrogen atmosphere, compound subBA-2 (15 g, 29.9 mmol) and compound Trz5 (8 g, 29.9 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (12.4 g, 89.8 mmol) was dissolved in 37 ml of water, stirred sufficiently, and then 0 (0.3 g, 0.3 mmol) was added. After reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.9 g of compound 1-16 (yield 60%, MS: [M+H]+= 607).

Manufacturing Example 1-17

In a nitrogen atmosphere, compound BA (15 g, 56.2 mmol) and phenylboronic acid (6.8 g, 56.2 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (23.3 g, 168.5 mmol) was dissolved in 70 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.6 mmol) was added. After reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.6 g of compound subBA-3 (yield 76%, MS: [M+H]+= 320).

In a nitrogen atmosphere, compound subBA-3 (15 g, 46.9 mmol) and compound Trz14 (20.8 g, 46.9 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (19.5 g, 140.7 mmol) was dissolved in 58 ml of water, stirred sufficiently, and then 0 (0.5 g, 0.5 mmol) was added. After reacting for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.4 g of compound 1-17 (yield 73%, MS: [M+H]+= 683).

Manufacturing Example 1-18

In a nitrogen atmosphere, compound BB (15 g, 56.2 mmol) and phenylboronic acid (6.8 g, 56.2 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (23.3 g, 168.5 mmol) was dissolved in 70 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.6 mmol) was added. After reacting for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.9 g of compound subBB-1 (yield 61%, MS: [M+H]+= 320).

In a nitrogen atmosphere, compounds subBB-1 (15 g, 46.9 mmol) and bis(pinacolato)diboron (13.1 g, 51.6 mmol) were refluxed and stirred in 300 ml of 1,4-dioxane. Afterwards, 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 7 hours, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then 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 subBB-2 (yield 79%, MS: [M+H]+= 412).

In a nitrogen atmosphere, compound subBB-2 (15 g, 36.5 mmol) and compound Trz15 (11.6 g, 36.5 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (15.1 g, 109.4 mmol) was dissolved in 45 ml of water, stirred sufficiently, and then 0 (0.4 g, 0.4 mmol) was added. After reacting for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.1 g of compound 1-18 (yield 78%, MS: [M+H]+= 567).

Manufacturing Example 1-19

In a nitrogen atmosphere, compound BB (15 g, 56.2 mmol) and dibenzo[b,d]furan-1-ylboronic acid (11.9 g, 56.2 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (23.3 g, 168.5 mmol) was dissolved in 70 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.6 mmol) was added. After reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.9 g of compound subBB-3 (yield 78%, MS: [M+H]+= 410).

In a nitrogen atmosphere, compounds subBB-3 (15 g, 46.9 mmol) and bis(pinacolato)diboron (13.1 g, 51.6 mmol) were refluxed in 300 ml of 1,4-dioxane and stirred. Afterwards, 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, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.1 g of compound subBB-4 (yield 77%, MS: [M+H]+= 502).

In a nitrogen atmosphere, compound subBB-4 (15 g, 29.9 mmol) and compound Trz5 (8 g, 29.9 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (12.4 g, 89.8 mmol) was dissolved in 37 ml of water, stirred sufficiently, and then 0 (0.3 g, 0.3 mmol) was added. After reacting for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.2 g of compound 1-19 (yield 62%, MS: [M+H]+= 607).

Manufacturing Example 1-20

In a nitrogen atmosphere, compound BC (15 g, 56.2 mmol) and dibenzo[b,d]thiophen-4-ylboronic acid (12.8 g, 56.2 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (23.3 g, 168.5 mmol) was dissolved in 70 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.6 mmol) was added. After reaction for 8 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then 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 subBC-1 (yield 64%, MS: [M+H]+= 426).

In a nitrogen atmosphere, compounds subBC-1 (15 g, 35.3 mmol) and bis(pinacolato)diboron (9.8 g, 38.8 mmol) were refluxed and stirred in 300 ml of 1,4-dioxane. Afterwards, potassium acetate (5.2 g, 52.9 mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.6 g, 1.1 mmol) and tricyclohexylphosphine (0.6 g, 2.1 mmol) were added. After reacting for 5 hours, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.5 g of compound subBC-2 (yield 63%, MS: [M+H]+= 518).

In a nitrogen atmosphere, compound subBC-2 (15 g, 29 mmol) and compound Trz5 (7.8 g, 29 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (12 g, 87 mmol) was dissolved in 36 ml of water, stirred sufficiently, and then 0 (0.3 g, 0.3 mmol) was added. After reacting for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.4 g of compound 1-20 (yield 80%, MS: [M+H]+= 623).

Manufacturing Example 1-21

In a nitrogen atmosphere, compound BD (15 g, 53.9 mmol) and phenylboronic acid (6.6 g, 53.9 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (22.4 g, 161.8 mmol) was dissolved in 67 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.9 g of compound subBD-1 (yield 69%, MS: [M+H]+= 320).

In a nitrogen atmosphere, compounds subBD-1 (15 g, 46.9 mmol) and bis(pinacolato)diboron (13.1 g, 51.6 mmol) were refluxed and stirred in 300 ml of 1,4-dioxane. Afterwards, 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 6 hours, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.2 g of compound subBD-2 (yield 63%, MS: [M+H]+= 412).

In a nitrogen atmosphere, compound subBD-2 (15 g, 36.5 mmol) and compound Trz5 (9.8 g, 36.5 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (15.1 g, 109.4 mmol) was dissolved in 45 ml of water, stirred sufficiently, and then 0 (0.4 g, 0.4 mmol) was added. After reaction for 8 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.7 g of compound 1-21 (yield 78%, MS: [M+H]+= 517).

Manufacturing Example 1-22

In a nitrogen atmosphere, compound subBD-2 (15 g, 36.5 mmol) and compound Trz16 (14.7 g, 36.5 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (15.1 g, 109.4 mmol) was dissolved in 45 ml of water, stirred sufficiently, and then 0 (0.4 g, 0.4 mmol) was added. After reacting for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.6 g of compound 1-22 (yield 75%, MS: [M+H]+= 643).

Manufacturing Example 1-23

In a nitrogen atmosphere, compound subBD-2 (15 g, 36.5 mmol) and compound Trz6 (13.1 g, 36.5 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (15.1 g, 109.4 mmol) was dissolved in 45 ml of water, stirred sufficiently, and then 0 (0.4 g, 0.4 mmol) was added. After reacting for 10 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.2 g of compound 1-23 (yield 78%, MS: [M+H]+= 607).

Manufacturing Example 1-24

In a nitrogen atmosphere, compound subBD-1 (15 g, 36.5 mmol) and compound Trz9 (14.7 g, 36.5 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (15.1 g, 109.4 mmol) was dissolved in 45 ml of water, stirred sufficiently, and then 0 (0.4 g, 0.4 mmol) was added. After reaction for 8 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.8 g of compound 1-24 (yield 76%, MS: [M+H]+= 643).

Manufacturing Example 1-25

In a nitrogen atmosphere, compound subBD-1 (15 g, 36.5 mmol) and compound Trz14 (16.2 g, 36.5 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (15.1 g, 109.4 mmol) was dissolved in 45 ml of water, stirred sufficiently, and then 0 (0.4 g, 0.4 mmol) was added. After reacting for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.9 g of compound 1-25 (yield 68%, MS: [M+H]+= 683).

Manufacturing Example 1-26

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. Afterwards, potassium carbonate (22.4 g, 161.8 mmol) was dissolved in 67 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 10 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then 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 subBE-1 (yield 78%, MS: [M+H]+= 320).

In a nitrogen atmosphere, compound subBE-1 (15 g, 46.9 mmol) and compound Trz17 (16.6 g, 46.9 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (19.5 g, 140.7 mmol) was dissolved in 58 ml of water, stirred sufficiently, and then 0 (0.5 g, 0.5 mmol) was added. After reacting for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.3 g of compound 1-26 (yield 73%, MS: [M+H]+= 593).

Manufacturing Example 1-27

In a nitrogen atmosphere, compound BE (15 g, 53.9 mmol) and naphthalen-2-ylboronic acid (9.3 g, 53.9 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (22.4 g, 161.8 mmol) was dissolved in 67 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reaction for 8 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.5 g of compound subBE-2 (yield 63%, MS: [M+H]+= 370).

In a nitrogen atmosphere, compounds subBE-2 (15 g, 40.6 mmol) and bis(pinacolato)diboron (11.3 g, 44.6 mmol) were refluxed and stirred in 300 ml of 1,4-dioxane. Afterwards, potassium acetate (6 g, 60.8 mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.7 g, 1.2 mmol) and tricyclohexylphosphine (0.7 g, 2.4 mmol) were added. After reacting for 6 hours, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.5 g of compound subBE-3 (yield 67%, MS: [M+H]+= 462).

In a nitrogen atmosphere, compound subBE-3 (15 g, 32.5 mmol) and compound Trz18 (11.6 g, 32.5 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (13.5 g, 97.5 mmol) was dissolved in 40 ml of water, stirred sufficiently, and then 0 (0.4 g, 0.3 mmol) was added. After reacting for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.7 g of compound 1-27 (yield 65%, MS: [M+H]+= 697).

Manufacturing Example 1-28

In a nitrogen atmosphere, 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. Afterwards, potassium carbonate (22.4 g, 161.8 mmol) was dissolved in 67 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 10 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.9 g of compound subBF-1 (yield 69%, MS: [M+H]+= 320).

In a nitrogen atmosphere, compound subBF-1 (15 g, 46.9 mmol) and compound Trz19 (18.9 g, 46.9 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (19.5 g, 140.7 mmol) was dissolved in 58 ml of water, stirred sufficiently, and then 0 (0.5 g, 0.5 mmol) was added. After reacting for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22 g of compound 1-28 (yield 73%, MS: [M+H]+= 643).

Manufacturing Example 1-29

In a nitrogen atmosphere, compound BF (15 g, 53.9 mmol) and naphthalen-2-ylboronic acid (9.3 g, 53.9 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (22.4 g, 161.8 mmol) was dissolved in 67 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.3 g of compound subBF-2 (yield 62%, MS: [M+H]+= 370).

In a nitrogen atmosphere, compounds subBF-2 (15 g, 40.6 mmol) and bis(pinacolato)diboron (11.3 g, 44.6 mmol) were refluxed and stirred in 300 ml of 1,4-dioxane. Afterwards, potassium acetate (6 g, 60.8 mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.7 g, 1.2 mmol) and tricyclohexylphosphine (0.7 g, 2.4 mmol) were added. After reacting for 5 hours, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.7 g of compound subBF-3 (yield 73%, MS: [M+H]+= 462).

In a nitrogen atmosphere, compound subBF-3 (15 g, 36.5 mmol) and compound Trz18 (13.1 g, 36.5 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (15.1 g, 109.4 mmol) was dissolved in 45 ml of water, stirred sufficiently, and then 0 (0.4 g, 0.4 mmol) was added. After reaction for 8 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.5 g of compound 1-29 (yield 61%, MS: [M+H]+= 697).

Manufacturing Example 1-30

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. Afterwards, potassium carbonate (21.1 g, 153 mmol) was dissolved in 63 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 10 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.8 g of compound subCA-1 (yield 69%, MS: [M+H]+= 336).

In a nitrogen atmosphere, compounds subCA-1 (15 g, 42.2 mmol) and bis(pinacolato)diboron (11.8 g, 46.4 mmol) were refluxed in 300 ml of 1,4-dioxane and stirred. Afterwards, potassium acetate (6.2 g, 63.2 mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.7 g, 1.3 mmol) and tricyclohexylphosphine (0.7 g, 2.5 mmol) were added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.2 g of compound subCA-2 (yield 62%, MS: [M+H]+= 428).

In a nitrogen atmosphere, compound subCA-2 (15 g, 35.1 mmol) and compound Trz20 (12.6 g, 35.1 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (14.6 g, 105.3 mmol) was dissolved in 44 ml of water, stirred sufficiently, and then 0 (0.4 g, 0.4 mmol) was added. After reaction for 8 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.6 g of compound 1-30 (yield 76%, MS: [M+H]+= 623).

Manufacturing Example 1-31

In a nitrogen atmosphere, compound CA (15 g, 51 mmol) and naphthalen-2-ylboronic acid (8.8 g, 51 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (21.1 g, 153 mmol) was dissolved in 63 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then 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 subCA-3 (yield 78%, MS: [M+H]+= 386).

In a nitrogen atmosphere, compound subCA-3 (15 g, 38.9 mmol) and compound Trz21 (15.3 g, 38.9 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (16.1 g, 116.6 mmol) was dissolved in 48 ml of water, stirred sufficiently, and then 0 (0.4 g, 0.4 mmol) was added. After reacting for 10 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.9 g of compound 1-31 (yield 65%, MS: [M+H]+= 709).

Manufacturing Example 1-32

In a nitrogen atmosphere, compound CB (15 g, 51 mmol) and naphthalen-2-ylboronic acid (8.8 g, 51 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (21.1 g, 153 mmol) was dissolved in 63 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reaction for 8 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.1 g of compound subCB-1 (yield 72%, MS: [M+H]+= 386).

In a nitrogen atmosphere, compounds subCB-1 (15 g, 38.9 mmol) and bis(pinacolato)diboron (10.9 g, 42.8 mmol) were refluxed in 300 ml of 1,4-dioxane and stirred. Afterwards, potassium acetate (5.7 g, 58.3 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 8 hours, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.1 g of compound subCB-2 (yield 65%, MS: [M+H]+= 478).

In a nitrogen atmosphere, compound subCB-2 (15 g, 38.9 mmol) and compound Trz16 (15.3 g, 38.9 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (16.1 g, 116.6 mmol) was dissolved in 48 ml of water, stirred sufficiently, and then 0 (0.4 g, 0.4 mmol) was added. After reacting for 10 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.9 g of compound 1-31 (yield 65%, MS: [M+H]+= 709).

Manufacturing Example 1-33

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. Afterwards, potassium carbonate (21.1 g, 153 mmol) was dissolved in 63 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.3 g of compound subCB-3 (yield 66%, MS: [M+H]+= 336).

In a nitrogen atmosphere, compound subCB-3 (15 g, 44.7 mmol) and compound Trz3 (18 g, 44.7 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (18.5 g, 134 mmol) was dissolved in 56 ml of water, stirred sufficiently, and then 0 (0.5 g, 0.4 mmol) was added. After reacting for 10 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.9 g of compound 1-33 (yield 71%, MS: [M+H]+= 659).

Manufacturing Example 1-34

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. Afterwards, potassium carbonate (21.1 g, 153 mmol) was dissolved in 63 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 10 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.2 g of compound subCC-1 (yield 77%, MS: [M+H]+= 336).

In a nitrogen atmosphere, compounds subCC-1 (15 g, 44.7 mmol) and bis(pinacolato)diboron (12.5 g, 49.1 mmol) were refluxed and stirred in 300 ml of 1,4-dioxane. Afterwards, 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, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.1 g of compound subCC-2 (yield 74%, MS: [M+H]+= 428).

In a nitrogen atmosphere, compound subCC-2 (15 g, 35.1 mmol) and compound Trz22 (13.8 g, 35.1 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (14.6 g, 105.3 mmol) was dissolved in 44 ml of water, stirred sufficiently, and then 0 (0.4 g, 0.4 mmol) was added. After reaction for 8 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.9 g of compound 1-34 (yield 73%, MS: [M+H]+= 659).

Manufacturing Example 1-35

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. Afterwards, potassium carbonate (21.1 g, 153 mmol) was dissolved in 63 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.3 g of compound subCD-1 (yield 60%, MS: [M+H]+= 336).

In a nitrogen atmosphere, compounds subCD-1 (15 g, 44.7 mmol) and bis(pinacolato)diboron (12.5 g, 49.1 mmol) were refluxed and stirred in 300 ml of 1,4-dioxane. Afterwards, 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, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.5 g of compound subCD-2 (yield 71%, MS: [M+H]+= 428).

In a nitrogen atmosphere, compound subCD-2 (15 g, 35.1 mmol) and compound Trz23 (13.8 g, 35.1 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (14.6 g, 105.3 mmol) was dissolved in 44 ml of water, stirred sufficiently, and then 0 (0.4 g, 0.4 mmol) was added. After reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18 g of compound 1-35 (yield 78%, MS: [M+H]+= 659).

Manufacturing Example 1-36

In a nitrogen atmosphere, compound subCD-1 (15 g, 38.9 mmol) and compound Trz7 (15.3 g, 38.9 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (16.1 g, 116.6 mmol) was dissolved in 48 ml of water, stirred sufficiently, and then 0 (0.4 g, 0.4 mmol) was added. After reacting for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.1 g of compound 1-36 (yield 62%, MS: [M+H]+= 709).

Manufacturing Example 1-37

In a nitrogen atmosphere, compound CD (15 g, 51 mmol) and dibenzo[b,d]furan-2-ylboronic acid (10.8 g, 51 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (21.1 g, 153 mmol) was dissolved in 63 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.2 g of compound subCD-3 (yield 66%, MS: [M+H]+= 424).

In a nitrogen atmosphere, compounds subCD-3 (15 g, 35.2 mmol) and bis(pinacolato)diboron (9.8 g, 38.7 mmol) were refluxed and stirred in 300 ml of 1,4-dioxane. Afterwards, potassium acetate (5.2 g, 52.8 mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.6 g, 1.1 mmol) and tricyclohexylphosphine (0.6 g, 2.1 mmol) were added. After reacting for 9 hours, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.8 g of compound subCD-4 (yield 65%, MS: [M+H]+= 518).

In a nitrogen atmosphere, compound subCD-4 (15 g, 29 mmol) and compound Trz5 (7.8 g, 29 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (12 g, 87 mmol) was dissolved in 36 ml of water, stirred sufficiently, and then 0 (0.3 g, 0.3 mmol) was added. After reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.8 g of compound 1-37 (yield 71%, MS: [M+H]+= 623).

Manufacturing Example 1-38

In a nitrogen atmosphere, compound CE (15 g, 51 mmol) and [1,1'-biphenyl]-4-ylboronic acid (10.1 g, 51 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (21.1 g, 153 mmol) was dissolved in 63 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 10 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.5 g of compound subCE-1 (yield 74%, MS: [M+H]+= 412).

In a nitrogen atmosphere, compounds subCE-1 (15 g, 36.4 mmol) and bis(pinacolato)diboron (10.2 g, 40.1 mmol) were refluxed and stirred in 300 ml of 1,4-dioxane. Afterwards, potassium acetate (5.4 g, 54.6 mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.6 g, 1.1 mmol) and tricyclohexylphosphine (0.6 g, 2.2 mmol) were added. After reacting for 6 hours, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.8 g of compound subCE-2 (yield 70%, MS: [M+H]+= 504).

In a nitrogen atmosphere, compound subCE-2 (15 g, 29.8 mmol) and compound Trz23 (11 g, 29.8 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (12.4 g, 89.4 mmol) was dissolved in 37 ml of water, stirred sufficiently, and then 0 (0.3 g, 0.3 mmol) was added. After reacting for 10 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then 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 1-38 (yield 76%, MS: [M+H]+= 709).

Manufacturing Example 1-39

In a nitrogen atmosphere, compound CE (15 g, 51 mmol) and phenylboronic acid (6.2 g, 51 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (21.1 g, 153 mmol) was dissolved in 63 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then 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 subCE-3 (yield 76%, MS: [M+H]+= 336).

In a nitrogen atmosphere, compound subCE-3 (15 g, 44.7 mmol) and compound Trz24 (18 g, 44.7 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (18.5 g, 134 mmol) was dissolved in 56 ml of water, stirred sufficiently, and then 0 (0.5 g, 0.4 mmol) was added. After reacting for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.9 g of compound 1-39 (yield 78%, MS: [M+H]+= 659).

Manufacturing Example 1-40

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. Afterwards, potassium carbonate (21.1 g, 153 mmol) was dissolved in 63 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reaction for 8 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.3 g of compound subCF-1 (yield 78%, MS: [M+H]+= 336).

In a nitrogen atmosphere, compounds subCF-1 (15 g, 44.7 mmol) and bis(pinacolato)diboron (12.5 g, 49.1 mmol) were refluxed and stirred in 300 ml of 1,4-dioxane. Afterwards, 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 10 hours, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.5 g of compound subCF-2 (yield 71%, MS: [M+H]+= 428).

In a nitrogen atmosphere, compound subCF-2 (15 g, 35.1 mmol) and compound Trz25 (14.7 g, 35.1 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (14.6 g, 105.3 mmol) was dissolved in 44 ml of water, stirred sufficiently, and then 0 (0.4 g, 0.4 mmol) was added. After reacting for 10 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18 g of compound 1-40 (yield 75%, MS: [M+H]+= 685).

Manufacturing Example 1-41

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, stirred, and refluxed. Afterwards, potassium carbonate (21.1 g, 153 mmol) was dissolved in 63 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 10 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.1 g of compound subCF-3 (yield 77%, MS: [M+H]+= 386).

In a nitrogen atmosphere, compound subCF-3 (15 g, 38.9 mmol) and compound Trz26 (17.6 g, 38.9 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (16.1 g, 116.6 mmol) was dissolved in 48 ml of water, stirred sufficiently, and then 0 (0.4 g, 0.4 mmol) was added. After reacting for 10 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.9 g of compound 1-41 (yield 71%, MS: [M+H]+= 759).

Manufacturing Example 1-42

In a nitrogen atmosphere, compound DA (15 g, 51 mmol) and naphthalen-2-ylboronic acid (8.8 g, 51 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (21.1 g, 153 mmol) was dissolved in 63 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.6 g of compound subDA-1 (yield 64%, MS: [M+H]+= 386).

In a nitrogen atmosphere, compounds subDA-1 (15 g, 38.9 mmol) and bis(pinacolato)diboron (10.9 g, 42.8 mmol) were refluxed in 300 ml of 1,4-dioxane and stirred. Afterwards, potassium acetate (5.7 g, 58.3 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, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.9 g of compound subDA-2 (yield 64%, MS: [M+H]+= 478).

In a nitrogen atmosphere, compound subDA-2 (15 g, 31.4 mmol) and compound Trz6 (11.2 g, 31.4 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (13 g, 94.3 mmol) was dissolved in 39 ml of water, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 10 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.8 g of compound 1-42 (yield 70%, MS: [M+H]+= 673).

Manufacturing Example 1-43

In a nitrogen atmosphere, compound DA (15 g, 51 mmol) and [1,1'-biphenyl]-4-ylboronic acid (10.1 g, 51 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (21.1 g, 153 mmol) was dissolved in 63 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.6 g of compound subDA-3 (yield 65%, MS: [M+H]+= 412).

In a nitrogen atmosphere, compounds subDA-3 (15 g, 36.4 mmol) and bis(pinacolato)diboron (10.2 g, 40.1 mmol) were refluxed in 300 ml of 1,4-dioxane and stirred. Afterwards, potassium acetate (5.4 g, 54.6 mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.6 g, 1.1 mmol) and tricyclohexylphosphine (0.6 g, 2.2 mmol) were added. After reacting for 5 hours, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.5 g of compound subDA-4 (yield 68%, MS: [M+H]+= 504).

In a nitrogen atmosphere, compound subDA-4 (15 g, 29.8 mmol) and compound Trz15 (9.5 g, 29.8 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (12.4 g, 89.4 mmol) was dissolved in 37 ml of water, stirred sufficiently, and then 0 (0.3 g, 0.3 mmol) was added. After reacting for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.3 g of compound 1-43 (yield 73%, MS: [M+H]+= 659).

Manufacturing Example 1-44

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. Afterwards, potassium carbonate (21.1 g, 153 mmol) was dissolved in 63 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reaction for 8 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.1 g of compound subDB-1 (yield 65%, MS: [M+H]+= 336).

In a nitrogen atmosphere, compounds subDB-1 (15 g, 44.7 mmol) and bis(pinacolato)diboron (12.5 g, 49.1 mmol) were refluxed and stirred in 300 ml of 1,4-dioxane. Afterwards, 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 5 hours, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.1 g of compound subDB-2 (yield 74%, MS: [M+H]+= 428).

In a nitrogen atmosphere, compound subDB-2 (15 g, 35.1 mmol) and compound Trz6 (12.6 g, 35.1 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (14.6 g, 105.3 mmol) was dissolved in 44 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.9 g of compound 1-44 (yield 73%, MS: [M+H]+= 623).

Manufacturing Example 1-45

In a nitrogen atmosphere, compound subDB-2 (15 g, 35.1 mmol) and compound Trz27 (12.1 g, 35.1 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (14.6 g, 105.3 mmol) was dissolved in 44 ml of water, stirred sufficiently, and then 0 (0.4 g, 0.4 mmol) was added. After reacting for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then 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 1-45 (yield 71%, MS: [M+H]+= 609).

Manufacturing Example 1-46

In a nitrogen atmosphere, compound DC (15 g, 51 mmol) and phenylboronic acid (6.2 g, 51 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (21.1 g, 153 mmol) was dissolved in 63 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 10 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.1 g of compound subDC-1 (yield 71%, MS: [M+H]+= 336).

In a nitrogen atmosphere, compounds subDC-1 (15 g, 44.7 mmol) and bis(pinacolato)diboron (12.5 g, 49.1 mmol) were refluxed and stirred in 300 ml of 1,4-dioxane. Afterwards, 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 6 hours, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.5 g of compound subDC-2 (yield 71%, MS: [M+H]+= 428).

In a nitrogen atmosphere, compound subDC-2 (15 g, 35.1 mmol) and compound Trz28 (13.1 g, 35.1 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (14.6 g, 105.3 mmol) was dissolved in 44 ml of water, stirred sufficiently, and then 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, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.3 g of compound 1-46 (yield 64%, MS: [M+H]+= 639).

Manufacturing Example 1-47

In a nitrogen atmosphere, compound DD (15 g, 51 mmol) and phenylboronic acid (6.2 g, 51 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (21.1 g, 153 mmol) was dissolved in 63 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.5 g of compound subDD-1 (yield 79%, MS: [M+H]+= 336).

In a nitrogen atmosphere, compounds subDD-1 (15 g, 44.7 mmol) and bis(pinacolato)diboron (12.5 g, 49.1 mmol) were refluxed in 300 ml of 1,4-dioxane and stirred. Afterwards, 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 6 hours, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.5 g of compound subDD-2 (yield 71%, MS: [M+H]+= 428).

In a nitrogen atmosphere, compound subDD-2 (15 g, 35.1 mmol) and compound Trz22 (13.8 g, 35.1 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (14.6 g, 105.3 mmol) was dissolved in 44 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then 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 1-47 (yield 66%, MS: [M+H]+= 659).

Manufacturing Example 1-48

In a nitrogen atmosphere, compound DD (15 g, 51 mmol) and [1,1'-biphenyl]-4-ylboronic acid (10.1 g, 51 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (21.1 g, 153 mmol) was dissolved in 63 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reaction for 8 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.8 g of compound subDD-3 (yield 61%, MS: [M+H]+= 412).

In a nitrogen atmosphere, compounds subDD-3 (15 g, 36.4 mmol) and bis(pinacolato)diboron (10.2 g, 40.1 mmol) were refluxed and stirred in 300 ml of 1,4-dioxane. Afterwards, potassium acetate (5.4 g, 54.6 mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.6 g, 1.1 mmol) and tricyclohexylphosphine (0.6 g, 2.2 mmol) were added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.3 g of compound subDD-4 (yield 78%, MS: [M+H]+= 504).

In a nitrogen atmosphere, compound subDD-4 (15 g, 29.8 mmol) and compound Trz18 (10.7 g, 29.8 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (12.4 g, 89.4 mmol) was dissolved in 37 ml of water, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.5 g of compound 1-48 (yield 65%, MS: [M+H]+= 699).

Manufacturing Example 1-49

In a nitrogen atmosphere, compound DD (15 g, 51 mmol) and dibenzo[b,d]furan-2-ylboronic acid (10.8 g, 51 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (21.1 g, 153 mmol) was dissolved in 63 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.6 g of compound subDD-5 (yield 72%, MS: [M+H]+= 426).

In a nitrogen atmosphere, compounds subDD-5 (15 g, 35.2 mmol) and bis(pinacolato)diboron (9.8 g, 38.7 mmol) were refluxed in 300 ml of 1,4-dioxane and stirred. Afterwards, potassium acetate (5.2 g, 52.8 mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.6 g, 1.1 mmol) and tricyclohexylphosphine (0.6 g, 2.1 mmol) were added. After reacting for 5 hours, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then 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 subDD-6 (yield 68%, MS: [M+H]+= 518).

In a nitrogen atmosphere, compound subDD-6 (15 g, 29 mmol) and compound Trz5 (7.8 g, 29 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (12 g, 87 mmol) was dissolved in 36 ml of water, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then 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 1-49 (yield 72%, MS: [M+H]+= 623).

Manufacturing Example 1-50

In a nitrogen atmosphere, compound DE (15 g, 51 mmol) and phenylboronic acid (6.2 g, 51 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (21.1 g, 153 mmol) was dissolved in 63 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.4 g of compound subDE-1 (yield 61%, MS: [M+H]+= 336).

In a nitrogen atmosphere, compounds subDE-1 (15 g, 44.7 mmol) and bis(pinacolato)diboron (12.5 g, 49.1 mmol) were refluxed in 300 ml of 1,4-dioxane and stirred. Afterwards, 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 10 hours, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.7 g of compound subDE-2 (yield 72%, MS: [M+H]+= 428).

In a nitrogen atmosphere, compound subDE-2 (15 g, 35.1 mmol) and compound Trz29 (13.1 g, 35.1 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (14.6 g, 105.3 mmol) was dissolved in 44 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.5 g of compound 1-50 (yield 69%, MS: [M+H]+= 639).

Manufacturing Example 1-51

In a nitrogen atmosphere, compound DE (15 g, 51 mmol) and naphthalen-2-ylboronic acid (8.8 g, 51 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (21.1 g, 153 mmol) was dissolved in 63 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reaction for 8 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.8 g of compound subDE-3 (yield 65%, MS: [M+H]+= 386).

In a nitrogen atmosphere, compounds subDE-3 (15 g, 38.9 mmol) and bis(pinacolato)diboron (10.9 g, 42.8 mmol) were refluxed and stirred in 300 ml of 1,4-dioxane. Afterwards, potassium acetate (5.7 g, 58.3 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 9 hours, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.5 g of compound subDE-4 (yield 62%, MS: [M+H]+= 478).

In a nitrogen atmosphere, compound subDE-4 (15 g, 31.4 mmol) and compound Trz27 (10.8 g, 31.4 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (13 g, 94.3 mmol) was dissolved in 39 ml of water, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 10 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.2 g of compound 1-51 (yield 64%, MS: [M+H]+= 659).

Manufacturing Example 1-52

In a nitrogen atmosphere, compound DF (15 g, 51 mmol) and phenylboronic acid (6.2 g, 51 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (21.1 g, 153 mmol) was dissolved in 63 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reaction for 8 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.3 g of compound subDF-1 (yield 78%, MS: [M+H]+= 336).

In a nitrogen atmosphere, compound subDF-1 (15 g, 44.7 mmol) and compound Trz30 (21.4 g, 44.7 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (18.5 g, 134 mmol) was dissolved in 56 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 10 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23 g of compound 1-52 (yield 70%, MS: [M+H]+= 735).

Manufacturing Example 1-53

In a nitrogen atmosphere, compounds subDF-1 (15 g, 44.7 mmol) and bis(pinacolato)diboron (12.5 g, 49.1 mmol) were refluxed in 300 ml of 1,4-dioxane and stirred. Afterwards, 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 8 hours, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.6 g of compound subDF-2 (yield 61%, MS: [M+H]+= 428).

In a nitrogen atmosphere, compound subDF-2 (15 g, 35.1 mmol) and compound Trz31 (12.9 g, 35.1 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (14.6 g, 105.3 mmol) was dissolved in 44 ml of water, stirred sufficiently, and then 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, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.9 g of compound 1-53 (yield 76%, MS: [M+H]+= 633).

Manufacturing Example 2-1

In a nitrogen atmosphere, compound subAA-3 (10 g, 31.3 mmol), compound amine1 (13.2 g, 31.3 mmol), and sodium tert-butoxide (10 g, 46.9 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 12.8 g of compound 2-1 (yield 58%, MS: [M+H]+= 705).

Manufacturing Example 2-2

In a nitrogen atmosphere, compound subAA-3 (10 g, 31.3 mmol), compound amine2 (10.8 g, 31.3 mmol), and sodium tert-butoxide (10 g, 46.9 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, the pressure was reduced, and the solvent was removed. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.6 g of compound 2-2 (yield 54%, MS: [M+H]+= 629).

Manufacturing Example 2-3

In a nitrogen atmosphere, compound subAA-3 (10 g, 31.3 mmol), compound amine3 (11 g, 31.3 mmol), and sodium tert-butoxide (10 g, 46.9 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 12.9 g of compound 2-3 (yield 65%, MS: [M+H]+= 635).

Manufacturing Example 2-4

In a nitrogen atmosphere, compound subAA-3 (15 g, 46.9 mmol) and compound amine4 (20.7 g, 46.9 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (19.5 g, 140.7 mmol) was dissolved in 58 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.5 mmol) was added. After reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24 g of compound 2-4 (yield 74%, MS: [M+H]+= 691).

Manufacturing Example 2-5

In a nitrogen atmosphere, formula AA (15 g, 53.9 mmol) and naphthalen-2-ylboronic acid (9.3 g, 53.9 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (22.4 g, 161.8 mmol) was dissolved in 67 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.7 g of compound subAA-4 (yield 79%, MS: [M+H]+= 370).

In a nitrogen atmosphere, compound subAA-4 (15 g, 40.6 mmol) and compound amine5 (16.8 g, 40.6 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (16.8 g, 121.7 mmol) was dissolved in 50 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.4 mmol) was added. After reacting for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.3 g of compound 2-5 (yield 64%, MS: [M+H]+= 705).

Manufacturing Example 2-6

In a nitrogen atmosphere, compound subAB-1 (10 g, 31.3 mmol), compound amine6 (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. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 2-6 (yield 69%, MS: [M+H]+= 695).

Manufacturing Example 2-7

In a nitrogen atmosphere, compound subAB-1 (10 g, 31.3 mmol), compound amine7 (10.9 g, 31.3 mmol), and sodium tert-butoxide (10 g, 46.9 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 2-7 (yield 66%, MS: [M+H]+= 633).

Manufacturing Example 2-8

In a nitrogen atmosphere, compound subAB-1 (15 g, 46.9 mmol) and compound amine8 (24.9 g, 46.9 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (19.5 g, 140.7 mmol) was dissolved in 58 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.5 mmol) was added. After reacting for 10 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 27.5 g of compound 2-8 (yield 76%, MS: [M+H]+= 771).

Manufacturing Example 2-9

In a nitrogen atmosphere, compound subAB-1 (15 g, 46.9 mmol) and compound amine9 (26.6 g, 46.9 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (19.5 g, 140.7 mmol) was dissolved in 58 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) was added. After reacting for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26.1 g of compound 2-9 (yield 69%, MS: [M+H]+= 807).

Manufacturing Example 2-10

In a nitrogen atmosphere, formula AB (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, stirred, and refluxed. Afterwards, potassium carbonate (22.4 g, 161.8 mmol) was dissolved in 67 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 10 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.9 g of compound subAB-3 (yield 70%, MS: [M+H]+= 396).

In a nitrogen atmosphere, compound subAB-3 (10 g, 25.3 mmol), compound amine10 (6.2 g, 25.3 mmol), and sodium tert-butoxide (8 g, 37.9 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 9.9 g of compound 2-10 (yield 65%, MS: [M+H]+= 605).

Manufacturing Example 2-11

Under a nitrogen atmosphere, chemical formula 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. Afterwards, potassium carbonate (22.4 g, 161.8 mmol) was dissolved in 67 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12 g of compound subAC-3 (yield 70%, MS: [M+H]+= 320).

In a nitrogen atmosphere, compound subAC-3 (10 g, 31.3 mmol), compound amine11 (14 g, 31.3 mmol), and sodium tert-butoxide (10 g, 46.9 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 13.9 g of compound 2-11 (yield 61%, MS: [M+H]+= 731).

Manufacturing Example 2-12

In a nitrogen atmosphere, compound subAC-3 (10 g, 31.3 mmol), compound amine12 (11.6 g, 31.3 mmol), and sodium tert-butoxide (10 g, 46.9 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 10.4 g of compound 2-12 (yield 51%, MS: [M+H]+= 655).

Manufacturing Example 2-13

In a nitrogen atmosphere, compound subAC-3 (10 g, 31.3 mmol), compound amine13 (11.3 g, 31.3 mmol), and sodium tert-butoxide (10 g, 46.9 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 13.7 g of compound 2-13 (yield 68%, MS: [M+H]+= 645).

Manufacturing Example 2-14

In a nitrogen atmosphere, compound subAC-3 (15 g, 46.9 mmol) and compound amine14 (19.5 g, 46.9 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (19.5 g, 140.7 mmol) was dissolved in 58 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.5 mmol) was added. After reacting for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.6 g of compound 2-14 (yield 77%, MS: [M+H]+= 655).

Manufacturing Example 2-15

In a nitrogen atmosphere, compound subAC-3 (15 g, 46.9 mmol) and compound amine15 (20.7 g, 46.9 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (19.5 g, 140.7 mmol) was dissolved in 58 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.5 mmol) was added. After reaction for 8 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23 g of compound 2-15 (yield 72%, MS: [M+H]+= 681).

Manufacturing Example 2-16

Under a nitrogen atmosphere, chemical formula AC (15 g, 53.9 mmol) and naphthalen-2-ylboronic acid (9.3 g, 53.9 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (22.4 g, 161.8 mmol) was dissolved in 67 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.7 g of compound subAC-4 (yield 64%, MS: [M+H]+= 370).

In a nitrogen atmosphere, compound subAC-4 (10 g, 27 mmol), compound amine16 (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. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9.4 g of compound 2-16 (yield 53%, MS: [M+H]+= 655).

Manufacturing Example 2-17

In a nitrogen atmosphere, compound subAD-1 (10 g, 31.3 mmol), compound amine17 (13.2 g, 31.3 mmol), and sodium tert-butoxide (10 g, 46.9 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 2-17 (yield 59%, MS: [M+H]+= 705).

Manufacturing Example 2-18

In a nitrogen atmosphere, compound subAD-1 (15 g, 40.6 mmol) and compound amine18 (23 g, 40.6 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (16.8 g, 121.7 mmol) was dissolved in 50 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.4 mmol) was added. After reacting for 10 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.9 g of compound 2-18 (yield 64%, MS: [M+H]+= 807).

Manufacturing Example 2-19

In a nitrogen atmosphere, compound subAD-1 (10 g, 31.3 mmol), compound amine19 (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. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 11.5 g of compound 2-19 (yield 53%, MS: [M+H]+= 694).

Manufacturing Example 2-20

In a nitrogen atmosphere, compound subAD-1 (15 g, 40.6 mmol) and compound amine20 (18.5 g, 40.6 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (16.8 g, 121.7 mmol) was dissolved in 50 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.4 mmol) was added. After reacting for 10 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.4 g of compound 2-20 (yield 69%, MS: [M+H]+= 695).

Manufacturing Example 2-21

In a nitrogen atmosphere, chemical formula AD (15 g, 53.9 mmol) and naphthalen-2-ylboronic acid (9.3 g, 53.9 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (22.4 g, 161.8 mmol) was dissolved in 67 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.5 g of compound subAD-5 (yield 68%, MS: [M+H]+= 370).

In a nitrogen atmosphere, compound subAD-5 (10 g, 27 mmol), compound amine21 (8 g, 27 mmol), and sodium tert-butoxide (8.6 g, 40.6 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 9.2 g of compound 2-21 (yield 54%, MS: [M+H]+= 630).

Manufacturing Example 2-22

In a nitrogen atmosphere, compound subAE-1 (10 g, 31.3 mmol), compound amine22 (13.2 g, 31.3 mmol), and sodium tert-butoxide (10 g, 46.9 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 2-22 (yield 60%, MS: [M+H]+= 705).

Manufacturing Example 2-23

In a nitrogen atmosphere, compound subAE-1 (15 g, 46.9 mmol) and compound amine23 (25.4 g, 46.9 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (19.5 g, 140.7 mmol) was dissolved in 58 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.5 mmol) was added. After reacting for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.4 g of compound 2-23 (yield 64%, MS: [M+H]+= 781).

Manufacturing Example 2-24

In a nitrogen atmosphere, compound subAE-1 (15 g, 46.9 mmol) and compound amine24 (23.1 g, 46.9 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (19.5 g, 140.7 mmol) was dissolved in 58 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.5 mmol) was added. After reaction for 8 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.3 g of compound 2-24 (yield 65%, MS: [M+H]+= 731).

Manufacturing Example 2-25

In a nitrogen atmosphere, chemical formula 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, stirred, and refluxed. Afterwards, potassium carbonate (22.4 g, 161.8 mmol) was dissolved in 67 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.2 g of compound subAE-4 (yield 62%, MS: [M+H]+= 396).

In a nitrogen atmosphere, compound subAE-4 (10 g, 25.3 mmol), compound amine16 (8.1 g, 25.3 mmol), and sodium tert-butoxide (8 g, 37.9 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 g of compound 2-25 (yield 64%, MS: [M+H]+= 681).

Manufacturing Example 2-26

In a nitrogen atmosphere, compound subAF-1 (15 g, 46.9 mmol) and compound amine25 (20.7 g, 46.9 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (19.5 g, 140.7 mmol) was dissolved in 58 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.5 mmol) was added. After reacting for 10 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.1 g of compound 2-26 (yield 65%, MS: [M+H]+= 757).

Manufacturing Example 2-27

In a nitrogen atmosphere, compound subBA-3 (15 g, 40.6 mmol) and compound amine26 (19.9 g, 40.6 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (16.8 g, 121.7 mmol) was dissolved in 50 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.4 mmol) was added. After reacting for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.1 g of compound 2-27 (yield 61%, MS: [M+H]+= 731).

Manufacturing Example 2-28

In a nitrogen atmosphere, compound subBA-3 (15 g, 40.6 mmol) and compound amine27 (19.1 g, 40.6 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (16.8 g, 121.7 mmol) was dissolved in 50 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.4 mmol) was added. After reaction for 8 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.6 g of compound 2-28 (yield 75%, MS: [M+H]+= 711).

Manufacturing Example 2-29

In a nitrogen atmosphere, compound subBA-3 (15 g, 40.6 mmol) and compound amine28 (17.9 g, 40.6 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (16.8 g, 121.7 mmol) was dissolved in 50 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.4 mmol) was added. After reacting for 10 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.6 g of compound 2-29 (yield 71%, MS: [M+H]+= 681).

Manufacturing Example 2-30

In a nitrogen atmosphere, compound subBB-1 (10 g, 31.3 mmol), compound amine29 (11.6 g, 31.3 mmol), and sodium tert-butoxide (10 g, 46.9 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 2-30 (yield 53%, MS: [M+H]+= 655).

Manufacturing Example 2-31

In a nitrogen atmosphere, compound subBB-1 (10 g, 31.3 mmol), compound amine30 (12.4 g, 31.3 mmol), and sodium tert-butoxide (10 g, 46.9 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 13.4 g of compound 2-31 (yield 63%, MS: [M+H]+= 681).

Manufacturing Example 2-32

In a nitrogen atmosphere, compound subBB-1 (15 g, 46.9 mmol) and compound amine31 (23.1 g, 46.9 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (19.5 g, 140.7 mmol) was dissolved in 58 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.5 mmol) was added. After reacting for 10 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 25 g of compound 2-32 (yield 73%, MS: [M+H]+= 731).

Manufacturing Example 2-33

In a nitrogen atmosphere, compound subBB-1 (15 g, 46.9 mmol) and compound amine32 (24.3 g, 46.9 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (19.5 g, 140.7 mmol) was dissolved in 58 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.5 mmol) was added. After reaction for 8 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.6 g of compound 2-33 (yield 61%, MS: [M+H]+= 757).

Manufacturing Example 2-34

In a nitrogen atmosphere, 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. Afterwards, potassium carbonate (22.4 g, 161.8 mmol) was dissolved in 67 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then 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 subBC-3 (yield 72%, MS: [M+H]+= 320).

In a nitrogen atmosphere, compound subBC-3 (10 g, 31.3 mmol), compound amine33 (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. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 2-34 (yield 61%, MS: [M+H]+= 695).

Manufacturing Example 2-35

In a nitrogen atmosphere, compound subBC-3 (10 g, 31.3 mmol), compound amine34 (14 g, 31.3 mmol), and sodium tert-butoxide (10 g, 46.9 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 12.8 g of compound 2-35 (yield 56%, MS: [M+H]+= 731).

Manufacturing Example 2-36

In a nitrogen atmosphere, compound subBC-3 (15 g, 46.9 mmol) and compound amine35 (19.5 g, 46.9 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (19.5 g, 140.7 mmol) was dissolved in 58 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.5 mmol) was added. After reacting for 10 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.4 g of compound 2-36 (yield 60%, MS: [M+H]+= 655).

Manufacturing Example 2-37

In a nitrogen atmosphere, compound subBC-3 (15 g, 46.9 mmol) and compound amine36 (18.5 g, 46.9 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (19.5 g, 140.7 mmol) was dissolved in 58 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.5 mmol) was added. After reacting for 10 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.8 g of compound 2-37 (yield 70%, MS: [M+H]+= 635).

Manufacturing Example 2-38

In a nitrogen atmosphere, BC (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, stirred, and refluxed. Afterwards, potassium carbonate (22.4 g, 161.8 mmol) was dissolved in 67 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reaction for 8 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.8 g of compound subBC-4 (yield 74%, MS: [M+H]+= 396).

In a nitrogen atmosphere, compound subBC-4 (10 g, 25.3 mmol), compound amine37 (10 g, 25.3 mmol), and sodium tert-butoxide (8 g, 37.9 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 2-38 (yield 62%, MS: [M+H]+= 757).

Manufacturing Example 2-39

In a nitrogen atmosphere, compound subBD-1 (10 g, 31.3 mmol), compound amine38 (10.8 g, 31.3 mmol), and sodium tert-butoxide (10 g, 46.9 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 2-39 (yield 60%, MS: [M+H]+= 629).

Manufacturing Example 2-40

In a nitrogen atmosphere, compound subBD-1 (10 g, 31.3 mmol), compound amine39 (11.6 g, 31.3 mmol), and sodium tert-butoxide (10 g, 46.9 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 13.7 g of compound 2-40 (yield 67%, MS: [M+H]+= 655).

Manufacturing Example 2-41

In a nitrogen atmosphere, compound subBD-1 (10 g, 31.3 mmol), compound amine40 (11.6 g, 31.3 mmol), and sodium tert-butoxide (10 g, 46.9 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 11.5 g of compound 2-41 (yield 56%, MS: [M+H]+= 655).

Manufacturing Example 2-42

In a nitrogen atmosphere, compound subBD-1 (10 g, 31.3 mmol), compound amine41 (14 g, 31.3 mmol), and sodium tert-butoxide (10 g, 46.9 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 14.8 g of compound 2-42 (yield 65%, MS: [M+H]+= 731).

Manufacturing Example 2-43

In a nitrogen atmosphere, BD (15 g, 53.9 mmol) and naphthalen-2-ylboronic acid (9.3 g, 53.9 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (22.4 g, 161.8 mmol) was dissolved in 67 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 10 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.7 g of compound subBD-3 (yield 69%, MS: [M+H]+= 370).

In a nitrogen atmosphere, compound subBD-3 (15 g, 40.6 mmol) and compound amine42 (18.5 g, 40.6 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (16.8 g, 121.7 mmol) was dissolved in 50 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.4 mmol) was added. After reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.7 g of compound 2-43 (yield 72%, MS: [M+H]+= 745).

Manufacturing Example 2-44

In a nitrogen atmosphere, compound subBE-1 (15 g, 46.9 mmol) and compound amine43 (22 g, 46.9 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (19.5 g, 140.7 mmol) was dissolved in 58 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.5 mmol) was added. After reacting for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26.6 g of compound 2-44 (yield 80%, MS: [M+H]+= 709).

Manufacturing Example 2-45

In a nitrogen atmosphere, compound subBE-1 (15 g, 46.9 mmol) and compound amine44 (22.6 g, 46.9 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (19.5 g, 140.7 mmol) was dissolved in 58 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.5 mmol) was added. After reacting for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.3 g of compound 2-45 (yield 69%, MS: [M+H]+= 721).

Manufacturing Example 2-46

In a nitrogen atmosphere, compound subBE-1 (15 g, 46.9 mmol) and compound amine45 (24.3 g, 46.9 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (19.5 g, 140.7 mmol) was dissolved in 58 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.5 mmol) was added. After reaction for 8 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26.3 g of compound 2-46 (yield 74%, MS: [M+H]+= 757).

Manufacturing Example 2-47

In a nitrogen atmosphere, compound subBE-2 (10 g, 27 mmol), compound amine37 (10.7 g, 27 mmol), and sodium tert-butoxide (8.6 g, 40.6 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 2-47 (yield 60%, MS: [M+H]+= 731).

Manufacturing Example 2-48

In a nitrogen atmosphere, compound subBF-1 (15 g, 46.9 mmol) and compound amine46 (23.1 g, 46.9 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (19.5 g, 140.7 mmol) was dissolved in 58 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.5 mmol) was added. After reacting for 10 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.2 g of compound 2-48 (yield 62%, MS: [M+H]+= 731).

Manufacturing Example 2-49

In a nitrogen atmosphere, compound subBF-1 (10 g, 31.3 mmol), compound amine47 (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. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 10.7 g of compound 2-49 (yield 59%, MS: [M+H]+= 579).

Manufacturing Example 2-50

In a nitrogen atmosphere, compound subBF-1 (15 g, 46.9 mmol) and compound amine48 (26.6 g, 46.9 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (19.5 g, 140.7 mmol) was dissolved in 58 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.5 mmol) was added. After reacting for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 28.4 g of compound 2-50 (yield 75%, MS: [M+H]+= 807).

Manufacturing Example 2-51

In a nitrogen atmosphere, compound subBF-2 (10 g, 27 mmol), compound amine49 (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. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 10.7 g of compound 2-51 (yield 59%, MS: [M+H]+= 669).

Manufacturing Example 2-52

In a nitrogen atmosphere, compound subBF-2 (15 g, 40.6 mmol) and compound amine50 (21 g, 40.6 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (16.8 g, 121.7 mmol) was dissolved in 50 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.4 mmol) was added. After reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20 g of compound 2-52 (yield 61%, MS: [M+H]+= 807).

Manufacturing Example 2-53

In a nitrogen atmosphere, compound subCA-1 (10 g, 29.8 mmol), compound amine51 (13.3 g, 29.8 mmol), and sodium tert-butoxide (9.5 g, 44.7 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 2-53 (yield 63%, MS: [M+H]+= 747).

Manufacturing Example 2-54

In a nitrogen atmosphere, compound subCA-1 (10 g, 29.8 mmol), compound amine52 (11.5 g, 29.8 mmol), and sodium tert-butoxide (9.5 g, 44.7 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.6 g of compound 2-54 (yield 52%, MS: [M+H]+= 685).

Manufacturing Example 2-55

In a nitrogen atmosphere, compound subCA-1 (15 g, 46.9 mmol) and compound amine53 (24.5 g, 46.9 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (18.5 g, 134 mmol) was dissolved in 56 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.4 mmol) was added. After reacting for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 27.9 g of compound 2-55 (yield 78%, MS: [M+H]+= 803).

Manufacturing Example 2-56

In a nitrogen atmosphere, compound subCA-2 (15 g, 48.3 mmol) and compound amine35 (16.1 g, 48.3 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (16.1 g, 116.6 mmol) was dissolved in 48 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.4 mmol) was added. After reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.9 g of compound 2-56 (yield 71%, MS: [M+H]+= 721).

Manufacturing Example 2-57

In a nitrogen atmosphere, compound subCB-3 (10 g, 29.8 mmol), compound amine54 (12.6 g, 29.8 mmol), and sodium tert-butoxide (9.5 g, 44.7 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 12.9 g of compound 2-57 (yield 60%, MS: [M+H]+= 721).

Manufacturing Example 2-58

In a nitrogen atmosphere, compound subCB-3 (10 g, 29.8 mmol), compound amine55 (11.8 g, 29.8 mmol), and sodium tert-butoxide (9.5 g, 44.7 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 g of compound 2-58 (yield 53%, MS: [M+H]+= 697).

Manufacturing Example 2-59

In a nitrogen atmosphere, compound subCB-3 (15 g, 44.7 mmol) and compound amine56 (21.5 g, 44.7 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (18.5 g, 134 mmol) was dissolved in 56 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.4 mmol) was added. After reacting for 10 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.4 g of compound 2-59 (yield 68%, MS: [M+H]+= 737).

Manufacturing Example 2-60

In a nitrogen atmosphere, compound subCB-3 (15 g, 44.7 mol) and compound amine57 (21.9 g, 44.7 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (18.5 g, 134 mmol) was dissolved in 56 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.4 mmol) was added. After reacting for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23 g of compound 2-60 (yield 69%, MS: [M+H]+= 747).

Manufacturing Example 2-61

In a nitrogen atmosphere, compound subCB-3 (15 g, 44.7 mmol) and compound amine58 (21.5 g, 44.7 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (18.5 g, 134 mmol) was dissolved in 56 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.4 mmol) was added. After reaction for 8 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.3 g of compound 2-61 (yield 74%, MS: [M+H]+= 737).

Manufacturing Example 2-62

In a nitrogen atmosphere, compound subCB-3 (15 g, 44.7 mmol) and compound amine59 (21.9 g, 44.7 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (18.5 g, 134 mmol) was dissolved in 56 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.4 mmol) was added. After reacting for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26 g of compound 2-62 (yield 78%, MS: [M+H]+= 747).

Manufacturing Example 2-63

In a nitrogen atmosphere, chemical formula CB (15 g, 51 mmol) and [1,1'-biphenyl]-4-ylboronic acid (10.1 g, 51 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (21.1 g, 153 mmol) was dissolved in 63 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.9 g of compound subCB-4 (yield 71%, MS: [M+H]+= 412).

In a nitrogen atmosphere, compound subCB-4 (10 g, 24.3 mmol), compound amine10 (6 g, 24.3 mmol), and sodium tert-butoxide (7.7 g, 36.4 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 8.9 g of compound 2-63 (yield 59%, MS: [M+H]+= 621).

Manufacturing Example 2-64

In a nitrogen atmosphere, compound subCC-1 (10 g, 29.8 mmol), compound amine60 (11.1 g, 29.8 mmol), and sodium tert-butoxide (9.5 g, 44.7 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 2-64 (yield 66%, MS: [M+H]+= 671).

Manufacturing Example 2-65

In a nitrogen atmosphere, compound subCC-1 (10 g, 29.8 mmol), compound amine61 (12.6 g, 29.8 mmol), and sodium tert-butoxide (9.5 g, 44.7 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 10.7 g of compound 2-65 (yield 50%, MS: [M+H]+= 721).

Manufacturing Example 2-66

In a nitrogen atmosphere, compound subCC-1 (15 g, 44.7 mmol) and compound amine62 (21.9 g, 44.7 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (18.5 g, 134 mmol) was dissolved in 56 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.4 mmol) was added. After reaction for 8 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.7 g of compound 2-66 (yield 68%, MS: [M+H]+= 747).

Manufacturing Example 2-67

In a nitrogen atmosphere, compound subCC-1 (15 g, 55.44.7 mmol) and compound amine63 (23.7 g, 44.7 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (18.5 g, 134 mmol) was dissolved in 56 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.4 mmol) was added. After reaction for 8 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26.3 g of compound 2-67 (yield 75%, MS: [M+H]+= 786).

Manufacturing Example 2-68

In a nitrogen atmosphere, CC (15 g, 51 mmol) and naphthalen-2-ylboronic acid (8.8 g, 51 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (21.1 g, 153 mmol) was dissolved in 63 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.8 g of compound subCC-3 (yield 60%, MS: [M+H]+= 386).

In a nitrogen atmosphere, compound subCC-3 (10 g, 25.9 mmol), compound amine16 (8.3 g, 25.9 mmol), and sodium tert-butoxide (8.3 g, 38.9 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 11.5 g of compound 2-68 (yield 66%, MS: [M+H]+= 671).

Manufacturing Example 2-69

In a nitrogen atmosphere, compound subCD-1 (10 g, 29.8 mmol), compound amine64 (11.1 g, 29.8 mmol), and sodium tert-butoxide (9.5 g, 44.7 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 2-69 (yield 60%, MS: [M+H]+= 671).

Manufacturing Example 2-70

In a nitrogen atmosphere, compound subCD-1 (10 g, 29.8 mmol), compound amine65 (11.8 g, 29.8 mmol), and sodium tert-butoxide (9.5 g, 44.7 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 11.2 g of compound 2-70 (yield 54%, MS: [M+H]+= 697).

Manufacturing Example 2-71

In a nitrogen atmosphere, compound subCD-1 (15 g, 44.7 mmol) and compound amine66 (25.1 g, 44.7 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (18.5 g, 134 mmol) was dissolved in 56 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.4 mmol) was added. After reacting for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 28.4 g of compound 2-71 (yield 78%, MS: [M+H]+= 817).

Manufacturing Example 2-72

In a nitrogen atmosphere, chemical formula CD (15 g, 51 mmol) and naphthalen-2-ylboronic acid (8.8 g, 51 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (21.1 g, 153 mmol) was dissolved in 63 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.7 g of compound subCD-5 (yield 70%, MS: [M+H]+= 386).

In a nitrogen atmosphere, compound subCD-5 (10 g, 27.3 mmol), compound amine21 (8.1 g, 27.3 mmol), and sodium tert-butoxide (8.7 g, 41 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 10.7 g of compound 2-72 (yield 61%, MS: [M+H]+= 645).

Manufacturing Example 2-73

In a nitrogen atmosphere, compound subCE-3 (10 g, 29.8 mmol), compound amine67 (13.3 g, 29.8 mmol), and sodium tert-butoxide (9.5 g, 44.7 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 15.3 g of compound 2-73 (yield 69%, MS: [M+H]+= 747).

Manufacturing Example 2-74

In a nitrogen atmosphere, compound subCE-3 (10 g, 29.8 mmol), compound amine17 (12.6 g, 29.8 mmol), and sodium tert-butoxide (9.5 g, 44.7 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 13.1 g of compound 2-74 (yield 61%, MS: [M+H]+= 721).

Manufacturing Example 2-75

In a nitrogen atmosphere, compound subCE-3 (15 g, 44.8 mmol) and compound amine68 (24.2 g, 44.8 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (18.6 g, 134.3 mmol) was dissolved in 56 ml of water, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 10 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 27.1 g of compound 2-75 (yield 76%, MS: [M+H]+= 797).

Manufacturing Example 2-76

In a nitrogen atmosphere, compound subCE-3 (15 g, 44.8 mmol) and compound amine69 (22 g, 44.8 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (18.6 g, 134.3 mmol) was dissolved in 56 ml of water, stirred sufficiently, and 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, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.4 g of compound 2-76 (yield 64%, MS: [M+H]+= 747).

Manufacturing Example 2-77

In a nitrogen atmosphere, compound subCE-1 (15 g, 36.4 mmol) and compound amine70 (13.3 g, 36.4 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (15.1 g, 109.2 mmol) was dissolved in 45 ml of water, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 10 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then 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 2-77 (yield 63%, MS: [M+H]+= 697).

Manufacturing Example 2-78

In a nitrogen atmosphere, compound subCF-1 (10 g, 29.8 mmol), compound amine71 (10.4 g, 29.8 mmol), and sodium tert-butoxide (9.5 g, 44.7 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 2-78 (yield 61%, MS: [M+H]+= 649).

Manufacturing Example 2-79

In a nitrogen atmosphere, compound subCF-1 (10 g, 29.8 mmol), compound amine72 (13.3 g, 29.8 mmol), and sodium tert-butoxide (9.5 g, 44.7 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 2-79 (yield 56%, MS: [M+H]+= 747).

Manufacturing Example 2-80

In a nitrogen atmosphere, compound subCF-1 (15 g, 44.8 mmol) and compound amine73 (23.2 g, 44.8 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (18.6 g, 134.3 mmol) was dissolved in 56 ml of water, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reaction for 8 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 25.9 g of compound 2-80 (yield 75%, MS: [M+H]+= 773).

Manufacturing Example 2-81

In a nitrogen atmosphere, CF (15 g, 51 mmol) and [1,1'-biphenyl]-4-ylboronic acid (10.1 g, 51 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (21.1 g, 153 mmol) was dissolved in 63 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reacting for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.5 g of compound subCF-4 (yield 74%, MS: [M+H]+= 412).

In a nitrogen atmosphere, compound subCF-4 (15 g, 36.4 mmol) and compound amine25 (16.1 g, 36.4 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (15.1 g, 109.2 mmol) was dissolved in 45 ml of water, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reaction for 8 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.8 g of compound 2-81 (yield 74%, MS: [M+H]+= 773).

Manufacturing Example 2-82

In a nitrogen atmosphere, DA (15 g, 51 mmol) and phenylboronic acid (6.2 g, 51 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (21.1 g, 153 mmol) was dissolved in 63 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.5 g of compound subDA-4 (yield 79%, MS: [M+H]+= 336).

In a nitrogen atmosphere, compound subDA-4 (10 g, 29.8 mmol), compound amine74 (12.6 g, 29.8 mmol), and sodium tert-butoxide (9.5 g, 44.7 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 11.4 g of compound 2-82 (yield 53%, MS: [M+H]+= 721).

Manufacturing Example 2-83

In a nitrogen atmosphere, compound subDA-4 (10 g, 29.8 mmol), compound amine75 (12.6 g, 29.8 mmol), and sodium tert-butoxide (9.5 g, 44.7 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 12.2 g of compound 2-83 (yield 57%, MS: [M+H]+= 721).

Manufacturing Example 2-84

In a nitrogen atmosphere, compound subDA-4 (15 g, 44.7 mmol) and compound amine63 (23.7 g, 44.7 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (18.5 g, 134 mmol) was dissolved in 56 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reaction for 8 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.1 g of compound 2-84 (yield 63%, MS: [M+H]+= 786).

Manufacturing Example 2-85

In a nitrogen atmosphere, compound subDB-1 (10 g, 29.8 mmol), compound amine40 (11.1 g, 29.8 mmol), and sodium tert-butoxide (9.5 g, 44.7 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 13.8 g of compound 2-85 (yield 69%, MS: [M+H]+= 671).

Manufacturing Example 2-86

In a nitrogen atmosphere, compound subDB-1 (10 g, 29.8 mmol), compound amine76 (10.4 g, 29.8 mmol), and sodium tert-butoxide (9.5 g, 44.7 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 11.4 g of compound 2-86 (yield 59%, MS: [M+H]+= 649).

Manufacturing Example 2-87

In a nitrogen atmosphere, chemical formula DB (15 g, 51 mmol) and [1,1'-biphenyl]-4-ylboronic acid (10.1 g, 51 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (21.1 g, 153 mmol) was dissolved in 63 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reaction for 8 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.6 g of compound subDB-3 (yield 79%, MS: [M+H]+= 412).

In a nitrogen atmosphere, compound subDB-3 (15 g, 36.4 mmol) and compound amine77 (16.6 g, 36.4 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (15.1 g, 109.2 mmol) was dissolved in 45 ml of water, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.3 g of compound 2-87 (yield 69%, MS: [M+H]+= 767).

Manufacturing Example 2-88

In a nitrogen atmosphere, compound subDC-1 (10 g, 29.8 mmol), compound amine78 (10 g, 29.8 mmol), and sodium tert-butoxide (9.5 g, 44.7 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 2-88 (yield 63%, MS: [M+H]+= 635).

Manufacturing Example 2-89

In a nitrogen atmosphere, compound subDC-1 (15 g, 44.7 mmol) and compound amine79 (23.1 g, 44.7 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (18.5 g, 134 mmol) was dissolved in 56 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reaction for 8 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.8 g of compound 2-89 (yield 69%, MS: [M+H]+= 773).

Manufacturing Example 2-90

In a nitrogen atmosphere, DC (15 g, 51 mmol) and [1,1'-biphenyl]-4-ylboronic acid (10.1 g, 51 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (21.1 g, 153 mmol) was dissolved in 63 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then 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 subDC-3 (yield 62%, MS: [M+H]+= 412).

In a nitrogen atmosphere, compound subDC-3 (10 g, 24.3 mmol), compound amine37 (9.6 g, 24.3 mmol), and sodium tert-butoxide (7.7 g, 36.4 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 10.5 g of compound 2-90 (yield 56%, MS: [M+H]+= 773).

Manufacturing Example 2-91

In a nitrogen atmosphere, compound subDD-1 (10 g, 29.8 mmol), compound amine65 (11.8 g, 29.8 mmol), and sodium tert-butoxide (9.5 g, 44.7 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 14.3 g of compound 2-91 (yield 69%, MS: [M+H]+= 697).

Manufacturing Example 2-92

In a nitrogen atmosphere, compound subDD-1 (10 g, 29.8 mmol), compound amine80 (13.3 g, 29.8 mmol), and sodium tert-butoxide (9.5 g, 44.7 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 11.3 g of compound 2-92 (yield 51%, MS: [M+H]+= 747).

Manufacturing Example 2-93

In a nitrogen atmosphere, compound subDD-1 (15 g, 44.8 mmol) and compound amine81 (20.8 g, 44.8 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (18.6 g, 134.3 mmol) was dissolved in 56 ml of water, stirred sufficiently, and 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, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.2 g of compound 2-93 (yield 75%, MS: [M+H]+= 721).

Manufacturing Example 2-94

In a nitrogen atmosphere, compound subDD-1 (15 g, 44.7 mmol) and compound amine82 (19.7 g, 44.7 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (18.5 g, 134 mmol) was dissolved in 56 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.7 g of compound 2-94 (yield 73%, MS: [M+H]+= 697).

Manufacturing Example 2-95

In a nitrogen atmosphere, chemical formula DD (15 g, 51 mmol) and naphthalen-2-ylboronic acid (8.8 g, 51 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (21.1 g, 153 mmol) was dissolved in 63 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.9 g of compound subDD-7 (yield 71%, MS: [M+H]+= 386).

In a nitrogen atmosphere, compound subDD-7 (15 g, 38.9 mmol) and compound amine77 (17.7 g, 38.9 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (16.1 g, 116.6 mmol) was dissolved in 48 ml of water, stirred sufficiently, and then 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, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.3 g of compound 2-95 (yield 72%, MS: [M+H]+= 761).

Manufacturing Example 2-96

In a nitrogen atmosphere, compound subDE-1 (10 g, 29.8 mmol), compound amine78 (13.3 g, 29.8 mmol), and sodium tert-butoxide (9.5 g, 44.7 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 13.6 g of compound 2-96 (yield 61%, MS: [M+H]+= 747).

Manufacturing Example 2-97

In a nitrogen atmosphere, compound subDE-1 (10 g, 29.8 mmol), compound amine79 (12.3 g, 29.8 mmol), and sodium tert-butoxide (9.5 g, 44.7 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.2 g of compound 2-97 (yield 67%, MS: [M+H]+= 712).

Manufacturing Example 2-98

In a nitrogen atmosphere, compound subDE-1 (15 g, 44.7 mmol) and compound amine80 (23.1 g, 44.7 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (18.5 g, 134 mmol) was dissolved in 56 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reaction for 8 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.1 g of compound 2-98 (yield 64%, MS: [M+H]+= 773).

Manufacturing Example 2-99

In a nitrogen atmosphere, compound subDE-1 (15 g, 44.7 mmol) and compound amine81 (25.3 g, 44.7 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (18.5 g, 134 mmol) was dissolved in 56 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.9 g of compound 2-99 (yield 65%, MS: [M+H]+= 823).

Manufacturing Example 2-100

In a nitrogen atmosphere, compound subDF-1 (10 g, 24.3 mmol), compound amine82 (9 g, 24.3 mmol), and sodium tert-butoxide (7.7 g, 36.4 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 8.8 g of compound 2-100 (yield 54%, MS: [M+H]+= 671).

Manufacturing Example 2-101

In a nitrogen atmosphere, compound subDF-1 (10 g, 29.8 mmol), compound amine19 (12.2 g, 29.8 mmol), and sodium tert-butoxide (9.5 g, 44.7 mmol) were added to 200 ml of Xylene, stirred, and refluxed. Afterwards, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, the reaction was cooled to room temperature, and the solvent was removed under reduced pressure. Afterwards, the compound was completely dissolved in chloroform, washed twice with water, 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 2-101 (yield 59%, MS: [M+H]+= 710).

Manufacturing Example 2-102

In a nitrogen atmosphere, compound subDF-1 (15 g, 44.8 mmol) and compound amine56 (21.6 g, 44.8 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (18.6 g, 134.3 mmol) was dissolved in 56 ml of water, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reaction for 8 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.7 g of compound 2-102 (yield 72%, MS: [M+H]+= 737).

Manufacturing Example 2-103

In a nitrogen atmosphere, compound subDF-1 (15 g, 44.8 mmol) and compound amine83 (21.1 g, 44.8 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (18.6 g, 134.3 mmol) was dissolved in 56 ml of water, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.4 g of compound 2-103 (yield 72%, MS: [M+H]+= 727).

Manufacturing Example 2-104

In a nitrogen atmosphere, DF (15 g, 51 mmol) and naphthalen-2-ylboronic acid (8.8 g, 51 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (21.1 g, 153 mmol) was dissolved in 63 ml of water, stirred sufficiently, and then Tetrakis(triphenylphosphine)palladium(0) (0.6 g, 0.5 mmol) was added. After reaction for 8 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.9 g of compound subDF-3 (yield 76%, MS: [M+H]+= 386).

In a nitrogen atmosphere, compound subDF-3 (15 g, 38.9 mmol) and compound amine50 (20.1 g, 38.9 mmol) were added to 300 ml of THF, stirred, and refluxed. Afterwards, potassium carbonate (16.1 g, 116.6 mmol) was dissolved in 48 ml of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reaction for 8 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.8 g of compound 2-104 (yield 62%, MS: [M+H]+= 823).

[Example]

Comparative example A

A glass substrate coated with a thin film of ITO (indium tin oxide) with a thickness of 1000 Å was placed in distilled water with a detergent dissolved in it and washed ultrasonically. At this time, a detergent from Fischer Co. was used, and distilled water filtered secondarily using a filter from Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, ultrasonic cleaning was repeated twice with distilled water for 10 minutes. After washing with distilled water, it was ultrasonic washed with solvents of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. Additionally, the substrate was cleaned for 5 minutes using oxygen plasma and then transported to a vacuum evaporator.

On the ITO transparent electrode prepared in this way, the following compound HI-1 was formed as a hole injection layer to a thickness of 1150 Å, and 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 with a film thickness of 800 Å. Next, the following compound EB-1 was vacuum deposited on the hole transport layer to a film thickness of 150 Å to form an electron blocking layer. Next, the following compound RH-1 and compound Dp-7 were vacuum deposited on the EB-1 deposition film at a weight ratio of 98:2 to form a red light-emitting layer with a thickness of 400 Å. The following compound HB-1 was vacuum deposited on the light emitting layer to a film thickness of 30 Å to form a hole blocking layer. Next, the following compound ET-1 and the following compound LiQ were vacuum deposited on the hole blocking layer at a weight ratio of 2:1 to form an electron injection and transport layer with a thickness of 300 Å. Lithium fluoride (LiF) to a thickness of 12 Å and aluminum to a thickness of 1000 Å were sequentially deposited on the electron injection and transport layer to form a cathode.

In the above process, the deposition rate of organic matter was maintained at 0.4 ~ 0.7 Å/sec, the deposition rate of lithium fluoride of the cathode was maintained at 0.3 Å/sec, and aluminum was maintained at 2 Å/sec, and the vacuum degree during deposition was 2×10 ^-7. An organic light emitting device was manufactured by maintaining ~5×10 ^-6 torr.

Examples 1 to 29

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

Comparative Examples 1 to 7

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

Examples 30 to 75

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

Comparative Examples 8 to 14

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

Examples 76 to 179

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

[Experimental example]

When current was applied to the organic light emitting devices manufactured in Examples 1 to 179, Comparative Example A, and Comparative Examples 1 to 14, the voltage and efficiency were measured (based on 15 mA/cm ² ) and the results were measured. Shown in Tables 1 to 3 below. Lifespan T95 refers to the time it takes for the luminance to decrease to 95% from the initial luminance of 7,000 nits.

division host driving voltage
(V) efficiency
(cd/A) life span
T95(hr) Luminous color Comparative example A Compound RH-1 3.91 16.54 113 Red Example 1 Compound 1-1 3.61 20.52 188 Red Example 2 Compound 1-4 3.69 20.93 188 Red Example 3 Compound 1-6 3.45 20.52 223 Red Example 4 Compound 1-7 3.55 20.93 215 Red Example 5 Compound 1-8 3.47 21.54 228 Red Example 6 Compound 1-9 3.45 20.80 208 Red Example 7 Compound 1-11 3.55 20.52 210 Red Example 8 Compound 1-13 3.49 20.36 156 Red Example 9 Compound 1-14 3.51 21.47 169 Red Example 10 Compound 1-17 3.49 21.72 216 Red Example 11 Compound 1-19 3.76 18.34 181 Red Example 12 Compound 1-22 3.70 20.69 205 Red Example 13 Compound 1-24 3.56 20.72 202 Red Example 14 Compound 1-25 3.68 20.58 212 Red Example 15 Compound 1-26 3.58 20.41 177 Red Example 16 Compound 1-29 3.55 20.31 194 Red Example 17 Compound 1-31 3.67 19.94 195 Red Example 18 Compound 1-33 3.68 18.72 215 Red Example 19 Compound 1-35 3.55 21.25 177 Red Example 20 Compound 1-38 3.84 18.58 182 Red Example 21 Compound 1-39 3.80 18.84 169 Red Example 22 Compound 1-40 3.59 20.39 221 Red Example 23 Compound 1-42 3.54 20.75 221 Red Example 24 Compound 1-44 3.47 20.84 212 Red Example 25 Compound 1-47 3.55 19.91 216 Red Example 26 Compound 1-49 3.73 19.03 211 Red Example 27 Compound 1-50 3.82 18.40 173 Red Example 28 Compound 1-52 3.79 18.69 179 Red Example 29 Compound 1-53 3.53 20.57 161 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 Electronic blocking layer driving voltage
(V) efficiency
(cd/A) life span
T95(hr) Luminous color Example 30 Compound 2-1 3.60 20.65 181 Red Example 31 Compound 2-4 3.53 19.10 178 Red Example 32 Compound 2-7 3.57 20.04 183 Red Example 33 Compound 2-9 3.61 19.41 177 Red Example 34 Compound 2-14 3.53 20.31 184 Red Example 35 Compound 2-15 3.62 20.47 181 Red Example 36 Compound 2-16 3.57 21.01 185 Red Example 37 Compound 2-19 3.58 20.06 191 Red Example 38 Compound 2-21 3.55 20.34 184 Red Example 39 Compound 2-23 3.58 19.84 190 Red Example 40 Compound 2-26 3.63 19.34 193 Red Example 41 Compound 2-29 3.71 18.51 174 Red Example 42 Compound 2-31 3.62 18.39 178 Red Example 43 Compound 2-34 3.68 18.53 184 Red Example 44 Compound 2-35 3.68 19.02 178 Red Example 45 Compound 2-36 3.69 18.95 172 Red Example 46 Compound 2-37 3.67 18.50 175 Red Example 47 Compound 2-38 3.60 18.48 181 Red Example 48 Compound 2-41 3.69 18.55 170 Red Example 49 Compound 2-45 3.70 18.29 177 Red Example 50 Compound 2-47 3.61 18.83 183 Red Example 51 Compound 2-50 3.70 18.82 170 Red Example 52 Compound 2-55 3.75 18.14 175 Red Example 53 Compound 2-58 3.77 17.65 162 Red Example 54 Compound 2-60 3.75 18.30 169 Red Example 55 Compound 2-62 3.78 17.75 165 Red Example 56 Compound 2-63 3.68 18.22 173 Red Example 57 Compound 2-65 3.73 17.58 169 Red Example 58 Compound 2-66 3.72 18.02 147 Red Example 59 Compound 2-68 3.72 18.23 152 Red Example 60 Compound 2-69 3.75 18.14 186 Red Example 61 Compound 2-74 3.77 17.65 195 Red Example 62 Compound 2-77 3.75 18.30 188 Red Example 63 Compound 2-79 3.78 17.75 188 Red Example 64 Compound 2-80 3.68 18.22 185 Red Example 65 Compound 2-82 3.82 16.94 157 Red Example 66 Compound 2-84 3.84 16.92 163 Red Example 67 Compound 2-85 3.81 17.70 160 Red Example 68 Compound 2-87 3.84 17.18 154 Red Example 69 Compound 2-89 3.77 17.45 151 Red Example 70 Compound 2-92 3.76 17.61 161 Red Example 71 Compound 2-93 3.68 19.94 175 Red Example 72 Compound 2-97 3.64 19.07 168 Red Example 73 Compound 2-98 3.60 19.43 179 Red Example 74 Compound 2-101 3.63 19.74 185 Red Example 75 Compound 2-104 3.65 19.49 171 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 4.31 14.96 62 Red

division first host 2nd host driving voltage
(V) efficiency
(cd/A) life span
T95(hr) Luminous color Example 76 Compound 1-4 Compound 2-4 3.37 23.40 223 Red Example 77 Compound 1-4 Compound 2-9 3.39 23.60 212 Red Example 78 Compound 1-4 Compound 2-29 3.41 23.46 217 Red Example 79 Compound 1-4 Compound 2-31 3.47 23.68 224 Red Example 80 Compound 1-4 Compound 2-55 3.37 23.42 223 Red Example 81 Compound 1-4 Compound 2-63 3.42 23.57 224 Red Example 82 Compound 1-4 Compound 2-84 3.46 23.59 209 Red Example 83 Compound 1-4 Compound 2-85 3.47 23.24 225 Red Example 84 Compound 1-5 Compound 2-7 3.37 23.40 266 Red Example 85 Compound 1-5 Compound 2-14 3.39 23.60 252 Red Example 86 Compound 1-5 Compound 2-34 3.41 23.46 244 Red Example 87 Compound 1-5 Compound 2-41 3.47 23.68 251 Red Example 88 Compound 1-5 Compound 2-58 3.37 23.42 252 Red Example 89 Compound 1-5 Compound 2-77 3.42 23.57 257 Red Example 90 Compound 1-5 Compound 2-87 3.46 23.59 245 Red Example 91 Compound 1-5 Compound 2-92 3.47 23.24 266 Red Example 92 Compound 1-6 Compound 2-15 3.41 23.06 248 Red Example 93 Compound 1-6 Compound 2-19 3.39 23.29 260 Red Example 94 Compound 1-6 Compound 2-35 3.42 23.58 259 Red Example 95 Compound 1-6 Compound 2-45 3.37 23.76 251 Red Example 96 Compound 1-6 Compound 2-62 3.52 23.88 257 Red Example 97 Compound 1-6 Compound 2-74 3.44 23.72 266 Red Example 98 Compound 1-6 Compound 2-89 3.43 23.78 264 Red Example 99 Compound 1-6 Compound 2-93 3.49 23.21 246 Red Example 100 Compound 1-8 Compound 2-21 3.47 23.15 252 Red Example 101 Compound 1-8 Compound 2-26 3.41 23.03 259 Red Example 102 Compound 1-8 Compound 2-38 3.43 23.88 258 Red Example 103 Compound 1-8 Compound 2-50 3.52 24.03 246 Red Example 104 Compound 1-8 Compound 2-68 3.44 23.39 260 Red Example 105 Compound 1-8 Compound 2-80 3.39 23.68 257 Red Example 106 Compound 1-8 Compound 2-98 3.40 23.55 257 Red Example 107 Compound 1-8 Compound 2-101 3.51 23.34 263 Red Example 108 Compound 1-14 Compound 2-4 3.39 23.30 225 Red Example 109 Compound 1-14 Compound 2-9 3.36 23.65 221 Red Example 110 Compound 1-14 Compound 2-29 3.38 23.65 217 Red Example 111 Compound 1-14 Compound 2-31 3.49 24.10 213 Red Example 112 Compound 1-14 Compound 2-55 3.42 23.38 221 Red Example 113 Compound 1-14 Compound 2-63 3.47 23.18 216 Red Example 114 Compound 1-14 Compound 2-84 3.40 23.48 226 Red Example 115 Compound 1-14 Compound 2-85 3.44 23.53 207 Red Example 116 Compound 1-17 Compound 2-7 3.47 23.33 245 Red Example 117 Compound 1-17 Compound 2-14 3.61 23.40 237 Red Example 118 Compound 1-17 Compound 2-34 3.57 22.73 234 Red Example 119 Compound 1-17 Compound 2-41 3.48 23.44 238 Red Example 120 Compound 1-17 Compound 2-58 3.58 22.33 245 Red Example 121 Compound 1-17 Compound 2-77 3.61 22.95 233 Red Example 122 Compound 1-17 Compound 2-87 3.62 22.78 237 Red Example 123 Compound 1-17 Compound 2-92 3.53 22.57 231 Red Example 124 Compound 1-19 Compound 2-15 3.71 21.65 237 Red Example 125 Compound 1-19 Compound 2-19 3.58 21.44 231 Red Example 126 Compound 1-19 Compound 2-35 3.70 21.65 237 Red Example 127 Compound 1-19 Compound 2-45 3.69 21.47 228 Red Example 128 Compound 1-19 Compound 2-62 3.68 22.35 225 Red Example 129 Compound 1-19 Compound 2-74 3.68 21.48 228 Red Example 130 Compound 1-19 Compound 2-89 3.72 21.45 227 Red Example 131 Compound 1-19 Compound 2-93 3.71 22.26 227 Red Example 132 Compound 1-24 Compound 2-21 3.58 23.19 243 Red Example 133 Compound 1-24 Compound 2-26 3.49 23.48 241 Red Example 134 Compound 1-24 Compound 2-38 3.57 22.52 246 Red Example 135 Compound 1-24 Compound 2-50 3.53 22.73 234 Red Example 136 Compound 1-24 Compound 2-68 3.62 22.92 233 Red Example 137 Compound 1-24 Compound 2-80 3.59 23.43 227 Red Example 138 Compound 1-24 Compound 2-98 3.55 23.15 242 Red Example 139 Compound 1-24 Compound 2-101 3.47 23.16 245 Red Example 140 Compound 1-33 Compound 2-4 3.56 24.01 239 Red Example 141 Compound 1-33 Compound 2-9 3.60 23.40 229 Red Example 142 Compound 1-33 Compound 2-29 3.54 23.70 247 Red Example 143 Compound 1-33 Compound 2-31 3.50 23.63 232 Red Example 144 Compound 1-33 Compound 2-55 3.49 24.02 242 Red Example 145 Compound 1-33 Compound 2-63 3.48 23.94 237 Red Example 146 Compound 1-33 Compound 2-84 3.49 23.07 233 Red Example 147 Compound 1-33 Compound 2-85 3.49 23.53 229 Red Example 148 Compound 1-40 Compound 2-7 3.62 21.50 262 Red Example 149 Compound 1-40 Compound 2-14 3.72 21.21 258 Red Example 150 Compound 1-40 Compound 2-34 3.60 21.49 257 Red Example 151 Compound 1-40 Compound 2-41 3.72 21.24 245 Red Example 152 Compound 1-40 Compound 2-58 3.68 21.68 249 Red Example 153 Compound 1-40 Compound 2-77 3.61 21.73 255 Red Example 154 Compound 1-40 Compound 2-87 3.58 21.17 259 Red Example 155 Compound 1-40 Compound 2-92 3.64 21.82 266 Red Example 156 Compound 1-44 Compound 2-15 3.50 23.81 252 Red Example 157 Compound 1-44 Compound 2-19 3.40 23.85 248 Red Example 158 Compound 1-44 Compound 2-35 3.38 23.20 266 Red Example 159 Compound 1-44 Compound 2-45 3.44 23.17 259 Red Example 160 Compound 1-44 Compound 2-62 3.40 23.89 255 Red Example 161 Compound 1-44 Compound 2-74 3.43 23.52 261 Red Example 162 Compound 1-44 Compound 2-89 3.50 23.57 255 Red Example 163 Compound 1-44 Compound 2-93 3.52 23.56 253 Red Example 164 Compound 1-49 Compound 2-21 3.68 22.26 235 Red Example 165 Compound 1-49 Compound 2-26 3.63 21.52 233 Red Example 166 Compound 1-49 Compound 2-38 3.59 21.21 225 Red Example 167 Compound 1-49 Compound 2-50 3.58 21.78 223 Red Example 168 Compound 1-49 Compound 2-68 3.58 21.86 232 Red Example 169 Compound 1-49 Compound 2-80 3.64 22.31 223 Red Example 170 Compound 1-49 Compound 2-98 3.57 21.82 231 Red Example 171 Compound 1-49 Compound 2-101 3.57 21.42 222 Red Example 172 Compound 1-52 Compound 2-4 3.54 22.48 243 Red Example 173 Compound 1-52 Compound 2-9 3.48 23.48 235 Red Example 174 Compound 1-52 Compound 2-29 3.57 22.37 245 Red Example 175 Compound 1-52 Compound 2-31 3.49 22.45 247 Red Example 176 Compound 1-52 Compound 2-55 3.61 23.25 228 Red Example 177 Compound 1-52 Compound 2-63 3.49 22.29 244 Red Example 178 Compound 1-52 Compound 2-84 3.58 22.27 228 Red Example 179 Compound 1-52 Compound 2-85 3.58 22.16 234 Red

When current was applied to the organic light emitting devices manufactured in Examples 1 to 179 and Comparative Examples 1 to 14, the results shown in Tables 1 to 3 were obtained.

As shown in Table 1 and Table 2, the organic light emitting device using the compound of the present invention in the light emitting layer or electron blocking layer shows a decrease in driving voltage and an increase in efficiency and lifespan compared to the comparative example compound. Additionally, as shown in Table 3, when the compounds of the present invention are co-deposited and used as a cohost, the driving voltage tends to decrease and efficiency and lifespan increase compared to when a single material is used as a host.

In conclusion, it can be confirmed that the driving voltage, luminous efficiency, and lifespan characteristics of an organic light-emitting device can be improved when the present invention is used as a host or electron blocking layer for a red light-emitting layer in a device expressing red.

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)

Compound represented by Formula 1:
[Formula 1]

In Formula 1,
A is a thiazole ring or oxazole ring fused to 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 substituted or unsubstituted C _6-60 aryl; or C _2-60 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O and S,
Wherein 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 C _6-60 aryl; or C _2-60 heteroaryl containing at least one selected from the group consisting of N, O and S,
D is deuterium,
n is an integer between 0 and 5.
According to paragraph 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 Formulas 1-1 to 1-4,
The descriptions of R ₁ , R ₂ , L ₁ , D and n are as defined in paragraph 1.
According to paragraph 1,
L ₁ is a single bond, phenylene, biphenyldiyl, naphthalenediyl, or dibenzofurandiyl,
compound.
According to paragraph 1,
Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, dibenzofuranyl, or dibenzothiophenyl,
compound.
According to paragraph 1,
Ar ₃ and Ar ₄ are each independently phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, dimethylfluorenyl, dibenzofuranyl, dibenzothiophenyl, phenyl carbazolyl, or phenyl naphthyl. person,
compound.
According to paragraph 1,
L ₂ and L ₃ are each independently a single bond, phenylene, biphenyldiyl, or naphthalenediyl,
compound.
According to paragraph 1,
L ₄ and L ₅ are each independently a single bond, phenylene, biphenyldiyl, naphthalenediyl, or carbazoldiyl,
compound.
According to paragraph 1,
At least one of Ar ₁ and Ar ₂ is substituted or unsubstituted C _6-60 aryl,
compound.
According to paragraph 1,
At least one of Ar ₃ and Ar ₄ is substituted or unsubstituted C _6-60 aryl,
compound.
According to paragraph 1,
R ₂ is phenyl, biphenylyl, naphthyl, dibenzofuranyl, or dibenzothiophenyl,
compound.
According to paragraph 1,
The compound represented by Formula 1 is any one selected from the group consisting of:
compound:

.
first electrode; a second electrode provided opposite to the first electrode; And an organic light-emitting device comprising at least one organic material layer provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer contains a compound according to any one of claims 1 to 11. Containing more than,
Organic light emitting device.
According to clause 12,
The organic material layer is a light emitting layer or an electron blocking layer,
Organic light emitting device.