ORGANIC LIGHT EMITTING DEVICE

Abstract

An organic light emitting device comprising an anode, a cathode, and a light emitting layer between the anode and the cathode, the light emitting layer including a compound represented by Chemical Formula 1 and a compound represented by Chemical Formula 2, and having improved driving voltage, efficiency and lifetime is provided.

Description

FIELD OF DISCLOSURE

The present disclosure relates to an organic light emitting device having improved driving voltage, efficiency and lifetime.

BACKGROUND

In general, an organic light emitting phenomenon refers to a phenomenon where electric energy is converted into light energy by using an organic material. The organic light emitting device using the organic light emitting phenomenon has characteristics such as a wide viewing angle, an excellent contrast, a fast response time, an excellent luminance, driving voltage and response speed, and thus many studies have proceeded.

The organic light emitting device generally has a structure which comprises an anode, a cathode, and an organic material layer between the anode and the cathode. The organic material layer frequently has a multilayered structure that comprises different materials in order to enhance efficiency and stability of the organic light emitting device, and for example, the organic material layer may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and the like. In the structure of the organic light emitting device, if a voltage is applied between two electrodes, the holes are injected from an anode into the organic material layer and the electrons are injected from the cathode into the organic material layer, and when the injected holes and electrons meet each other, an exciton is formed, and light is emitted when the exciton falls to a ground state again.

There is a continuing need for the development of an organic material used in the organic light emitting device as described above.

RELATED ART

Korean Unexamined Patent Publication No. 10-2000-0051826

SUMMARY

It is an object of the present disclosure to provide an organic light emitting device having improved driving voltage, efficiency and lifetime.

According to the present disclosure, there is provided the following organic light emitting device:

• • an organic light emitting device comprising:
  • an anode;
  • a cathode; and
  • a light emitting layer between the anode and the cathode,
  • wherein the light emitting layer includes a compound represented by the following Chemical Formula 1 and a compound represented by the following Chemical Formula 2:

• • in Chemical Formula 1,
  • Ar₁ and Ar₂ are each independently a substituted or unsubstituted C_6-60 aryl; or a substituted or unsubstituted C_2-60 heteroaryl containing one or more selected from the group consisting of N, O and S,
  • L₁ is a single bond or one selected from the group consisting of

• •  wherein D is deuterium, n1 to n3 and n5 are each independently an integer of 0 to 4, and n4, n6 and n7 are each independently an integer of 0 to 6,
  • L₂ and L₃ are each independently a single bond; or a substituted or unsubstituted C_6-60 arylene,
  • R₁ is each independently hydrogen; deuterium; a substituted or unsubstituted C_6-60 aryl; or a substituted or unsubstituted C_2-60 heteroaryl containing one or more selected from the group consisting of N, O and S, with the proviso that at least one R₁ is deuterium, phenyl substituted with deuterium, a substituted or unsubstituted C_10-60 aryl or a substituted or unsubstituted C_2-60 heteroaryl containing one or more selected from the group consisting of N, O and S, and
  • a is an integer of 1 to 7,
  • wherein the compound represented by Chemical Formula 1 may not contain any deuterium or may contain at least one deuterium,

• • in Chemical Formula 2,
  • A is a benzene ring or a naphthalene ring,
  • Ar₃ and Ar₄ are each independently a substituted or unsubstituted C_6-60 aryl; or a substituted or unsubstituted C_2-60 heteroaryl containing one or more selected from the group consisting of N, O and S,
  • L₄ is a substituted or unsubstituted C_6-60 arylene, and
  • L₅ and L₆ are each independently a single bond, a substituted or unsubstituted C_6-60 arylene, or a substituted or unsubstituted C_2-60 heteroarylene containing one or more selected from the group consisting of N, O and S.

The above-mentioned organic light emitting device includes the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 in the light emitting layer, and thus can improve the efficiency, achieve low driving voltage and/or improve lifetime characteristics in the organic light emitting device.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows an example of an organic light emitting device comprising a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4.

FIG. 2 shows an example of an organic light emitting device comprising a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 7, a light emitting layer 3, a hole blocking layer 8, an electron injection and transport layer 9, and a cathode 4.

DETAILED DESCRIPTION

Hereinafter, embodiments of the present disclosure will be described in more detail to facilitate understanding of the invention.

As used herein, the notation

means a bond linked to another substituent group.

As used herein, the term “substituted or unsubstituted” means being unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium; a halogen group; a nitrile group; a nitro group; a hydroxy group; a carbonyl group; an ester group; an imide group; an amino group; a phosphine oxide group; an alkoxy group; an aryloxy group; an alkylthioxy group; an arylthioxy group; an alkylsulfoxy group; an arylsulfoxy group; a silyl group; a boron group; an alkyl group; a cycloalkyl group; an alkenyl group; an aryl group; an aralkyl group; an aralkenyl group; an alkylaryl group; an alkylamine group; an aralkylamine group; a heteroarylamine group; an arylamine group; an arylphosphine group; and a heteroaryl group containing at least one of N, O and S atoms, or being unsubstituted or substituted with a substituent from the above substituent group which is further substituted by one or more selected from the above substituent group.

In the present disclosure, the carbon number of a carbonyl group is not particularly limited, but is preferably 1 to 40. Specifically, the carbonyl group may be a substituent having the following structural formulas, but is not limited thereto.

In the present disclosure, an ester group may have a structure in which oxygen of the ester group may be substituted by a straight-chain, branched-chain, or cyclic alkyl group having 1 to 25 carbon atoms, or an aryl group having 6 to 25 carbon atoms. Specifically, the ester group may be a substituent having the following structural formulas, but is not limited thereto.

In the present disclosure, the carbon number of an imide group is not particularly limited, but is preferably 1 to 25. Specifically, the imide group may be a substituent having the following structural formulas, but is not limited thereto.

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

In the present disclosure, a boron group specifically includes a trimethylboron group, a triethylboron group, a t-butyldimethylboron group, a triphenylboron group, and a phenylboron group, but is not limited thereto.

In the present disclosure, examples of a halogen group include fluorine, chlorine, bromine, or iodine.

In the present disclosure, the alkyl group may be straight-chain or branched-chain, and the carbon number thereof 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 the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but are not limited thereto.

In the present disclosure, the alkenyl group may be straight-chain or branched-chain, and the carbon number thereof is not particularly limited, but is preferably 2 to 40. According to one embodiment, the carbon number of the alkenyl group is 2 to 20. According to another embodiment, the carbon number of the alkenyl group is 2 to 10. According to still another embodiment, the carbon number of the alkenyl group is 2 to 6. Specific examples thereof 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, a stilbenyl group, a styrenyl group, and the like, but are not limited thereto.

In the present disclosure, a cycloalkyl group is not particularly limited, but the carbon number thereof is preferably 3 to 60. According to one embodiment, the carbon number of the cycloalkyl group is 3 to 30. According to another embodiment, the carbon number of the cycloalkyl group is 3 to 20. According to still another embodiment, the carbon number of the cycloalkyl group is 3 to 6. Specific examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto.

In the present disclosure, an aryl group is not particularly limited, but the carbon number thereof is preferably 6 to 60, and it may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the carbon number of the aryl group is 6 to 30. According to one embodiment, the carbon number of the aryl group is 6 to 20. The aryl group may be a phenyl group, a biphenyl group, a terphenyl group or the like as the monocyclic aryl group, but is not limited thereto. The polycyclic aryl group includes a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, a perylenyl group, a chrysenyl group, or the like, but is not limited thereto.

In the present disclosure, the fluorenyl group may be substituted, and two substituents may be linked with each other to form a spiro structure. In the case where the fluorenyl group is substituted,

and the like can be formed. However, the structure is not limited thereto.

In the present disclosure, a heteroaryl group is a heteroaryl group containing at least one of O, N, Si and S as a heteroatom, and the carbon number thereof is not particularly limited, but is preferably 2 to 60. According to an exemplary embodiment of heteroaryl, the heteroaryl group has 6 to 30 carbon atoms. According to an exemplary embodiment, the heteroaryl group has 6 to 20 carbon atoms. Examples of heteroaryl groups include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazol group, an oxadiazol group, a triazol group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazine group, an acridyl group, a pyridazine group, a pyrazinyl group, a quinolinyl group, a quinazoline group, a quinoxalinyl group, a phthalazinyl group, a pyridopyrimidinyl group, a pyridopyrazinyl group, a pyrazinopyrazinyl group, an isoquinoline group, an indole group, a carbazole group, a benzoxazole group, a benzoimidazole group, a benzothiazol group, a benzocarbazole group, a benzothiophene group, a dibenzothiophene group, a benzofuranyl group, a phenanthroline group, an isoxazolyl group, a thiadiazolyl group, a phenothiazinyl group, a dibenzofuranyl group, and the like, but are not limited thereto.

In the present disclosure, the aryl group in the aralkyl group, the aralkenyl group, the alkylaryl group and the arylamine group is the same as the above-mentioned examples of the aryl group. In the present disclosure, the alkyl group in the aralkyl group, the alkylaryl group and the alkylamine group is the same as the above-mentioned examples of the alkyl group. In the present disclosure, the heteroaryl in the heteroarylamine may be applied to the above-mentioned description of the heteroaryl group. In the present disclosure, the alkenyl group in the aralkenyl group is the same as the above-mentioned examples of the alkenyl group. In the present disclosure, the above-mentioned description of the aryl group may be applied except that the arylene is a divalent group. In the present disclosure, the above-mentioned description of the heteroaryl group may be applied except that the heteroarylene is a divalent group. In the present disclosure, the above-mentioned description of the aryl group or cycloalkyl group may be applied except that the hydrocarbon ring is not a monovalent group but formed by combining two substituent groups. In the present disclosure, the above-mentioned description of the heteroaryl group may be applied, except that the heteroaryl is not a monovalent group but formed by combining two substituent groups.

In the present disclosure, the term “deuterated or substituted with deuterium” means that at least one available hydrogen in each Chemical Formula is substituted with deuterium. Specifically, “substituted with deuterium” in the definition of each Chemical Formula or substituent means that at least one or more positions at which hydrogen can be bonded in the molecule are substituted with deuterium.

Additionally, in the present disclosure, the term “deuterium substitution rate” means the percentage of the number of substituted deuterium relative to the total number of hydrogens that may be present in each chemical formula.

Below, the present disclosure will be described in detail for each configuration.

Anode and Cathode

An anode and a cathode used in the present disclosure mean electrodes used in an organic light emitting device.

As the anode material, generally, a material having a large work function is preferably used so that holes can be smoothly injected into the organic material layer. Specific examples of the anode material include metals such as vanadium, chrome, copper, zinc, and gold, or an alloy thereof; metal oxides such as zinc oxides, indium oxides, indium tin oxides (ITO), and indium zinc oxides (IZO); a combination of metals and oxides, such as ZnO:Al or SNO₂:Sb; conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDOT), polypyrrole, and polyaniline, and the like, but are not limited thereto.

As the cathode material, generally, a material having a small work function is preferably used so that electrons can be easily injected into the organic material layer. Specific examples of the cathode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or an alloy thereof; a multilayered structure material such as LiF/Al or LiO₂/Al, and the like, but are not limited thereto.

Hole Injection Layer

The organic light emitting device according to the present disclosure may further include a hole injection layer on the anode, if necessary.

The hole injection layer is a layer for injecting holes from the electrode, and the hole injection material is preferably a compound which has a capability of transporting the holes, thus has a hole injecting effect in the anode and an excellent hole injecting effect to the light emitting layer or the light emitting material, prevents excitons produced in the light emitting layer from moving to a hole injection layer or the electron injection material, and further is excellent in the ability to form a thin film. Further, it is preferable that a HOMO (highest occupied molecular orbital) of the hole injection material is between the work function of the anode material and a HOMO of a peripheral organic material layer.

Specific examples of the hole injection material include metal porphyrine, oligothiophene, an arylamine-based organic material, a hexanitrilehexaazatriphenylene-based organic material, a quinacridone-based organic material, a perylene-based organic material, anthraquinone, polyaniline and polythiophene-based conductive compound, and the like, but are not limited thereto.

Hole Transport Layer

The organic light emitting device according to the present disclosure may include a hole transport layer on the anode (or on the hole injection layer if the hole injection layer exists), if necessary.

The hole transport layer is a layer that can receive the holes from the anode or the hole injection layer and transport the holes to the light emitting layer, and the hole transport material is suitably a material having large mobility to the holes, which may receive holes from the anode or the hole injection layer and transfer the holes to the light emitting layer.

Specific examples thereof include an arylamine-based organic material, a conductive polymer, a block copolymer in which a conjugate portion and a non-conjugate portion are present together, and the like, but are not limited thereto.

Electron Blocking Layer

The organic light emitting device according to the present disclosure may include an electron blocking layer between a hole transport layer and a light emitting layer, if necessary. The electron blocking layer refers to a layer which is formed on the hole transport layer, and preferably, is provided in contact with the light emitting layer, and thus serves to control hole mobility, to prevent excessive movement of electrons, and to increase the probability of hole-electron bonding, thereby improving the efficiency of the organic light emitting device. The electron blocking layer includes an electron blocking material, and as an example of such an electron blocking material, an arylamine-based organic material or the like can be used, but is not limited thereto.

Light Emitting Layer

The light emitting layer used in the present disclosure is a layer that can emit light in the visible light region by combining holes and electrons transported from the anode and the cathode. Generally, the light emitting layer includes a host material and a dopant material, and in the present disclosure, the light emitting layer includes the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 as a host.

The compound represented by Chemical Formula 1 may contain no deuterium or may contain at least one deuterium.

Preferably, Ar₁ and Ar₂ may be each independently a substituted or unsubstituted C_6-20 aryl; or a substituted or unsubstituted C_2-20 heteroaryl containing one or more selected from the group consisting of N, O and S.

More preferably, Ar₁ and Ar₂ may be each independently phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, dibenzofuranyl, dibenzothiophenyl, or triphenylsilyl phenyl, each of which may be unsubstituted or substituted with deuterium.

Most preferably, Ar₁ and Ar₂ may be each independently one selected from the following:

Preferably L₁ may be a single bond or one selected from the following:

in the above listed groups, n1 to n7 are the same as defined in Chemical Formula 1.

Preferably, L₂ and L₃ may be each independently a single bond, or may be a substituted or unsubstituted C_6-20 arylene.

More preferably, L₂ and L₃ may be each independently a single bond, phenylene, biphenylylene, or naphthalenediyl, each of which, except a single bond, may be unsubstituted or substituted with deuterium.

In the present disclosure, a represents the number of R₁, and when a is two or more, two or more R₁ may be the same as or different from each other.

Preferably, R₁ is each independently hydrogen; deuterium; a substituted or unsubstituted C_6-20 aryl; or a substituted or unsubstituted C_2-20 heteroaryl containing one or more selected from the group consisting of N, O and S, with the proviso that at least one R₁ may be deuterium, phenyl substituted with deuterium, a substituted or unsubstituted C_10-20 aryl or a substituted or unsubstituted C_2-20 heteroaryl containing one or more selected from the group consisting of N, O and S.

More preferably, R₁ is each independently hydrogen, deuterium, phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, triphenylenyl, fluoranthenyl, naphthyl phenyl, phenyl naphthyl, dihydroindenyl, dibenzofuranyl, dibenzothiophenyl, benzonaphthofuranyl, or benzonaphthothiophenyl, with the proviso that at least one R₁ may be deuterium, phenyl substituted with deuterium, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, triphenylenyl, fluoranthenyl, naphthyl phenyl, phenyl naphthyl, dibenzofuranyl, dibenzothiophenyl, benzonaphthofuranyl, or benzonaphthothiophenyl, each of which, except for deuterium and phenyl substituted with deuterium, may be unsubstituted or substituted with deuterium.

Most preferably, R₁ may be each independently deuterium, phenyl substituted with deuterium, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, triphenylenyl, fluoranthenyl, naphthyl phenyl, phenyl naphthyl, dihydroindenyl, dibenzofuranyl, dibenzothiophenyl, benzonaphthofuranyl, or benzonaphthothiophenyl, each of which, except for deuterium and phenyl substituted with deuterium, may be unsubstituted or substituted with deuterium.

Further, the compound represented by Chemical Formula 1 may contain no deuterium or may contain at least one deuterium.

As an example, when the compound contains deuterium, the deuterium substitution rate of the compound may be 1% to 100%. Specifically, the deuterium substitution rate of the compound may be 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 75% or more, 80% or more, or 90% or more, and less than 100%. The deuterium substitution rate of such a compound is calculated as the number of substituted deuterium relative to the total number of hydrogens that can be present in the Chemical Formula, wherein the number of substituted deuterium may be obtained through MALDI-TOF MS (Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometer) analysis.

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

Among the above listed compounds, the compound represented by ‘[structural formula] D_n’ is a compound of which the corresponding ‘structural formula’ is substituted with n deuteriums.

The compound represented by Chemical Formula 1, in which a is 1, and R₁ is a substituted or unsubstituted C_6-60 aryl; or a substituted or unsubstituted C_2-60 heteroaryl containing one or more selected from the group consisting of N, O and S, can be prepared by a preparation method as shown in the following Reaction Scheme 1 as an example, and other remaining compounds can be prepared in a similar manner.

In Reaction Scheme 1, R₁, Ar₁, Ar₂ and L₁ to L₃ are the same as defined in Chemical Formula 1, and X₁ and X₂ are each independently halogen, and preferably X₁ and X₂ are each independently chloro or bromo.

Reaction Scheme 1 is a Suzuki coupling reaction, which is preferably carried out in the presence of a palladium catalyst and a base, and a reactive group for the Suzuki coupling reaction can be modified as known in the art. The preparation method can be further embodied in Preparation Examples described hereinafter.

Preferably, the compound represented by Chemical Formula 2 may be represented by one of the following Chemical Formulas 2-1 to 2-4:

• • in Chemical Formulas 2-1 to 2-4,
  • Ar₃, Ar₄ and L₄ to L₆ are the same as defined in Chemical Formula 2.

Preferably, Ar₃ and Ar₄ are each independently a substituted or unsubstituted C_6-20 aryl, or a substituted or unsubstituted C_2-20 heteroaryl containing one or more selected from the group consisting of N, O and S.

More preferably, Ar₃ and Ar₄ may be each independently phenyl, biphenylyl, terphenylyl, quaterphenylyl, triphenylmethyl phenyl, triphenylsilyl phenyl, naphthyl, phenanthrenyl, triphenylenyl, fluoranthenyl, chrysenyl, benzo[c]phenanthrenyl, carbazolyl, phenyl carbazolyl, dimethylfluorenyl, dibenzofuranyl, or dibenzothiophenyl.

Most preferably, Ar₃ and Ar₄ may be each independently one selected from the following:

Preferably, L₄ may be a substituted or unsubstituted C_6-60 arylene.

More preferably, L₄ is phenylene, biphenyldiyl, terphenyldiyl, quarterphenyldiyl, naphthalenediyl, phenylnaphthalenediyl, or phenylnaphthalenediyl substituted with one phenyl.

Most preferably, L₄ may be one selected from the following:

Preferably, L₅ and L₆ may be each independently a single bond, a substituted or unsubstituted C_6-20 arylene, or a substituted or unsubstituted C_2-20 heteroarylene containing one or more selected from the group consisting of N, O and S.

More preferably, L₅ and L₆ may be each independently a single bond, phenylene, biphenyldiyl, naphthalenediyl, phenylnaphthalenediyl, or carbazolediyl.

Most preferably, L₅ and L₆ may be each independently a single bond, or one selected from the following:

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

Among the above listed compounds, the compound represented by ‘[structural formula] D_n’ is a compound of which the corresponding ‘structural formula’ is substituted with n deuteriums.

The compound represented by Chemical Formula 2 can be prepared by a preparation method as shown in the following Reaction Scheme 2 as an example, and other remaining compounds can be prepared in a similar manner.

In Reaction Scheme 2, Ar₃, Ar₄ and L₄ to L₆ are the same as defined in Chemical Formula 2, and X′ is halogen, and preferably X′ is chloro or bromo.

Reaction Scheme 2 is an amine substitution reaction, which is preferably carried out in the presence of a palladium catalyst and a base, and a reactive group for the amine substitution reaction can be modified as known in the art. The preparation method can be further embodied in Preparation Examples described hereinafter.

Preferably, the weight ratio of the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 in the light emitting layer is 10:90 to 90:10, more preferably 20:80 to 80:20, 30:70 to 70:30, or 40:60 to 60:40.

Meanwhile, the light emitting layer may further include a dopant in addition to the host. The dopant material is not particularly limited as long as it is a material used for the organic light emitting device. As an example, an aromatic amine derivative, a styrylamine compound, a boron complex, a fluoranthene compound, a metal complex, and the like can be mentioned. Specific examples of the aromatic amine derivatives include substituted or unsubstituted fused aromatic ring derivatives having an arylamino group, examples thereof include pyrene, anthracene, chrysene, and periflanthene having the arylamino group, and the like. The styrylamine compound is a compound where at least one arylvinyl group is substituted in substituted or unsubstituted arylamine, in which one or two or more substituent groups selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamino group are substituted or unsubstituted. Specific examples thereof include styrylamine, styryldiamine, styryltriamine, styryltetramine, and the like, but are not limited thereto. Further, examples of the metal complex include an iridium complex, a platinum complex, and the like, but are not limited thereto.

Preferably, the dopant material may be one selected from the following, but is not limited thereto:

Hole Blocking Layer

The organic light emitting device according to the present disclosure may include a hole blocking layer between the light emitting layer and the electron transport layer described later, if necessary. The hole blocking layer refers to a layer which is formed on the light emitting layer, and preferably, is provided in contact with the light emitting layer, and thus severs to control electron mobility, to prevent excessive movement of holes, and to increase the probability of hole-electron bonding, thereby improving the efficiency of the organic light emitting device. The hole blocking layer includes a hole blocking material, and as an example of such hole blocking material, a compound into which an electron-withdrawing group is introduced, such as azine derivatives including triazine; triazole derivatives; oxadiazole derivatives; phenanthroline derivatives; phosphine oxide derivatives can be used, but is not limited thereto.

Electron Transport Layer

The organic light emitting device according to the present disclosure may include an electron transport layer on the light emitting layer, if necessary.

The electron transport layer is a layer that receives the electrons from the cathode or the electron injection layer formed on the cathode and transports the electrons to the light emitting layer, and that suppress the transfer of holes from the light emitting layer, and an electron transport material is suitably a material which may receive electrons well from a cathode and transfer the electrons to a light emitting layer, and has a large mobility for electrons.

Specific examples of the electron transport material include: an Al complex of 8-hydroxyquinoline; a complex including Alq₃; an organic radical compound; a hydroxyflavone-metal complex, and the like, but are not limited thereto. The electron transport layer may be used with any desired cathode material, as used according to a conventional technique. In particular, appropriate examples of the cathode material are a typical material which has a low work function, followed by an aluminum layer or a silver layer. Specific examples thereof include cesium, barium, calcium, ytterbium, and samarium, in each case followed by an aluminum layer or a silver layer.

Electron Injection Layer

The organic light emitting device according to the present disclosure may further include an electron injection layer on the light emitting layer (or on the electron transport layer, if the electron transport layer exists).

The electron injection layer is a layer which injects electrons from an electrode, and is preferably a compound which has a capability of transporting electrons, has an effect of injecting electrons from a cathode and an excellent effect of injecting electrons into a light emitting layer or a light emitting material, prevents excitons produced from the light emitting layer from moving to a hole injection layer, and is also excellent in the ability to form a thin film.

Specific examples of the electron injection layer include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidene methane, anthrone, and the like, and derivatives thereof, a metal complex compound, a nitrogen-containing 5-membered ring derivative, and the like, but are not limited thereto.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h]quinolinato)beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)(o-cresolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtholato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtholato)gallium, and the like, but are not limited thereto.

Meanwhile, in the present disclosure, the “electron injection and transport layer” is a layer that performs both the roles of the electron injection layer and the electron transport layer, and the materials that perform the roles of each layer may be used alone or in combination, without being limited thereto.

Organic Light Emitting Device

The structure of the organic light emitting device according to the present disclosure is illustrated in FIGS. 1 and 2. FIG. 1 shows an example of an organic light emitting device comprising a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4. FIG. 2 shows an example of an organic light emitting device comprising a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 7, a light emitting layer 3, a hole blocking layer 8, an electron injection and transport layer 9, and a cathode 4.

The organic light emitting device according to the present disclosure can be manufactured by sequentially stacking the above-described structures. In this case, the organic light emitting device may be manufactured by depositing a metal, metal oxides having conductivity, or an alloy thereof on the substrate by using a PVD (physical vapor deposition) method such as a sputtering method or an e-beam evaporation method to form the anode, forming the respective layers described above thereon, and then depositing a material that can be used as the cathode thereon. In addition to such a method, the organic light emitting device may be manufactured by sequentially depositing from the cathode material to the anode material on a substrate in the reverse order of the above-mentioned configuration (WO 2003/012890). Further, the light emitting layer may be formed by subjecting hosts and dopants to a vacuum deposition method and a solution coating method. Herein, the solution coating method means a spin coating, a dip coating, a doctor blading, an inkjet printing, a screen printing, a spray method, a roll coating, or the like, but is not limited thereto.

Meanwhile, the organic light emitting device according to the present disclosure may be a bottom emission device, a top emission device, or a double-sided light emitting device, and particularly, may be a bottom emission device that requires relatively high luminous efficiency.

Below, preferable embodiments are presented to assist in the understanding of the present disclosure. the following examples are only provided for a better understanding of the present disclosure, and is not intended to limit the content of the present disclosure.

Synthesis Example 1-1

(2-Chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and Compound Trz1 (26.7 g, 63.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.5 g of Compound 1-1_P1. (Yield: 69%, MS: [M+H]+=584).

Compound 1-1_P1 (15 g, 25.7 mmol) and naphthalen-2-ylboronic acid (4.6 g, 27 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (10.6 g, 77 mmol) was dissolved in 32 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After the reaction for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-1. (Yield: 70%, MS: [M+H]⁺=676).

Synthesis Example 1-2

(2-Chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and Compound Trz2 (30.9 g, 63.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 2 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26.5 g of Compound 1-2_P1. (Yield: 67%, MS: [M+H]⁺=650).

Compound 1-2_P1 (15 g, 23.1 mmol) and dibenzo[b,d]furan-2-ylboronic acid (5.1 g, 24.2 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (9.6 g, 69.2 mmol) was dissolved in 29 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After the reaction for 2 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-2. (Yield: 73%, MS: [M+H]⁺=782).

Synthesis Example 1-3

(2-Chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and Compound Trz3 (27.1 g, 63.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 4 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-3_P1. (Yield: 66%, MS: [M+H]⁺=580).

Compound 1-3_P1 (15 g, 25.4 mmol) and [1,1′-biphenyl]-4-ylboronic acid (5.3 g, 26.7 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (10.5 g, 76.3 mmol) was dissolved in 32 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After the reaction for 5 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-3. (Yield: 75%, MS: [M+H]⁺=708).

Synthesis Example 1-4

(3-chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and Compound Trz4 (28.4 g, 63.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 27.4 g of Compound 1-4_P1. (Yield: 74%, MS: [M+H]⁺=610).

Compound 1-4_P1 (15 g, 24.6 mmol) and naphthalen-2-ylboronic acid (4.4 g, 25.8 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (10.2 g, 73.8 mmol) was dissolved in 31 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added After the reaction for 5 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-4. (Yield: 65%, MS: [M+H]⁺=702).

Synthesis Example 1-5

(3-Chlorodibenzo[b,d] furan-1-yl)boronic acid (15 g, 60.9 mmol) and Compound Trz5 (17.1 g, 63.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.7 g of Compound 1-5_P1. (Yield: 71%, MS: [M+H]⁺=434).

Compound 1-5_P1 (15 g, 34.6 mmol) and fluoranthen-3-ylboronic acid (8.9 g, 36.3 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (14.3 g, 103.7 mmol) was dissolved in 43 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After the reaction for 4 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-5. (Yield: 72%, MS: [M+H]⁺=600).

Synthesis Example 1-6

Compound 1-5_P1 (15 g, 34.6 mmol) and naphtho[2,3-b]benzofuran-1-ylboronic acid (9.5 g, 36.3 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (14.3 g, 103.7 mmol) was dissolved in 43 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After the reaction for 4 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-6. (Yield: 65%, MS: [M+H]⁺=616).

Synthesis Example 1-7

(3-Chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and Compound Trz6 (32.9 g, 63.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 4 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 27.4 g of Compound 1-7_P1. (Yield: 71%, MS: [M+H]⁺=636).

Compound 1-7_P1 (15 g, 23.6 mmol) and naphthalen-2-ylboronic acid (4.3 g, 24.8 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (9.8 g, 70.7 mmol) was dissolved in 29 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After the reaction for 4 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-7. (Yield: 67%, MS: [M+H]⁺=728).

Synthesis Example 1-8

Trifluoromethanesulfonic anhydride (30.1 g, 106.6 mmol) and deuterium oxide (10.7 g, 532.8 mmol) were added at 0° C. and stirred for 5 hours to prepare a solution. 1-Bromo-4-chlorodibenzo[b,d]furan (15 g, 53.3 mmol) was added to 120 ml of 1,2,4-trichlorobenzene, and the mixture was stirred. Then, the prepared mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was slowly added dropwise to the mixed solution of 1-bromo-4-chlorodibenzo[b,d]furan and 1,2,4-trichlorobenzene, and the mixture was stirred while heating up to 140° C. and then keeping that temperature. After the reaction for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 6.5 g of compound sub1-1-1. (Yield: 43%, MS: [M+H]⁺=283)

Compound Sub1-1-1 (15 g, 52.9 mmol) and bis(pinacolato)diboron (14.8 g, 58.2 mmol) were added to 300 ml of 1,4-dioxane, and the mixture was stirred under reflux. Then, potassium acetate (7.8 g, 79.4 mmol) was added thereto, the mixture was sufficiently stirred, and then bis(dibenzylideneacetone)palladium(0) (0.9 g, 1.6 mmol) and tricyclohexylphosphine (0.9 g, 3.2 mmol) were added. After the reaction for 6 hours, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and then the organic layer was distilled. This was dissolved again in chloroform, washed twice with water, and the organic layer was then separated. Anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.8 g of Compound Sub1-1-2. (Yield: 62%, MS: [M+H]+=331)

Compound Sub1-1-2 (15 g, 45.4 mmol) and Compound Trz7 (28.1 g, 47.6 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (18.8 g, 136.1 mmol) was dissolved in 56 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After the reaction for 2 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-8_P1. (Yield: 72%, MS: [M+H]⁺=714).

Compound 1-8_P1 (15 g, 21 mmol) and phenylboronic acid (2.7 g, 22.1 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (8.7 g, 63 mmol) was dissolved in 26 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After the reaction for 5 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 g of Compound 1-8. (Yield: 63%, MS: [M+H]⁺=756).

Synthesis Example 1-9

Compound Sub1-1-2 (15 g, 45.4 mmol) and Compound Trz8 (29.6 g, 47.6 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (18.8 g, 136.1 mmol) was dissolved in 56 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After the reaction for 5 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 25.3 g of Compound 1-9_P1. (Yield: 75%, MS: [M+H]⁺=744).

Compound 1-9_P1 (15 g, 20.2 mmol) and phenylboronic acid (2.6 g, 21.2 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (8.4 g, 60.5 mmol) was dissolved in 25 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added After the reaction for 5 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-9. (Yield: 70%, MS: [M+H]⁺=786).

Synthesis Example 1-10

Trifluoromethanesulfonic anhydride (60.1 g, 213.1 mmol) and deuterium oxide (21.4 g, 1065.6 mmol) were added at 0° C. and stirred for hours to prepare a solution. 1-Bromo-4-chlorodibenzo[b,d]furan (15 g, 53.3 mmol) was added to 120 ml of 1,2,4-trichlorobenzene, and the mixture was stirred. Then, the prepared mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was slowly added dropwise to the mixed solution of 1-bromo-4-chlorodibenzo[b,d]furan and 1,2,4-trichlorobenzene, and the mixture was stirred while heating up to 140° C. and then keeping that temperature. After the reaction for 10 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 5.3 g of compound Sub1-2-1. (Yield: 35%, MS: [M+H]⁺=285)

Compound Sub1-2-1 (15 g, 52.5 mmol) and bis(pinacolato)diboron (14.7 g, 57.8 mmol) were added to 300 ml of 1,4-dioxane, and the mixture was stirred under reflux. Then, potassium acetate (7.7 g, 78.8 mmol) was added thereto, the mixture was sufficiently stirred, and then bis(dibenzylideneacetone) palladium(0) (0.9 g, 1.6 mmol) and tricyclohexylphosphine (0.9 g, 3.2 mmol) were added. After the reaction for 6 hours, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and then the organic layer was distilled. This was dissolved again in chloroform, washed twice with water, and the organic layer was then separated. Anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11 g of Compound Sub1-2-2. (Yield: 63%, MS: [M+H]⁺=333)

Compound Sub1-2-2 (15 g, 45.1 mmol) and Compound Trz9 (15.8 g, 47.4 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (18.7 g, 135.3 mmol) was dissolved in 56 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After the reaction for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.6 g of Compound 1-10_P1. (Yield: 66%, MS: [M+H]⁺=493).

Compound 1-10_P1 (15 g, 30.4 mmol) and dibenzo[b,d]furan-1-ylboronic acid (6.8 g, 31.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (12.6 g, 91.3 mmol) was dissolved in 38 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After the reaction for 2 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-10. (Yield: 70%, MS: [M+H]⁺=625).

Synthesis Example 1-11

(3-Chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and Compound Trz10 (25.2 g, 63.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 2 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.1 g of Compound 1-11_P1. (Yield: 62%, MS: [M+H]⁺=560).

Compound 1-11_P1 (15 g, 26.8 mmol) and phenylboronic acid (3.4 g, 28.1 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (11.1 g, 80.3 mmol) was dissolved in 33 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After the reaction for 2 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-11_P2. (Yield: 73%, MS: [M+H]⁺=602).

Compound 1-11_P2 (10 g, 16.6 mmol), PtO₂ (1.1 g, 5 mmol) and D₂O (83 ml) were added to a shaker tube, and then the tube was sealed and heated at 250° C. and 600 psi for 12 hours. When the reaction was completed, chloroform was added, and the reaction solution was transferred to a separatory funnel, and extracted. The extract was dried over MgSO₄ and concentrated, and then the sample was purified by silica gel column chromatography to prepare 3.1 g of Compound 1-11. (Yield: 30%, MS[M+H]+=626)

Synthesis Example 1-12

(3-Chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and Compound Trz11 (23.5 g, 63.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 2 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-12_P1. (Yield: 72%, MS: [M+H]⁺=534).

Compound 1-12_P1 (15 g, 28.1 mmol) and dibenzo[b,d]thiophen-4-ylboronic acid (6.7 g, 29.5 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (11.6 g, 84.3 mmol) was dissolved in 35 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After the reaction for 4 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-12_P2. (Yield: 65%, MS: [M+H]⁺=682).

Compound 1-12_P2 (10 g, 14.7 mmol), PtO₂ (1 g, 4.4 mmol) and D₂O (73 ml) were added to a shaker tube, and then the tube was sealed and heated at 250° C. and 600 psi for 12 hours. When the reaction was completed, chloroform was added, and the reaction solution was transferred to a separatory funnel, and extracted. The extract was dried over MgSO₄ and concentrated, and then the sample was purified by silica gel column chromatography to prepare 5.1 g of Compound 1-12. (Yield: 49%, MS: [M+H]⁺=706)

Synthesis Example 1-13

(4-Chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and Compound Trz12 (30 g, 63.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.4 g of Compound 1-13_P1. (Yield: 63%, MS: [M+H]⁺=636).

Compound 1-13_P1 (15 g, 23.6 mmol) and naphthalen-2-ylboronic acid (4.3 g, 24.8 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (9.8 g, 70.7 mmol) was dissolved in 29 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After the reaction for 5 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.5 g of Compound 1-13. (Yield: 61%, MS: [M+H]⁺=728).

Synthesis Example 1-14

(4-Chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and Compound Trz13 (22 g, 63.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-14_P1. (Yield: 72%, MS: [M+H]⁺=510).

Compound 1-14_P1 (15 g, 29.4 mmol) and naphtho[2,3-b]benzofuran-4-ylboronic acid (8.1 g, 30.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (12.2 g, 88.2 mmol) was dissolved in 37 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After the reaction for 4 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-14. (Yield: 70%, MS: [M+H]⁺=692).

Synthesis Example 1-15

(4-Chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and Compound Trz14 (26.1 g, 63.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 2 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.8 g of Compound 1-15_P1. (Yield: 71%, MS: [M+H]⁺=574).

Compound 1-15_P1 (15 g, 26.1 mmol) and dibenzo[b,d]furan-1-ylboronic acid (5.8 g, 27.4 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (10.8 g, 78.4 mmol) was dissolved in 33 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After the reaction for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-15. (Yield: 60%, MS: [M+H]⁺=706).

Synthesis Example 1-16

Trifluoromethanesulfonic anhydride (45.1 g, 159.8 mmol) and deuterium oxide (16 g, 799.2 mmol) were added at 0° C. and stirred for 5 hours to prepare a solution. 1-Bromo-4-chlorodibenzo[b,d]furan (15 g, 53.3 mmol) was added to 120 ml of 1,2,4-trichlorobenzene, and the mixture was stirred. Then, the prepared mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was slowly added dropwise to the mixed solution of 1-bromo-4-chlorodibenzo[b,d]furan and 1,2,4-trichlorobenzene, and the mixture was stirred while heating up to 140° C. and then keeping that temperature. After the reaction for 7 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 5.6 g of compound Sub1-3-1. (Yield: 37%, MS: [M+H]⁺=284)

Compound Sub1-3-1 (15 g, 52.7 mmol) and bis(pinacolato)diboron (14.7 g, 58 mmol) were added to 300 ml of 1,4-dioxane, and the mixture was stirred under reflux. Then, potassium acetate (7.8 g, 79.1 mmol) was added thereto, the mixture was sufficiently stirred, and then bis(dibenzylideneacetone) palladium(0) (0.9 g, 1.6 mmol) and tricyclohexylphosphine (0.9 g, 3.2 mmol) were added. After the reaction for 6 hours, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and then the organic layer was distilled. This was dissolved again in chloroform, washed twice with water, and the organic layer was then separated. Anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.1 g of Compound Sub1-3-2. (Yield: 58%, MS: [M+H]⁺=332)

Compound Sub1-3-2 (15 g, 45.2 mmol) and Compound Trz15 (17.7 g, 47.5 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (18.8 g, 135.7 mmol) was dissolved in 56 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After the reaction for 2 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.4 g of Compound 1-16_P1. (Yield: 63%, MS: [M+H]⁺=542).

Compound 1-16_P1 (15 g, 27.7 mmol) and (phenyl-d5)boronic acid (3.7 g, 29.1 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (11.5 g, 83 mmol) was dissolved in 34 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After the reaction for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-16. (Yield: 73%, MS: [M+H]⁺=589).

Synthesis Example 1-17

(6-Chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and Compound Trz16 (23.5 g, 63.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 2 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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_P1. (Yield: 72%, MS: [M+H]⁺=534).

Compound 1-17_P1 (15 g, 28.1 mmol) and naphthalen-2-ylboronic acid (5.1 g, 29.5 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (11.6 g, 84.3 mmol) was dissolved in 35 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After the reaction for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-17. (Yield: 71%, MS: [M+H]⁺=626).

Synthesis Example 1-18

(6-Chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and Compound Trz17 (29.7 g, 63.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 5 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.6 g of Compound 1-18_P1. (Yield: 69%, MS: [M+H]⁺=586).

Compound 1-18_P1 (15 g, 25.6 mmol) and naphthalen-2-ylboronic acid (4.6 g, 26.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (10.6 g, 76.8 mmol) was dissolved in 32 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After the reaction for 2 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-18. (Yield: 63%, MS: [M+H]⁺=678).

Synthesis Example 1-19

(6-Chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and Compound Trz18 (31.2 g, 63.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.5 g of Compound 1-19_P1. (Yield: 66%, MS: [M+H]⁺=610).

Compound 1-19_P1 (15 g, 24.6 mmol) and naphthalen-2-ylboronic acid (4.4 g, 25.8 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (10.2 g, 73.8 mmol) was dissolved in 31 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After the reaction for 2 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.4 g of Compound 1-19. (Yield: 66%, MS: [M+H]⁺=702).

Synthesis Example 1-20

(6-Chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and Compound Trz19 (20.3 g, 63.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 5 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.1 g of Compound 1-20_P1. (Yield: 65%, MS: [M+H]⁺=484).

Compound 1-20_P1 (15 g, 31 mmol) and phenanthren-9-ylboronic acid (7.2 g, 32.5 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (12.9 g, 93 mmol) was dissolved in 39 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After the reaction for 2 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-20. (Yield: 62%, MS: [M+H]⁺=626).

Synthesis Example 1-21

Trifluoromethanesulfonic anhydride (30.1 g, 106.6 mmol) and deuterium oxide (10.7 g, 532.8 mmol) were added at 0° C. and stirred for 5 hours to prepare a solution. 1-Bromo-6-chlorodibenzo[b,d]furan (15 g, 53.3 mmol) was added to 120 ml of 1,2,4-trichlorobenzene, and the mixture was stirred. Then, the prepared mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was slowly added dropwise to the mixed solution of 1-bromo-6-chlorodibenzo[b,d]furan and 1,2,4-trichlorobenzene, and the mixture was stirred while heating up to 140° C. and then keeping that temperature. After the reaction for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 6.8 g of compound Sub2-1-1. (Yield: 45%, MS: [M+H]⁺=283)

Compound Sub2-1-1 (15 g, 52.9 mmol) and bis(pinacolato)diboron (14.8 g, 58.2 mmol) were added to 300 ml of 1,4-dioxane, and the mixture was stirred under reflux. Then, potassium acetate (7.8 g, 79.4 mmol) was added thereto, the mixture was sufficiently stirred, and then bis(dibenzylideneacetone) palladium(0) (0.9 g, 1.6 mmol) and tricyclohexylphosphine (0.9 g, 3.2 mmol) were added. After the reaction for 6 hours, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and then the organic layer was distilled. This was dissolved again in chloroform, washed twice with water, and the organic layer was then separated. Anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.1 g of Compound Sub2-1-2. (Yield: 75%, MS: [M+H]⁺=331)

Compound Sub2-1-2 (15 g, 45.4 mmol) and Compound Trz20 (22.6 g, 47.6 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (18.8 g, 136.1 mmol) was dissolved in 56 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After the reaction for 4 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-21_P1. (Yield: 61%, MS: [M+H]⁺=643).

Compound 1-21_P1 (15 g, 23.3 mmol) and (phenyl-d5)boronic acid (3.1 g, 24.5 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (9.7 g, 70 mmol) was dissolved in 29 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After the reaction for 4 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-21. (Yield: 74%, MS: [M+H]⁺=690).

Synthesis Example 1-22

Compound Sub2-1-2 (15 g, 45.4 mmol) and Compound Trz21 (21.1 g, 47.6 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (18.8 g, 136.1 mmol) was dissolved in 56 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After the reaction for 4 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.6 g of Compound 1-22_P1. (Yield: 67%, MS: [M+H]⁺=612).

Compound 1-22_P1 (15 g, 24.5 mmol) and (phenyl-d5)boronic acid (3.3 g, 25.7 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (10.2 g, 73.5 mmol) was dissolved in 30 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After the reaction for 2 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 g of Compound 1-22. (Yield: 62%, MS: [M+H]⁺=659).

Synthesis Example 1-23

Trifluoromethanesulfonic anhydride (60.1 g, 213.1 mmol) and deuterium oxide (21.4 g, 1065.6 mmol) were added at 0° C. and stirred for hours to prepare a solution. 1-Bromo-6-chlorodibenzo[b,d]furan (15 g, 53.3 mmol) was added to 120 ml of 1,2,4-trichlorobenzene, and the mixture was stirred. Then, the prepared mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was slowly added dropwise to the mixed solution of 1-bromo-6-chlorodibenzo[b,d]furan and 1,2,4-trichlorobenzene, and the mixture was stirred while heating up to 140° C. and then keeping that temperature. After the reaction for 10 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 6.5 g of compound Sub2-2-1. (Yield: 43%, MS: [M+H]⁺=285)

Compound Sub2-2-1 (15 g, 52.5 mmol) and bis(pinacolato)diboron (14.7 g, 57.8 mmol) were added to 300 ml of 1,4-dioxane, and the mixture was stirred under reflux. Then, potassium acetate (7.7 g, 78.8 mmol) was added thereto, the mixture was sufficiently stirred, and then bis(dibenzylideneacetone) palladium(0) (0.9 g, 1.6 mmol) and tricyclohexylphosphine (0.9 g, 3.2 mmol) were added. After the reaction for 5 hours, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and then the organic layer was distilled. This was dissolved again in chloroform, washed twice with water, and the organic layer was then separated. Anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.1 g of Compound Sub2-2-2. (Yield: 75%, MS: [M+H]⁺=333)

Compound Sub2-2-2 (15 g, 60.9 mmol) and Compound Trz22 (36.1 g, 63.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 28.9 g of Compound 1-23_P1. (Yield: 69%, MS: [M+H]⁺=690).

Compound 1-23_P1 (15 g, 21.7 mmol) and phenylboronic acid (2.8 g, 22.8 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (9 g, 65.2 mmol) was dissolved in 27 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After the reaction for 5 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.5 g of Compound 1-23. (Yield: 60%, MS: [M+H]⁺=732).

Synthesis Example 1-24

Compound 1-18 (10 g, 14.8 mmol), PtO₂ (1 g, 4.4 mmol) and D₂O (74 ml) were added to a shaker tube, and then the tube was sealed and heated at 250° C. and 600 psi for 12 hours. When the reaction was completed, chloroform was added, and the reaction solution was transferred to a separatory funnel, and extracted. The extract was dried over MgSO₄ and concentrated, and then the sample was purified by silica gel column chromatography to prepare 5.1 g of Compound 1-24. (Yield: 49%, MS: [M+H]⁺=706)

Synthesis Example 1-25

(6-Chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and Compound Trz23 (25.2 g, 63.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.7 g of Compound 1-25_P1. (Yield: 63%, MS: [M+H]⁺=540).

Compound 1-25_P1 (15 g, 27.8 mmol) and dibenzo[b,d]furan-1-ylboronic acid (6.2 g, 29.2 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (11.5 g, 83.3 mmol) was dissolved in 35 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After the reaction for 5 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.4 g of Compound 1-25_P2. (Yield: 61%, MS: [M+H]⁺=672).

Compound 1-25_P2 (10 g, 14.9 mmol), PtO₂ (1 g, 4.5 mmol) and D₂O (74 ml) were added to a shaker tube, and then the tube was sealed and heated at 250° C. and 600 psi for 12 hours. When the reaction was completed, chloroform was added, and the reaction solution was transferred to a separatory funnel, and extracted. The extract was dried over MgSO₄ and concentrated, and then the sample was purified by silica gel column chromatography to prepare 3.7 g of Compound 1-25. (Yield: 36%, MS: [M+H]⁺=695)

Synthesis Example 1-26

(7-Chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and Compound Trz19 (20.3 g, 63.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 4 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-26_P1. (Yield: 60%, MS: [M+H]⁺=484).

Compound 1-26_P1 (15 g, 31 mmol) and naphthalen-2-ylboronic acid (5.6 g, 32.5 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (12.9 g, 93 mmol) was dissolved in 39 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After the reaction for 2 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-26. (Yield: 73%, MS: [M+H]⁺=576).

Synthesis Example 1-27

(7-Chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and Compound Trz24 (22.9 g, 63.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 5 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.4 g of Compound 1-27_P1. (Yield: 64%, MS: [M+H]⁺=524).

Compound 1-27_P1 (15 g, 28.6 mmol) and naphthalen-2-ylboronic acid (5.2 g, 30.1 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (11.9 g, 85.9 mmol) was dissolved in 36 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After the reaction for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-27. (Yield: 62%, MS: [M+H]⁺=616).

Synthesis Example 1-28

(7-Chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and Compound Trz25 (22.9 g, 63.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 2 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.6 g of Compound 1-28_P1. (Yield: 71%, MS: [M+H]⁺=524).

Compound 1-28_P1 (15 g, 28.6 mmol) and phenanthren-3-ylboronic acid (6.7 g, 30.1 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (11.9 g, 85.9 mmol) was dissolved in 36 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After the reaction for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-28. (Yield: 68%, MS: [M+H]⁺=666).

Synthesis Example 1-29

(7-Chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and Compound Trz26 (25.2 g, 63.9 mmol) were added to 300 ml of THE, and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 2 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.1 g of Compound 1-29_P1. (Yield: 62%, MS: [M+H]⁺=560).

Compound 1-29_P1 (15 g, 26.8 mmol) and dibenzo[b,d]thiophen-4-ylboronic acid (6.4 g, 28.1 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (11.1 g, 80.3 mmol) was dissolved in 33 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After the reaction for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-29. (Yield: 65%, MS: [M+H]⁺=708).

Synthesis Example 1-30

(7-Chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and Compound Trz27 (38.6 g, 63.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 5 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 29.1 g of Compound 1-30_P1. (Yield: 66%, MS: [M+H]⁺=726).

Compound 1-30_P1 (15 g, 20.7 mmol) and naphthalen-2-ylboronic acid (3.7 g, 21.7 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (8.6 g, 62 mmol) was dissolved in 26 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After the reaction for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.6 g of Compound 1-30. (Yield: 63%, MS: [M+H]⁺=818).

Synthesis Example 1-31

Trifluoromethanesulfonic anhydride (30.1 g, 106.6 mmol) and deuterium oxide (10.7 g, 532.8 mmol) were added at 0° C. and stirred for 5 hours to prepare a solution. 1-Bromo-7-chlorodibenzo[b,d]furan (15 g, 53.3 mmol) was added to 120 ml of 1,2,4-trichlorobenzene, and the mixture was stirred. Then, the prepared mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was slowly added dropwise to the mixed solution of 1-bromo-7-chlorodibenzo[b,d]furan and 1,2,4-trichlorobenzene, and the mixture was stirred while heating up to 140° C. and then keeping that temperature. After the reaction for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 6 g of compound Sub3-1-1. (Yield: 40%, MS: [M+H]⁺=283)

Compound Sub3-1-1 (15 g, 52.9 mmol) and bis(pinacolato)diboron (14.8 g, 58.2 mmol) were added to 300 ml of 1,4-dioxane, and the mixture was stirred under reflux. Then, potassium acetate (7.8 g, 79.4 mmol) was added thereto, the mixture was sufficiently stirred, and then bis(dibenzylideneacetone) palladium(0) (0.9 g, 1.6 mmol) and tricyclohexylphosphine (0.9 g, 3.2 mmol) were added. After the reaction for 4 hours, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and then the organic layer was distilled. This was dissolved again in chloroform, washed twice with water, and the organic layer was then separated. Anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.4 g of Compound Sub3-1-2. (Yield: 65%, MS: [M+H]⁺=331)

Compound Sub3-1-2 (15 g, 45.4 mmol) and Compound Trz28 (28.6 g, 47.6 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (18.8 g, 136.1 mmol) was dissolved in 56 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After the reaction for 2 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-31_P1. (Yield: 62%, MS: [M+H]⁺=723).

Compound 1-31_P1 (15 g, 20.7 mmol) and phenanthren-3-ylboronic acid (4.8 g, 21.8 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (8.6 g, 62.2 mmol) was dissolved in 26 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After the reaction for 2 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-31. (Yield: 64%, MS: [M+H]⁺=866).

Synthesis Example 1-32

Trifluoromethanesulfonic anhydride (60.1 g, 213.1 mmol) and deuterium oxide (21.4 g, 1065.6 mmol) were added at 0° C. and stirred for hours to prepare a solution. 1-Bromo-7-chlorodibenzo[b,d]furan (15 g, 53.3 mmol) was added to 120 ml of 1,2,4-trichlorobenzene, and the mixture was stirred. Then, the prepared mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was slowly added dropwise to the mixed solution of 1-bromo-7-chlorodibenzo[b,d]furan and 1,2,4-trichlorobenzene, and the mixture was stirred while heating up to 140° C. and then keeping that temperature. After the reaction for 10 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 6.7 g of Compound Sub3-2-1. (Yield: 44%, MS: [M+H]⁺=285)

Compound Sub3-2-1 (15 g, 52.5 mmol) and bis(pinacolato)diboron (14.7 g, 57.8 mmol) were added to 300 ml of 1,4-dioxane, and the mixture was stirred under reflux. Then, potassium acetate (7.7 g, 78.8 mmol) was added thereto, the mixture was sufficiently stirred, and then bis(dibenzylideneacetone) palladium(0) (0.9 g, 1.6 mmol) and tricyclohexylphosphine (0.9 g, 3.2 mmol) were added. After the reaction for 6 hours, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and then the organic layer was distilled. This was dissolved again in chloroform, washed twice with water, and the organic layer was then separated. Anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.7 g of Compound Sub3-2-2. (Yield: 67%, MS: [M+H]⁺=333)

Compound Sub3-2-2 (15 g, 45.1 mmol) and Compound Trz29 (18.7 g, 47.4 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (18.7 g, 135.3 mmol) was dissolved in 56 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After the reaction for 2 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-32_P1. (Yield: 71%, MS: [M+H]⁺=564).

Compound 1-32_P1 (15 g, 26.6 mmol) and (phenyl-d5)boronic acid (3.5 g, 27.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (11 g, 79.8 mmol) was dissolved in 33 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After the reaction for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.4 g of Compound 1-32. (Yield: 70%, MS: [M+H]⁺=611).

Synthesis Example 1-33

Compound Sub3-2-2 (15 g, 45.1 mmol) and Compound Trz30 (24.8 g, 47.4 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (18.7 g, 135.3 mmol) was dissolved in 56 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After the reaction for 2 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-33_P1. (Yield: 63%, MS: [M+H]⁺=650).

Compound 1-33_P1 (15 g, 23.1 mmol) and phenylboronic acid (3 g, 24.2 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (9.6 g, 69.2 mmol) was dissolved in 29 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After the reaction for 2 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-33. (Yield: 72%, MS: [M+H]⁺=692).

Synthesis Example 1-34

Compound 1-26 (10 g, 17.4 mmol), PtO₂ (1.2 g, 5.2 mmol) and D₂O (87 ml) were added to a shaker tube, and then the tube was sealed and heated at 250° C. and 600 psi for 12 hours. When the reaction was completed, chloroform was added, and the reaction solution was transferred to a separatory funnel, and extracted. The extract was dried over MgSO₄ and concentrated, and then the sample was purified by silica gel column chromatography to prepare 3.9 g of Compound 1-34. (Yield: 38%, MS: [M+H]⁺=598)

Synthesis Example 1-35

(7-Chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and Compound Trz29 (25.2 g, 63.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 2 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-35_P1. (Yield: 70%, MS: [M+H]⁺=560).

Compound 1-35_P1 (15 g, 26.8 mmol) and phenylboronic acid (3.4 g, 28.1 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (11.1 g, 80.3 mmol) was dissolved in 33 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After the reaction for 5 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-35_P2. (Yield: 70%, MS: [M+H]⁺=602).

Compound 1-35_P2 (10 g, 16.6 mmol), PtO₂ (1.1 g, 5 mmol) and D₂O (83 ml) were added to a shaker tube, and then the tube was sealed and heated at 250° C. and 600 psi for 12 hours. When the reaction was completed, chloroform was added, and the reaction solution was transferred to a separatory funnel, and extracted. The extract was dried over MgSO₄ and concentrated, and then the sample was purified by silica gel column chromatography to prepare 3.7 g of Compound 1-35. (Yield: 36%, MS: [M+H]⁺=626)

Synthesis Example 1-36

Compound 1-27 (10 g, 16.2 mmol), PtO₂ (1.1 g, 4.9 mmol) and D₂O (81 ml) were added to a shaker tube, and then the tube was sealed and heated at 250° C. and 600 psi for 12 hours. When the reaction was completed, chloroform was added, and the reaction solution was transferred to a separatory funnel, and extracted. The extract was dried over MgSO₄ and concentrated, and then the sample was purified by silica gel column chromatography to prepare 3.9 g of Compound 1-36. (Yield: 38%, MS: [M+H]⁺=639)

Synthesis Example 1-37

(8-Chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and Compound Trz31 (26.8 g, 63.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 5 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26.7 g of Compound 1-37_P1. (Yield: 75%, MS: [M+H]⁺=586).

Compound 1-37_P1 (15 g, 25.6 mmol) and naphthalen-2-ylboronic acid (4.6 g, 26.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (10.6 g, 76.8 mmol) was dissolved in 32 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After the reaction for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-37. (Yield: 73%, MS: [M+H]⁺=678).

Synthesis Example 1-38

(8-Chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and Compound Trz5 (17.1 g, 63.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 2 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.3 g of Compound 1-38_P1. (Yield: 62%, MS: [M+H]⁺=434).

Compound 1-38_P1 (15 g, 34.6 mmol) and triphenylen-2-ylboronic acid (9.9 g, 36.3 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (14.3 g, 103.7 mmol) was dissolved in 43 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After the reaction for 4 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-38. (Yield: 68%, MS: [M+H]⁺=626).

Synthesis Example 1-39

(8-Chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and Compound Trz32 (32.9 g, 63.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 2 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 27.8 g of Compound 1-39_P1. (Yield: 72%, MS: [M+H]⁺=636).

Compound 1-39_P1 (15 g, 23.6 mmol) and dibenzo[b,d]furan-4-ylboronic acid (5.2 g, 24.8 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (9.8 g, 70.7 mmol) was dissolved in 29 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After the reaction for 5 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-39. (Yield: 64%, MS: [M+H]⁺=769).

Synthesis Example 1-40

Trifluoromethanesulfonic anhydride (60.1 g, 213.1 mmol) and deuterium oxide (21.4 g, 1065.6 mmol) were added at 0° C. and stirred for hours to prepare a solution. 1-Bromo-8-chlorodibenzo[b,d]furan (15 g, 53.3 mmol) was added to 120 ml of 1,2,4-trichlorobenzene, and the mixture was stirred. Then, the prepared mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was slowly added dropwise to the mixed solution of 1-bromo-8-chlorodibenzo[b,d]furan and 1,2,4-trichlorobenzene, and the mixture was stirred while heating up to 140° C. and then keeping that temperature. After the reaction for 10 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 6.4 g of Compound Sub4-1-1. (Yield: 42%, MS: [M+H]⁺=285)

Compound Sub4-1-1 (15 g, 52.5 mmol) and bis(pinacolato)diboron (14.7 g, 57.8 mmol) were added to 300 ml of 1,4-dioxane, and the mixture was stirred under reflux. Then, potassium acetate (7.7 g, 78.8 mmol) was added thereto, the mixture was sufficiently stirred, and then bis(dibenzylideneacetone) palladium(0) (0.9 g, 1.6 mmol) and tricyclohexylphosphine (0.9 g, 3.2 mmol) were added. After the reaction for 6 hours, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and then the organic layer was distilled. This was dissolved again in chloroform, washed twice with water, and the organic layer was then separated.

Anhydrous magnesium sulfate was added thereto, stirred, 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 Sub4-1-2. (Yield: 69%, MS: [M+H]⁺=333)

Compound Sub4-1-2 (15 g, 45.1 mmol) and Compound Trz33 (17.8 g, 47.4 mmol) were added to 300 ml of THE, and the mixture was stirred and refluxed. Then, potassium carbonate (18.7 g, 135.3 mmol) was dissolved in 56 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After the reaction for 5 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-40_P1. (Yield: 65%, MS: [M+H]⁺=546).

Compound 1-40_P1 (15 g, 27.5 mmol) and dibenzo[b,d]furan-4-ylboronic acid (6.1 g, 28.8 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (11.4 g, 82.4 mmol) was dissolved in 34 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After the reaction for 2 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-40. (Yield: 62%, MS: [M+H]⁺=678).

Synthesis Example 1-41

Compound Sub4-1-2 (15 g, 45.1 mmol) and Compound Trz34 (20.3 g, 47.4 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (18.7 g, 135.3 mmol) was dissolved in 56 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After the reaction for 4 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-41_P1. (Yield: 72%, MS: [M+H]⁺=599).

Compound 1-41_P1 (15 g, 25 mmol) and phenylboronic acid (3.2 g, 26.3 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (10.4 g, 75.1 mmol) was dissolved in 31 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After the reaction for 2 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.8 g of Compound 1-41. (Yield: 61%, MS: [M+H]⁺=641).

Synthesis Example 1-42

Compound Sub4-1-2 (15 g, 45.1 mmol) and Compound Trz35 (21.3 g, 47.4 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (18.7 g, 135.3 mmol) was dissolved in 56 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After the reaction for 4 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 g of Compound 1-42_P1. (Yield: 61%, MS: [M+H]⁺=619).

Compound 1-42_P1 (15 g, 24.2 mmol) and (phenyl-d5)boronic acid (3.2 g, 25.4 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (10 g, 72.7 mmol) was dissolved in 30 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After the reaction for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-42. (Yield: 69%, MS: [M+H]⁺=666).

Synthesis Example 1-43

Compound 1-38 (10 g, 16 mmol), PtO₂ (1.1 g, 4.8 mmol) and D₂O (80 ml) were added to a shaker tube, and then the tube was sealed and heated at 250° C. and 600 psi for 12 hours. When the reaction was completed, chloroform was added, and the reaction solution was transferred to a separatory funnel, and extracted. The extract was dried over MgSO₄ and concentrated, and then the sample was purified by silica gel column chromatography to prepare 3.5 g of Compound 1-43. (Yield: 34%, MS: [M+H]⁺=649)

Synthesis Example 1-44

Trifluoromethanesulfonic anhydride (24 g, 85 mmol) and deuterium oxide (8.5 g, 424.9 mmol) were added at 0° C. and stirred for 5 hours to prepare a solution. 1-Bromodibenzo[b,d]furan (15 g, 60.7 mmol) was added to 120 ml of 1,2,4-trichlorobenzene, and the mixture was stirred. Then, the prepared mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was slowly added dropwise to the mixed solution of 1-bromodibenzo[b,d]furan and 1,2,4-trichlorobenzene, and the mixture was stirred while heating up to 140° C. and then keeping that temperature. After the reaction for 5 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 5.7 g of compound Sub5-1-1. (Yield: 38%, MS: [M+H]⁺=248)

Compound Sub5-1-1 (15 g, 60.5 mmol) and bis(pinacolato)diboron (16.9 g, 66.5 mmol) were added to 300 ml of 1,4-dioxane, and the mixture was stirred under reflux. Then, potassium acetate (8.9 g, 90.7 mmol) was added thereto, the mixture was sufficiently stirred, and then bis(dibenzylideneacetone) palladium(0) (1 g, 1.8 mmol) and tricyclohexylphosphine (1 g, 3.6 mmol) were added. After the reaction for 6 hours, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and then the organic layer was distilled. This was dissolved again in chloroform, washed twice with water, and the organic layer was then separated. Anhydrous magnesium sulfate was added thereto, stirred, 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 Sub5-1-2. (Yield: 75%, MS: [M+H]⁺=296)

Compound Sub5-1-2 (15 g, 50.8 mmol) and Compound Trz36 (25.8 g, 53.4 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 63 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After the reaction for 5 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.9 g of Compound 1-44. (Yield: 72%, MS: [M+H]⁺=518).

Synthesis Example 1-45

Trifluoromethanesulfonic anhydride (48 g, 170 mmol) and deuterium oxide (17 g, 849.9 mmol) were added at 0° C. and stirred for 5 hours to prepare a solution. 1-Bromodibenzo[b,d]furan (15 g, 60.7 mmol) was added to 120 ml of 1,2,4-trichlorobenzene, and the mixture was stirred. Then, the prepared mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was slowly added dropwise to the mixed solution of 1-bromodibenzo[b,d]furan and 1,2,4-trichlorobenzene, and the mixture was stirred while heating up to 140° C. and then keeping that temperature. After the reaction for 8 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 6 g of compound Sub5-2-1. (Yield: 40%, MS: [M+H]⁺=249)

Compound Sub5-2-1 (15 g, 60.2 mmol) and bis(pinacolato)diboron (16.8 g, 66.2 mmol) were added to 300 ml of 1,4-dioxane, and the mixture was stirred under reflux. Then, potassium acetate (8.9 g, 90.3 mmol) was added thereto, the mixture was sufficiently stirred, and then bis(dibenzylideneacetone) palladium(0) (1 g, 1.8 mmol) and tricyclohexylphosphine (1 g, 3.6 mmol) were added. After the reaction for 4 hours, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and then the organic layer was distilled. This was dissolved again in chloroform, washed twice with water, and the organic layer was then separated. Anhydrous magnesium sulfate was added thereto, stirred, 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 Sub5-2-2. (Yield: 70%, MS: [M+H]⁺=297)

Compound Sub5-2-2 (15 g, 50.6 mmol) and Compound Trz37 (23.9 g, 53.2 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (21 g, 151.9 mmol) was dissolved in 63 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After the reaction for 2 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.5 g of Compound 1-45. (Yield: 66%, MS: [M+H]⁺=583).

Synthesis Example 1-46

Compound Sub5-2-2 (15 g, 50.6 mmol) and Compound Trz38 (28 g, 53.2 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (21 g, 151.9 mmol) was dissolved in 63 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After the reaction for 5 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-46. (Yield: 64%, MS: [M+H]⁺=660).

Synthesis Example 1-47

Compound Sub5-2-2 (15 g, 50.6 mmol) and Compound Trz39 (21.9 g, 53.2 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (21 g, 151.9 mmol) was dissolved in 63 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After the reaction for 5 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.1 g of Compound 1-47. (Yield: 69%, MS: [M+H]⁺=546).

Synthesis Example 1-48

Compound Sub5-2-2 (15 g, 50.6 mmol) and Compound Trz40 (31.7 g, 53.2 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (21 g, 151.9 mmol) was dissolved in 63 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After the reaction for 2 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-48. (Yield: 69%, MS: [M+H]⁺=685).

Synthesis Example 1-49

Compound Sub5-2-2 (15 g, 50.6 mmol) and Compound Trz41 (25.4 g, 53.2 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (21 g, 151.9 mmol) was dissolved in 63 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After the reaction for 4 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.5 g of Compound 1-49. (Yield: 75%, MS: [M+H]⁺=568).

Synthesis Example 1-50

Trifluoromethanesulfonic anhydride (71.9 g, 255 mmol) and deuterium oxide (25.5 g, 1274.8 mmol) were added at 0° C. and stirred for hours to prepare a solution. 1-bromodibenzo[b,d]furan (15 g, 60.7 mmol) was added to 120 ml of 1,2,4-trichlorobenzene, and the mixture was stirred. Then, the prepared mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was slowly added dropwise to the mixed solution of 1-bromodibenzo[b,d]furan and 1,2,4-trichlorobenzene, and the mixture was stirred while heating up to 140° C. and then keeping that temperature. After the reaction for 14 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 6.3 g of compound Sub5-3-1. (Yield: 42%, MS: [M+H]⁺=250)

Compound Sub5-3-1 (15 g, 60 mmol) and bis(pinacolato)diboron (16.8 g, 66 mmol) were added to 300 ml of 1,4-dioxane, and the mixture was stirred under reflux. Then, potassium acetate (8.8 g, 90 mmol) was added thereto, the mixture was sufficiently stirred, and then bis(dibenzylideneacetone) palladium(0) (1 g, 1.8 mmol) and tricyclohexylphosphine (1 g, 3.6 mmol) were added. After the reaction for 6 hours, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and then the organic layer was distilled. This was dissolved again in chloroform, washed twice with water, and the organic layer was then separated. Anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.4 g of Compound Sub5-3-2. (Yield: 64%, MS: [M+H]⁺=298)

Compound Sub5-3-2 (15 g, 50.5 mmol) and Compound Trz42 (25.2 g, 53 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (20.9 g, 151.4 mmol) was dissolved in 63 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After the reaction for 2 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-50. (Yield: 66%, MS: [M+H]⁺=610).

Synthesis Example 1-51

Compound Sub5-3-2 (15 g, 50.5 mmol) and Compound Trz43 (23.5 g, 53 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (20.9 g, 151.4 mmol) was dissolved in 63 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After the reaction for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.6 g of Compound 1-51. (Yield: 69%, MS: [M+H]⁺=534).

Synthesis Example 1-52

Compound Sub5-3-2 (15 g, 50.5 mmol) and Compound Trz44 (22.8 g, 53 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (20.9 g, 151.4 mmol) was dissolved in 63 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After the reaction for 4 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.1 g of Compound 1-52. (Yield: 74%, MS: [M+H]⁺=565).

Synthesis Example 1-53

Trifluoromethanesulfonic anhydride (95.9 g, 340 mmol) and deuterium oxide (34 g, 1699.8 mmol) were added at 0° C. and stirred for 5 hours to prepare a solution. 1-bromodibenzo[b,d]furan (15 g, 60.7 mmol) was added to 120 ml of 1,2,4-trichlorobenzene, and the mixture was stirred. Then, the prepared mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was slowly added dropwise to the mixed solution of 1-bromodibenzo[b,d]furan and 1,2,4-trichlorobenzene, and the mixture was stirred while heating up to 140° C. and then keeping that temperature. After the reaction for 20 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 5.6 g of compound Sub5-4-1. (Yield: 37%, MS: [M+H]⁺=251)

Compound Sub5-4-1 (15 g, 59.7 mmol) and bis(pinacolato)diboron (16.7 g, 65.7 mmol) were added to 300 ml of 1,4-dioxane, and the mixture was stirred under reflux. Then, potassium acetate (8.8 g, 89.6 mmol) was added thereto, the mixture was sufficiently stirred, and then bis(dibenzylideneacetone) palladium(0) (1 g, 1.8 mmol) and tricyclohexylphosphine (1 g, 3.6 mmol) were added. After the reaction for 5 hours, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and then the organic layer was distilled. This was dissolved again in chloroform, washed twice with water, and the organic layer was then separated. Anhydrous magnesium sulfate was added thereto, stirred, 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 Sub5-4-2. (Yield: 70%, MS: [M+H]⁺=299)

Compound Sub5-4-2 (15 g, 50.3 mmol) and Compound Trz45 (28.1 g, 52.8 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (20.9 g, 150.9 mmol) was dissolved in 63 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After the reaction for 4 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-53. (Yield: 71%, MS: [M+H]⁺=668).

Synthesis Example 1-54

Trifluoromethanesulfonic anhydride (119.9 g, 424.9 mmol) and deuterium oxide (42.6 g, 2124.7 mmol) were added at 0° C. and stirred for hours to prepare a solution. 1-Bromodibenzo[b,d]furan (15 g, 60.7 mmol) was added to 120 ml of 1,2,4-trichlorobenzene, and the mixture was stirred. Then, the prepared mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was slowly added dropwise to the mixed solution of 1-bromodibenzo[b,d]furan and 1,2,4-trichlorobenzene, and the mixture was stirred while heating up to 140° C. and then keeping that temperature. After the reaction for 24 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 5.9 g of compound Sub5-5-1. (Yield: 39%, MS: [M+H]⁺=252)

Compound Sub5-5-1 (15 g, 59.5 mmol) and bis(pinacolato)diboron (16.6 g, 65.4 mmol) were added to 300 ml of 1,4-dioxane, and the mixture was stirred under reflux. Then, potassium acetate (8.8 g, 89.2 mmol) was added thereto, the mixture was sufficiently stirred, and then bis(dibenzylideneacetone) palladium(0) (1 g, 1.8 mmol) and tricyclohexylphosphine (1 g, 3.6 mmol) were added. After the reaction for 4 hours, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and then the organic layer was distilled. This was dissolved again in chloroform, washed twice with water, and the organic layer was then separated. Anhydrous magnesium sulfate was added thereto, stirred, 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 Sub5-5-2. (Yield: 63%, MS: [M+H]⁺=300)

Compound Sub5-5-2 (15 g, 50.1 mmol) and Compound Trz46 (27.6 g, 52.6 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (20.8 g, 150.4 mmol) was dissolved in 62 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After the reaction for 5 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-54. (Yield: 73%, MS: [M+H]⁺=581).

Synthesis Example 1-55

Compound Sub5-5-2 (15 g, 50.1 mmol) and Compound Trz47 (27.6 g, 52.6 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (20.8 g, 150.4 mmol) was dissolved in 62 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After the reaction for 4 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.9 g of Compound 1-55. (Yield: 75%, MS: [M+H]⁺=662).

Synthesis Example 1-56

Compound Sub5-5-2 (15 g, 50.1 mmol) and Compound Trz22 (29.7 g, 52.6 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (20.8 g, 150.4 mmol) was dissolved in 62 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After the reaction for 4 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-56. (Yield: 71%, MS: [M+H]⁺=657).

Synthesis Example 1-57

Compound Sub5-5-2 (15 g, 50.1 mmol) and Compound Trz48 (27.3 g, 52.6 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (20.8 g, 150.4 mmol) was dissolved in 62 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After the reaction for 4 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 g of Compound 1-57. (Yield: 62%, MS: [M+H]⁺=612).

Synthesis Example 1-58

Compound Sub5-5-2 (15 g, 50.1 mmol) and Compound Trz49 (27.1 g, 52.6 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (20.8 g, 150.4 mmol) was dissolved in 62 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After the reaction for 5 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.5 g of Compound 1-58. (Yield: 64%, MS: [M+H]⁺=607).

Synthesis Example 1-59

Trifluoromethanesulfonic anhydride (167.8 g, 594.9 mmol) and deuterium oxide (59.6 g, 2974.6 mmol) were added at 0° C. and stirred for hours to prepare a solution. 1-Bromodibenzo[b,d]furan (15 g, 60.7 mmol) was added to 120 ml of 1,2,4-trichlorobenzene, and the mixture was stirred. Then, the prepared mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was slowly added dropwise to the mixed solution of 1-bromodibenzo[b,d]furan and 1,2,4-trichlorobenzene, and the mixture was stirred while heating up to 140° C. and then keeping that temperature. After the reaction for 36 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. Then, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 6.1 g of compound Sub5-6-1. (Yield: 40%, MS: [M+H]⁺=254)

Compound Sub5-6-1 (15 g, 59 mmol) and bis(pinacolato)diboron (16.5 g, 64.9 mmol) were added to 300 ml of 1,4-dioxane, and the mixture was stirred under reflux. Then, potassium acetate (8.7 g, 88.5 mmol) was added thereto, the mixture was sufficiently stirred, and then bis(dibenzylideneacetone) palladium(0) (1 g, 1.8 mmol) and tricyclohexylphosphine (1 g, 3.5 mmol) were added. After the reaction for 4 hours, the reaction mixture was cooled to room temperature, the organic layer was separated using chloroform and water, and then the organic layer was distilled. This was dissolved again in chloroform, washed twice with water, and the organic layer was then separated. Anhydrous magnesium sulfate was added thereto, stirred, 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 Sub5-6-2. (Yield: 65%, MS: [M+H]⁺=302)

Compound Sub5-6-2 (15 g, 50 mmol) and Compound Trz50 (24.2 g, 52.5 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (20.7 g, 149.9 mmol) was dissolved in 62 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After the reaction for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.5 g of Compound 1-59. (Yield: 75%, MS: [M+H]⁺=601).

Synthesis Example 1-60

Compound Sub5-6-2 (15 g, 50 mmol) and Compound Trz51 (24.1 g, 52.5 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (20.7 g, 149.9 mmol) was dissolved in 62 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After the reaction for 5 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-60. (Yield: 74%, MS: [M+H]⁺=599).

Synthesis Example 1-61

Compound Sub5-6-2 (15 g, 50 mmol) and Compound Trz52 (25.3 g, 52.5 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (20.7 g, 149.9 mmol) was dissolved in 62 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After the reaction for 5 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-61. (Yield: 75%, MS: [M+H]⁺=577).

Synthesis Example 1-62

Compound Sub5-6-2 (15 g, 50 mmol) and Compound Trz53 (32 g, 52.5 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (20.7 g, 149.9 mmol) was dissolved in 62 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After the reaction for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-62. (Yield: 74%, MS: [M+H]⁺=704).

Synthesis Example 1-63

Compound Sub5-6-2 (15 g, 50 mmol) and Compound Trz54 (27.3 g, 52.5 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (20.7 g, 149.9 mmol) was dissolved in 62 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After the reaction for 5 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, 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 1-63. (Yield: 60%, MS: [M+H]⁺=615).

Synthesis Example 1-64

Dibenzo[b,d]furan-1-ylboronic acid (15 g, 70.8 mmol) and Compound Trz55 (45.7 g, 74.3 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (29.3 g, 212.3 mmol) was dissolved in 88 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added. After the reaction for 5 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 32.2 g of Compound 1-64_P1. (Yield: 65%, MS: [M+H]⁺=702).

Compound 1-64_P1 (10 g, 14.2 mmol), PtO₂ (1 g, 4.3 mmol) and D₂O (71 ml) were added to a shaker tube, and then the tube was sealed and heated at 250° C. and 600 psi for 12 hours. When the reaction was completed, chloroform was added, and the reaction solution was transferred to a separatory funnel, and extracted. The extract was dried over MgSO₄ and concentrated, and then the sample was purified by silica gel column chromatography to prepare 4 g of Compound 1-64. (Yield: 39%, MS: [M+H]⁺=727)

Synthesis Example 1-65

Dibenzo[b,d]furan-1-ylboronic acid (15 g, 70.8 mmol) and Compound Trz56 (33 g, 74.3 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (29.3 g, 212.3 mmol) was dissolved in 88 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added. After the reaction for 5 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 29.7 g of Compound 1-65_P1. (Yield: 73%, MS: [M+H]⁺=576).

Compound 1-65_P1 (10 g, 17.4 mmol), PtO₂ (1.2 g, 5.2 mmol) and D₂O (87 ml) were added to a shaker tube, and then the tube was sealed and heated at 250° C. and 600 psi for 12 hours. When the reaction was completed, chloroform was added, and the reaction solution was transferred to a separatory funnel, and extracted. The extract was dried over MgSO₄ and concentrated, and then the sample was purified by silica gel column chromatography to prepare 5.1 g of Compound 1-65. (Yield: 49%, MS: [M+H]⁺=599)

Synthesis Example 1-66

Dibenzo[b,d]furan-1-ylboronic acid (15 g, 70.8 mmol) and Compound Trz46 (33 g, 74.3 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (29.3 g, 212.3 mmol) was dissolved in 88 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added. After the reaction for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.8 g of Compound 1-66_P1. (Yield: 61%, MS: [M+H]⁺=576).

Compound 1-66_P1 (10 g, 17.4 mmol), PtO₂ (1.2 g, 5.2 mmol) and D₂O (87 ml) were added to a shaker tube, and then the tube was sealed and heated at 250° C. and 600 psi for 12 hours. When the reaction was completed, chloroform was added, and the reaction solution was transferred to a separatory funnel, and extracted. The extract was dried over MgSO₄ and concentrated, and then the sample was purified by silica gel column chromatography to prepare 5 g of Compound 1-66. (Yield: 48%, MS: [M+H]⁺=598)

Synthesis Example 1-67

Dibenzo[b,d]furan-1-ylboronic acid (15 g, 70.8 mmol) and Compound Trz57 (33 g, 74.3 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (29.3 g, 212.3 mmol) was dissolved in 88 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added. After the reaction for 5 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26.5 g of Compound 1-67_P1. (Yield: 65%, MS: [M+H]⁺=576).

Compound 1-67_P1 (10 g, 17.4 mmol), PtO₂ (1.2 g, 5.2 mmol) and D₂O (87 ml) were added to a shaker tube, and then the tube was sealed and heated at 250° C. and 600 psi for 12 hours. When the reaction was completed, chloroform was added, and the reaction solution was transferred to a separatory funnel, and extracted. The extract was dried over MgSO₄ and concentrated, and then the sample was purified by silica gel column chromatography to prepare 4.4 g of Compound 1-67. (Yield: 42%, MS: [M+H]⁺=598)

Synthesis Example 1-68

Dibenzo[b,d]furan-1-ylboronic acid (15 g, 70.8 mmol) and Compound Trz58 (33 g, 74.3 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (29.3 g, 212.3 mmol) was dissolved in 88 ml of water and added thereto, and the mixture was sufficiently stirred and then bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added. After the reaction for 4 hours, the reaction mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated and then the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26.5 g of Compound 1-68_P1. (Yield 65% MS: [M+H]⁺=576).

Compound 1-68_P1 (10 g, 17.4 mmol), PtO₂ (1.2 g, 5.2 mmol) and D₂O (87 ml) were added to a shaker tube, and then the tube was sealed and heated at 250° C. and 600 psi for 12 hours. When the reaction was completed, chloroform was added, and the reaction solution was transferred to a separatory funnel, and extracted. The extract was dried over MgSO₄ and concentrated, and then the sample was purified by silica gel column chromatography to prepare 3.6 g of Compound 1-68. (Yield: 35%, MS: [M+H]⁺=598)

Synthesis Example 2-1

9H-carbazole (10 g, 59.8 mmol), 1-bromo-4-chlorobenzene (12 g, 62.8 mmol) and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subA-1. (Yield: 62%, MS: [M+H]⁺=278)

Compound subA-1 (10 g, 36 mmol), Compound amine1 (15 g, 37.8 mmol) and sodium tert-butoxide (4.5 g, 46.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-1. (Yield: 62%, MS: [M+H]⁺=639)

Synthesis Example 2-2

Compound subA-1 (10 g, 36 mmol), Compound amine2 (15.9 g, 37.8 mmol) and sodium tert-butoxide (4.5 g, 46.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.4 g of Compound 2-2. (Yield: 73%, MS: [M+H]⁺=663) Synthesis Example 2-3

Compound subA-1 (10 g, 36 mmol), Compound amine3 (15.5 g, 37.8 mmol) and sodium tert-butoxide (4.5 g, 46.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-3. (Yield: 61%, MS: [M+H]⁺=651)

Synthesis Example 2-4

Compound subA-1 (10 g, 36 mmol), Compound amine4 (15.6 g, 37.8 mmol) and sodium tert-butoxide (4.5 g, 46.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-4. (Yield: 61%, MS: [M+H]⁺=653)

Synthesis Example 2-5

Compound subA-1 (10 g, 36 mmol), Compound amine5 (15.5 g, 37.8 mmol) and sodium tert-butoxide (4.5 g, 46.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15 g of Compound 2-5. (Yield: 64%, MS: [M+H]⁺=652)

Synthesis Example 2-6

Compound subA-1 (10 g, 36 mmol), Compound amine6 (13.7 g, 37.8 mmol) and sodium tert-butoxide (4.5 g, 46.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-6. (Yield: 73%, MS: [M+H]⁺=603)

Synthesis Example 2-7

9H-carbazole (10 g, 59.8 mmol), 2-bromo-5-chloro-1,1′-bipheny (16.8 g, 62.8 mmol) and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subA-2. (Yield: 70%, MS: [M+H]⁺=354)

Compound subA-2 (10 g, 28.3 mmol), Compound amine7 (14.5 g, 29.7 mmol) and sodium tert-butoxide (3.5 g, 36.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-7. (Yield: 69%, MS: [M+H]⁺=805)

Synthesis Example 2-8

Compound subA-2 (10 g, 28.3 mmol), Compound amine8 (14 g, 29.7 mmol) and sodium tert-butoxide (3.5 g, 36.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-8. (Yield: 61%, MS: [M+H]⁺=789)

Synthesis Example 2-9

9H-carbazole (10 g, 59.8 mmol), 5-bromo-2-chloro-1,1′-biphenyl (16.8 g, 62.8 mmol) and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subA-3. (Yield: 74%, MS: [M+H]⁺=354)

Compound subA-3 (10 g, 28.3 mmol), Compound amine9 (14 g, 29.7 mmol) and sodium tert-butoxide (3.5 g, 36.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-9. (Yield: 60%, MS: [M+H]⁺=789)

Synthesis Example 2-10

Compound subA-2 (10 g, 28.3 mmol), Compound amine10 (13.2 g, 29.7 mmol) and sodium tert-butoxide (3.5 g, 36.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-10. (Yield: 74%, MS: [M+H]⁺=763)

Synthesis Example 2-11

9H-carbazole (10 g, 59.8 mmol), 1-bromo-4-chloronaphthalene (15.2 g, 62.8 mmol) and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subA-4. (Yield: 65%, MS: [M+H]⁺=328)

Compound subA-4 (10 g, 30.5 mmol), Compound amine11 (12.8 g, 32 mmol) and sodium tert-butoxide (3.8 g, 39.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-11. (Yield: 66%, MS: [M+H]⁺=691)

Synthesis Example 2-12

9H-carbazole (10 g, 59.8 mmol), 4-bromo-4′-chloro-1,1′-biphenyl (16.8 g, 62.8 mmol) and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.4 g of Compound subA-5. (Yield: 73%, MS: [M+H]⁺=354)

Compound subA-5 (10 g, 28.3 mmol), Compound amine12 (9.5 g, 29.7 mmol) and sodium tert-butoxide (3.5 g, 36.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-12. (Yield: 62%, MS: [M+H]⁺=639)

Synthesis Example 2-13

Compound subA-5 (10 g, 28.3 mmol), Compound amine13 (10.4 g, 29.7 mmol) and sodium tert-butoxide (3.5 g, 36.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-13. (Yield: 72%, MS: [M+H]⁺=664)

Synthesis Example 2-14

Compound subA-5 (10 g, 28.3 mmol), Compound amine14 (10.7 g, 29.7 mmol) and sodium tert-butoxide (3.5 g, 36.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-14. (Yield: 65%, MS: [M+H]⁺=679)

Synthesis Example 2-15

Compound subA-5 (10 g, 28.3 mmol), Compound amine15 (14.9 g, 29.7 mmol) and sodium tert-butoxide (3.5 g, 36.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.6 g of Compound 2-15. (Yield: 63%, MS: [M+H]⁺=821)

Synthesis Example 2-16

Compound subA-5 (10 g, 28.3 mmol), Compound amine16 (13.3 g, 29.7 mmol) and sodium tert-butoxide (3.5 g, 36.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-16. (Yield: 72%, MS: [M+H]⁺=765)

Synthesis Example 2-17

9H-carbazole (10 g, 59.8 mmol), 4-bromo-4′-chloro-1,1′:3′,1″-terphenyl (21.6 g, 62.8 mmol) and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.4 g of Compound subA-6. (Yield: 60%, MS: [M+H]⁺=430)

Compound subA-6 (10 g, 23.3 mmol), Compound amine12 (7.8 g, 24.4 mmol) and sodium tert-butoxide (2.9 g, 30.2 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-17. (Yield: 69%, MS: [M+H]⁺=715)

Synthesis Example 2-18

9H-carbazole (10 g, 59.8 mmol), 1-bromo-4-(4-chlorophenyl) naphthalene (19.9 g, 62.8 mmol) and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subA-7. (Yield: 65%, MS: [M+H]⁺=404)

Compound subA-7 (10 g, 24.8 mmol), Compound amine17 (11.6 g, 26 mmol) and sodium tert-butoxide (3.1 g, 32.2 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.1 g of Compound 2-18. (Yield: 65%, MS: [M+H]⁺=815)

Synthesis Example 2-19

9H-carbazole (10 g, 59.8 mmol), 1-bromo-4-(5-chloro-[1,1′-biphenyl]-2-yl) naphthalene (24.7 g, 62.8 mmol) and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.6 g of Compound subA-8. (Yield: 65%, MS: [M+H]⁺=480)

Compound subA-8 (10 g, 20.8 mmol), Compound amine18 (9.8 g, 21.9 mmol) and sodium tert-butoxide (2.6 g, 27.1 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butyl phosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-19. (Yield: 73%, MS: [M+H]⁺=891)

Synthesis Example 2-20

9H-carbazole (10 g, 59.8 mmol), 4′-bromo-4-chloro-1,1′:2′,1″-terphenyl (21.6 g, 62.8 mmol) and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subA-9. (Yield: 61%, MS: [M+H]⁺=430)

Compound subA-9 (10 g, 23.3 mmol), Compound amine19 (9.8 g, 24.4 mmol) and sodium tert-butoxide (2.9 g, 30.2 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-20. (Yield: 63%, MS: [M+H]⁺=793)

Synthesis Example 2-21

9H-carbazole (10 g, 59.8 mmol), 1-(4-bromophenyl)-4-chloronaphthalene (19.9 g, 62.8 mmol) and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.4 g of Compound subA-10. (Yield: 72%, MS: [M+H]⁺=404)

Compound subA-10 (10 g, 24.8 mmol), Compound amine20 (8.4 g, 26 mmol) and sodium tert-butoxide (3.1 g, 32.2 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-21. (Yield: 74%, MS: [M+H]⁺=689)

Synthesis Example 2-22

9H-carbazole (10 g, 59.8 mmol), 2-bromo-4′-chloro-1,1′-biphenyl (16.8 g, 62.8 mmol) and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subA-11. (Yield: 74%, MS: [M+H]⁺=354)

Compound subA-11 (10 g, 28.3 mmol), Compound amine21 (12.5 g, 29.7 mmol) and sodium tert-butoxide (3.5 g, 36.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-22. (Yield: 62%, MS: [M+H]⁺=739)

Synthesis Example 2-23

Compound subA-11 (10 g, 28.3 mmol), Compound amine22 (13.3 g, 29.7 mmol) and sodium tert-butoxide (3.5 g, 36.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-23. (Yield: 63%, MS: [M+H]⁺=765)

Synthesis Example 2-24

Compound subA-11 (10 g, 28.3 mmol), Compound amine23 (13.3 g, 29.7 mmol) and sodium tert-butoxide (3.5 g, 36.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-24. (Yield: 62%, MS: [M+H]⁺=765)

Synthesis Example 2-25

Compound subA-11 (10 g, 28.3 mmol), Compound amine24 (14 g, 29.7 mmol) and sodium tert-butoxide (3.5 g, 36.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-25. (Yield: 70%, MS: [M+H]⁺=789)

Synthesis Example 2-26

Compound subA-11 (10 g, 28.3 mmol), Compound amine25 (13.3 g, 29.7 mmol) and sodium tert-butoxide (3.5 g, 36.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-26. (Yield: 67%, MS: [M+H]⁺=765)

Synthesis Example 2-27

Compound subA-11 (10 g, 28.3 mmol), Compound amine26 (14 g, 29.7 mmol) and sodium tert-butoxide (3.5 g, 36.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-27. (Yield: 74%, MS: [M+H]⁺=789)

Synthesis Example 2-28

Compound subA-11 (10 g, 28.3 mmol), Compound amine27 (11 g, 29.7 mmol) and sodium tert-butoxide (3.5 g, 36.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.7 g of Compound 2-28. (Yield: 60%, MS: [M+H]⁺=689)

Synthesis Example 2-29

Compound subA-11 (10 g, 28.3 mmol), Compound amine28 (14.9 g, 29.7 mmol) and sodium tert-butoxide (3.5 g, 36.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-29. (Yield: 61%, MS: [M+H]⁺=821)

Synthesis Example 2-30

Compound subA-11 (10 g, 28.3 mmol), Compound amine29 (13.3 g, 29.7 mmol) and sodium tert-butoxide (3.5 g, 36.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-30. (Yield: 71%, MS: [M+H]⁺=765)

Synthesis Example 2-31

Compound subA-11 (10 g, 28.3 mmol), Compound amine30 (11.4 g, 29.7 mmol) and sodium tert-butoxide (3.5 g, 36.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.1 g of Compound 2-31. (Yield: 66%, MS: [M+H]⁺=703)

Synthesis Example 2-32

Compound subA-11 (10 g, 28.3 mmol), Compound amine31 (12.5 g, 29.7 mmol) and sodium tert-butoxide (3.5 g, 36.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-32. (Yield: 68%, MS: [M+H]⁺=739)

Synthesis Example 2-33

9H-carbazole (10 g, 59.8 mmol), 2-bromo-4′-chloro-1,1′:2′,1″-terphenyl (21.6 g, 62.8 mmol) and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subA-12. (Yield: 66%, MS: [M+H]⁺=430)

Compound subA-12 (10 g, 23.3 mmol), Compound amine32 (9.1 g, 24.4 mmol) and sodium tert-butoxide (2.9 g, 30.2 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-33. (Yield: 71%, MS: [M+H]⁺=765)

Synthesis Example 2-34

9H-carbazole (10 g, 59.8 mmol), 2′-bromo-4-chloro-1,1′:3′,1″-terphenyl (21.6 g, 62.8 mmol) and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subA-13. (Yield: 64%, MS: [M+H]⁺=430)

Compound subA-13 (10 g, 23.3 mmol), Compound amine12 (7.8 g, 24.4 mmol) and sodium tert-butoxide (2.9 g, 30.2 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-34. (Yield: 71%, MS: [M+H]⁺=715)

Synthesis Example 2-35

Compound subA-12 (10 g, 23.3 mmol), Compound amine33 (9.1 g, 24.4 mmol) and sodium tert-butoxide (2.9 g, 30.2 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-35. (Yield: 69%, MS: [M+H]⁺=765)

Synthesis Example 2-36

9H-carbazole (10 g, 59.8 mmol), 3′-bromo-4″-chloro-1,1′:2′,1″-terphenyl (21.6 g, 62.8 mmol) and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subA-14. (Yield: 61%, MS: [M+H]⁺=430)

Compound subA-14 (10 g, 23.3 mmol), Compound amine34 (10.3 g, 24.4 mmol) and sodium tert-butoxide (2.9 g, 30.2 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-36. (Yield: 72%, MS: [M+H]⁺=815)

Synthesis Example 2-37

9H-carbazole (10 g, 59.8 mmol), 3-bromo-4′-chloro-1,1′-biphenyl (16.8 g, 62.8 mmol) and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subA-15. (Yield: 63%, MS: [M+H]⁺=354)

Compound subA-15 (10 g, 28.3 mmol), Compound amine35 (11.0 g, 29.7 mmol) and sodium tert-butoxide (3.5 g, 36.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-37. (Yield: 68%, MS: [M+H]⁺=689)

Synthesis Example 2-38

Compound subA-15 (10 g, 28.3 mmol), Compound amine36 (10.0 g, 29.7 mmol) and sodium tert-butoxide (3.5 g, 36.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-38. (Yield: 69%, MS: [M+H]⁺=653)

Synthesis Example 2-39

Compound subA-15 (10 g, 28.3 mmol), Compound amine37 (14.5 g, 29.7 mmol) and sodium tert-butoxide (3.5 g, 36.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-39. (Yield: 60%, MS: [M+H]⁺=805)

Synthesis Example 2-40

9H-carbazole (10 g, 59.8 mmol), 5′-bromo-4-chloro-1,1′:3′,1″-terphenyl (21.6 g, 62.8 mmol) and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subA-16. (Yield: 70%, MS: [M+H]⁺=430)

Compound subA-16 (10 g, 23.3 mmol), Compound amine38 (9 g, 24.4 mmol) and sodium tert-butoxide (2.9 g, 30.2 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-40. (Yield: 71%, MS: [M+H]⁺=763)

Synthesis Example 2-41

9H-carbazole (10 g, 59.8 mmol), 5′-bromo-4-chloro-1,1′:2′,1″-terphenyl (21.6 g, 62.8 mmol) and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.4 g of Compound subA-17. (Yield: 60%, MS: [M+H]⁺=430)

Compound subA-17 (10 g, 23.3 mmol), Compound amine39 (9.1 g, 24.4 mmol) and sodium tert-butoxide (2.9 g, 30.2 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.7 g of Compound 2-41. (Yield: 66%, MS: [M+H]⁺=766)

Synthesis Example 2-42

9H-carbazole (10 g, 59.8 mmol), 3-bromo-4′-chloro-1,1′:2′,1″-terphenyl (21.6 g, 62.8 mmol) and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19 g of Compound subA-18. (Yield: 74%, MS: [M+H]⁺=430)

Compound subA-18 (10 g, 23.3 mmol), Compound amine40 (7.8 g, 24.4 mmol) and sodium tert-butoxide (2.9 g, 30.2 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-42. (Yield: 73%, MS: [M+H]⁺=715)

Synthesis Example 2-43

9H-carbazole (10 g, 59.8 mmol), 3-bromo-4′-chloro-1,1′:3′,1″-terphenyl (21.6 g, 62.8 mmol) and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subA-19. (Yield: 65%, MS: [M+H]⁺=430).

Compound subA-19 (10 g, 23.3 mmol), Compound amine41 (9.1 g, 24.4 mmol) and sodium tert-butoxide (2.9 g, 30.2 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-43. (Yield: 71%, MS: [M+H]⁺=765)

Synthesis Example 2-44

9H-carbazole (10 g, 59.8 mmol), 3-bromo-3′-chloro-1,1′-biphenyl (16.8 g, 62.8 mmol) and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subA-20. (Yield: 67%, MS: [M+H]⁺=354)

Compound subA-20 (10 g, 28.3 mmol), Compound amine42 (11.1 g, 29.7 mmol) and sodium tert-butoxide (3.5 g, 36.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-44. (Yield: 62%, MS: [M+H]⁺=689)

Synthesis Example 2-45

9H-carbazole (10 g, 59.8 mmol), 2-bromo-3′-chloro-1,1′-biphenyl (16.8 g, 62.8 mmol) and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subA-21. (Yield: 63%, MS: [M+H]⁺=354)

Compound subA-21 (10 g, 28.3 mmol), Compound amine43 (11.7 g, 29.7 mmol) and sodium tert-butoxide (3.5 g, 36.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-45. (Yield: 73%, MS: [M+H]⁺=713)

Synthesis Example 2-46

9H-carbazole (10 g, 59.8 mmol), 6′-bromo-3-chloro-1,1′:3′,1″-terphenyl (21.6 g, 62.8 mmol) and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subA-22. (Yield: 64%, MS: [M+H]⁺=430)

Compound subA-22 (10 g, 23.3 mmol), Compound amine44 (7.8 g, 24.4 mmol) and sodium tert-butoxide (2.9 g, 30.2 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.1 g of Compound 2-46. (Yield: 61%, MS: [M+H]⁺=715)

Synthesis Example 2-47

Compound subA-20 (10 g, 28.3 mmol), Compound amine45 (13.3 g, 29.7 mmol) and sodium tert-butoxide (3.5 g, 36.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-47. (Yield: 64%, MS: [M+H]⁺=765)

Synthesis Example 2-48

9H-carbazole (10 g, 59.8 mmol), 1-bromo-2-chlorobenzene (12 g, 62.8 mmol) and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subA-23. (Yield: 72%, MS: [M+H]⁺=278)

Compound subA-23 (10 g, 36 mmol), Compound amine46 (13.1 g, 37.8 mmol) and sodium tert-butoxide (4.5 g, 46.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-48. (Yield: 66%, MS: [M+H]⁺=587)

Synthesis Example 2-49

9H-carbazole (10 g, 59.8 mmol), 1-bromo-3-chlorobenzene (12 g, 62.8 mmol) and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.9 g of Compound subA-24. (Yield: 60%, MS: [M+H]⁺=278)

Compound subA-24 (10 g, 36 mmol), Compound amine47 (16.8 g, 37.8 mmol) and sodium tert-butoxide (4.5 g, 46.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-49. (Yield: 73%, MS: [M+H]⁺=687)

Synthesis Example 2-50

Compound subA-24 (10 g, 36 mmol), Compound amine48 (16.9 g, 37.8 mmol) and sodium tert-butoxide (4.5 g, 46.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17 g of Compound 2-50. (Yield: 69%, MS: [M+H]⁺=687)

Synthesis Example 2-51

9H-carbazole (10 g, 59.8 mmol), 2-bromo-4-chloro-1,1′-biphenyl (16.8 g, 62.8 mmol) and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subA-25. (Yield: 75%, MS: [M+H]⁺=354)

Compound subA-25 (10 g, 28.3 mmol), Compound amine49 (9.5 g, 29.7 mmol) and sodium tert-butoxide (3.5 g, 36.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-51. (Yield: 75%, MS: [M+H]⁺=637)

Synthesis Example 2-52

9H-carbazole (10 g, 59.8 mmol), 4-bromo-2-chloro-1,1′-biphenyl (16.8 g, 62.8 mmol) and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15 g of Compound subA-26. (Yield: 71%, MS: [M+H]⁺=354)

Compound subA-26 (10 g, 28.3 mmol), Compound amine50 (14 g, 29.7 mmol) and sodium tert-butoxide (3.5 g, 36.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-52. (Yield: 67%, MS: [M+H]⁺=789)

Synthesis Example 2-53

9H-carbazole (10 g, 59.8 mmol), 3-bromo-5-chloro-1,1′-biphenyl (16.8 g, 62.8 mmol) and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subA-27. (Yield: 74%, MS: [M+H]⁺=354)

Compound subA-27 (10 g, 2.8 mmol), Compound amine43 (1.2 g, 3 mmol) and sodium tert-butoxide (0.4 g, 3.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0 g, 0 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 1.2 g of Compound 2-53. (Yield: 60%, MS: [M+H]⁺=713)

Synthesis Example 2-54

Compound subA-27 (10 g, 2.8 mmol), Compound amine51 (0.9 g, 3 mmol) and sodium tert-butoxide (0.4 g, 3.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0 g, 0 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 1 g of Compound 2-54. (Yield: 60%, MS: [M+H]⁺=613)

Synthesis Example 2-55

Compound subA-20 (10 g, 28.3 mmol), Compound amine52 (12.5 g, 29.7 mmol) and sodium tert-butoxide (3.5 g, 36.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-55. (Yield: 71%, MS: [M+H]⁺=739)

Synthesis Example 2-56

9H-carbazole (10 g, 59.8 mmol), 3-bromo-5′-chloro-1,1′:2′,1″-terphenyl (21.6 g, 62.8 mmol) and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.4 g of Compound subA-28. (Yield: 60%, MS: [M+H]⁺=430)

Compound subA-28 (10 g, 23.3 mmol), Compound amine53 (9.1 g, 24.4 mmol) and sodium tert-butoxide (2.9 g, 30.2 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-56. (Yield: 71%, MS: [M+H]⁺=765)

Synthesis Example 2-57

9H-carbazole (10 g, 59.8 mmol), 3-bromo-5′-chloro-1,1′:3′,1″-terphenyl (21.6 g, 62.8 mmol) and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subA-29. (Yield: 61%, MS: [M+H]⁺=430)

Compound subA-29 (10 g, 23.3 mmol), Compound amine39 (9.1 g, 24.4 mmol) and sodium tert-butoxide (2.9 g, 30.2 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-57. (Yield: 73%, MS: [M+H]⁺=765)

Synthesis Example 2-58

9H-carbazole (10 g, 59.8 mmol), 2-bromo-2′-chloro-1,1′-biphenyl (16.8 g, 62.8 mmol) and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15 g of Compound subA-30. (Yield: 71%, MS: [M+H]⁺=354)

Compound subA-30 (10 g, 28.3 mmol), Compound amine54 (12.5 g, 29.7 mmol) and sodium tert-butoxide (3.5 g, 36.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-58. (Yield: 61%, MS: [M+H]⁺=739)

Synthesis Example 2-59

Compound subA-30 (10 g, 28.3 mmol), Compound amine55 (11.8 g, 29.7 mmol) and sodium tert-butoxide (3.5 g, 36.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-59. (Yield: 69%, MS: [M+H]⁺=715)

Synthesis Example 2-60

9H-carbazole (10 g, 59.8 mmol), 3′-bromo-2-chloro-1,1′-biphenyl (16.8 g, 62.8 mmol) and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.1 g of Compound subA-31. (Yield: 62%, MS: [M+H]⁺=354)

Compound subA-31 (10 g, 28.3 mmol), Compound amine56 (12.5 g, 29.7 mmol) and sodium tert-butoxide (3.5 g, 36.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-60. (Yield: 71%, MS: [M+H]⁺=739)

Synthesis Example 2-61

9H-carbazole (10 g, 59.8 mmol), 3-bromo-6′-chloro-1,1′:2′,1″-terphenyl (21.6 g, 62.8 mmol) and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.5 g of Compound subA-32. (Yield: 68%, MS: [M+H]⁺=430)

Compound subA-32 (10 g, 23.3 mmol), Compound amine57 (9.7 g, 24.4 mmol) and sodium tert-butoxide (2.9 g, 30.2 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-61. (Yield: 73%, MS: [M+H]⁺=791)

Synthesis Example 2-62

9H-carbazole (10 g, 59.8 mmol), 4″-bromo-3′-chloro-1,1′:2′,1″-terphenyl (21.6 g, 62.8 mmol) and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subA-33. (Yield: 66%, MS: [M+H]⁺=430)

Compound subA-33 (10 g, 23.3 mmol) and Compound amine40 (7.8 g, 24.4 mmol), sodium tert-butoxide (2.9 g, 30.2 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.1 g of Compound 2-62. (Yield: 61%, MS: [M+H]⁺=715)

Synthesis Example 2-63

Compound subA-31 (10 g, 28.3 mmol), Compound amine58 (14 g, 29.7 mmol) and sodium tert-butoxide (3.5 g, 36.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-63. (Yield: 65%, MS: [M+H]⁺=789)

Synthesis Example 2-64

11H-benzo[a]carbazole (10 g, 46 mmol), 1-bromo-4-chlorobenzene (9.3 g, 48.3 mmol) and sodium tert-butoxide (5.7 g, 59.8 mmol) were added 10 to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.5 g of Compound subB-1. (Yield: 63%, MS: [M+H]⁺=328)

Compound subB-1 (10 g, 30.5 mmol), Compound amine59 (10.3 g, 32 mmol) and sodium tert-butoxide (3.8 g, 39.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.1 g of Compound 2-64. (Yield: 70%, MS: [M+H]⁺=613)

Synthesis Example 2-65

Compound subB-1 (10 g, 30.5 mmol), Compound amine60 (11.9 g, 32 mmol) and sodium tert-butoxide (3.8 g, 39.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-65. (Yield: 62%, MS: [M+H]⁺=663)

Synthesis Example 2-66

Compound subB-1 (10 g, 30.5 mmol), Compound amine61 (23.3 g, 32 mmol) and sodium tert-butoxide (3.8 g, 39.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-66. (Yield: 65%, MS: [M+H]⁺=719)

Synthesis Example 2-67

Compound subB-1 (10 g, 30.5 mmol), Compound amine62 (13.6 g, 32 mmol) and sodium tert-butoxide (3.8 g, 39.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-67. (Yield: 75%, MS: [M+H]⁺=716)

Synthesis Example 2-68

11H-benzo[a]carbazole (10 g, 46 mmol), 5-bromo-2-chloro-1,1′-biphenyl (12.9 g, 48.3 mmol) and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subB-2. (Yield: 75%, MS: [M+H]⁺=404)

Compound subB-2 (10 g, 24.8 mmol), Compound amine63 (9.7 g, 26 mmol) and sodium tert-butoxide (3.1 g, 32.2 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-68. (Yield: 72%, MS: [M+H]⁺=739)

Synthesis Example 2-69

11H-benzo[a]carbazole (10 g, 46 mmol), 2-bromo-5-chloro-1,1′-biphenyl (12.9 g, 48.3 mmol) and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subB-3. (Yield: 67%, MS: [M+H]⁺=404)

Compound subB-3 (10 g, 24.8 mmol), Compound amine49 (8.3 g, 26 mmol) and sodium tert-butoxide (3.1 g, 32.2 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-69. (Yield: 68%, MS: [M+H]⁺=687)

Synthesis Example 2-70

11H-benzo[a]carbazole (10 g, 46 mmol) and 4-bromo-4′-chloro-1,1′-biphenyl (12.9 g, 48.3 mmol), sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subB-4. (Yield: 65%, MS: [M+H]⁺=404)

Compound subB-4 (10 g, 24.8 mmol), Compound amine64 (7.7 g, 26 mmol) and sodium tert-butoxide (3.1 g, 32.2 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-70. (Yield: 71%, MS: [M+H]⁺=663)

Synthesis Example 2-71

Compound subB-4 (10 g, 24.8 mmol), Compound amine65 (7.7 g, 26 mmol) and sodium tert-butoxide (3.1 g, 32.2 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-71. (Yield: 71%, MS: [M+H]⁺=663)

Synthesis Example 2-72

11H-benzo[a]carbazole (10 g, 46 mmol), 1-bromo-4-(4-chlorophenyl) naphthalene (15.3 g, 48.3 mmol) and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subB-5. (Yield: 73%, MS: [M+H]⁺=454)

Compound subB-5 (10 g, 22 mmol), Compound amine66 (9.1 g, 23.1 mmol) and sodium tert-butoxide (2.8 g, 28.6 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-72. (Yield: 68%, MS: [M+H]⁺=813)

Synthesis Example 2-73

11H-benzo[a]carbazole (10 g, 46 mmol), 4′-bromo-4-chloro-1,1′:2′,1″-terphenyl (16.6 g, 48.3 mmol) and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15 g of Compound subB-6. (Yield: 68%, MS: [M+H]⁺=480)

Compound subB-6 (10 g, 20.8 mmol), Compound amine67 (8.7 g, 21.9 mmol) and sodium tert-butoxide (2.6 g, 27.1 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-73. (Yield: 71%, MS: [M+H]⁺=839)

Synthesis Example 2-74

11H-benzo[a]carbazole (10 g, 46 mmol), 2-bromo-4′-chloro-1,1′-biphenyl (12.9 g, 48.3 mmol) and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subB-7. (Yield: 71%, MS: [M+H]⁺=404)

Compound subB-7 (10 g, 24.8 mmol), Compound amine25 (11.6 g, 26 mmol) and sodium tert-butoxide (3.1 g, 32.2 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-74. (Yield: 66%, MS: [M+H]⁺=815)

Synthesis Example 2-75

Compound subB-7 (10 g, 24.8 mmol), Compound amine42 (9.7 g, 26 mmol) and sodium tert-butoxide (3.1 g, 32.2 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-75. (Yield: 67%, MS: [M+H]⁺=739)

Synthesis Example 2-76

11H-benzo[a]carbazole (10 g, 46 mmol), 3′-bromo-4″-chloro-1,1′:2′,1″-terphenyl (16.6 g, 48.3 mmol) and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subB-8. (Yield: 65%, MS: [M+H]⁺=480)

Compound subB-8 (10 g, 20.8 mmol), Compound amine68 (7.6 g, 21.9 mmol) and sodium tert-butoxide (2.6 g, 27.1 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-76. (Yield: 73%, MS: [M+H]⁺=789)

Synthesis Example 2-77

11H-benzo[a]carbazole (10 g, 46 mmol), 2-bromo-4′-chloro-1,1′:3′,1″-terphenyl (16.6 g, 48.3 mmol) and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subB-9. (Yield: 71%, MS: [M+H]⁺=480)

Compound subB-9 (10 g, 20.8 mmol), Compound amine69 (7 g, 21.9 mmol) and sodium tert-butoxide (2.6 g, 27.1 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.6 g of Compound 2-77. (Yield: 60%, MS: [M+H]⁺=765)

Synthesis Example 2-78

11H-benzo[a]carbazole (10 g, 46 mmol), 2-bromo-4′-chloro-1,1′:2′,1″-terphenyl (16.6 g, 48.3 mmol) and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.6 g of Compound subB-10. (Yield: 66%, MS: [M+H]⁺=480)

Compound subB-10 (10 g, 20.8 mmol), Compound amine70 (7.3 g, 21.9 mmol) and sodium tert-butoxide (2.6 g, 27.1 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-78. (Yield: 73%, MS: [M+H]⁺=779)

Synthesis Example 2-79

11H-benzo[a]carbazole (10 g, 46 mmol), 3-bromo-5-chloro-1,1′-biphenyl (12.9 g, 48.3 mmol) and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subB-11. (Yield: 73%, MS: [M+H]⁺=404)

Compound subB-11 (10 g, 24.8 mmol), Compound amine71 (9.7 g, 26 mmol) and sodium tert-butoxide (3.1 g, 32.2 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-79. (Yield: 73%, MS: [M+H]⁺=739)

Synthesis Example 2-80

11H-benzo[a]carbazole (10 g, 46 mmol), 3-bromo-4′-chloro-1,1′-biphenyl (12.9 g, 48.3 mmol) and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subB-12. (Yield: 72%, MS: [M+H]⁺=404)

Compound subB-12 (10 g, 24.8 mmol), Compound amine31 (11 g, 26 mmol) and sodium tert-butoxide (3.1 g, 32.2 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-80. (Yield: 62%, MS: [M+H]⁺=789)

Synthesis Example 2-81

11H-benzo[a]carbazole (10 g, 46 mmol), 5′-bromo-4-chloro-1,1′:3′,1″-terphenyl (16.6 g, 48.3 mmol) and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subB-13. (Yield: 69%, MS: [M+H]⁺=480)

Compound subB-13 (10 g, 20.8 mmol), Compound amine20 (7 g, 21.9 mmol) and sodium tert-butoxide (2.6 g, 27.1 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-81. (Yield: 70%, MS: [M+H]⁺=765)

Synthesis Example 2-82

11H-benzo[a]carbazole (10 g, 46 mmol), 3-bromo-4′-chloro-1,1′:2′,1″-terphenyl (16.6 g, 48.3 mmol) and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subB-14. (Yield: 62%, MS: [M+H]⁺=480)

Compound subB-14 (10 g, 20.8 mmol), Compound amine72 (7.6 g, 21.9 mmol) and sodium tert-butoxide (2.6 g, 27.1 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-82. (Yield: 70%, MS: [M+H]⁺=789)

Synthesis Example 2-83

11H-benzo[a]carbazole (10 g, 46 mmol), 3-bromo-4′-chloro-1,1′:3′,1″-terphenyl (16.6 g, 48.3 mmol) and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subB-15. (Yield: 75%, MS: [M+H]⁺=480)

Compound subB-15 (10 g, 20.8 mmol), Compound amine73 (8.7 g, 21.9 mmol) and sodium tert-butoxide (2.6 g, 27.1 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-83. (Yield: 69%, MS: [M+H]⁺=839)

Synthesis Example 2-84

11H-benzo[a]carbazole (10 g, 46 mmol), 3-bromo-3′-chloro-1,1′-biphenyl (12.9 g, 48.3 mmol) and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subB-16. (Yield: 65%, MS: [M+H]⁺=404)

Compound subB-16 (10 g, 24.8 mmol), Compound amine74 (9.7 g, 26 mmol) and sodium tert-butoxide (3.1 g, 32.2 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-84. (Yield: 67%, MS: [M+H]⁺=739)

Synthesis Example 2-85

11H-benzo[a]carbazole (10 g, 46 mmol), 4″-bromo-3′-chloro-1,1′:2′,1″-terphenyl (16.6 g, 48.3 mmol) and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.6 g of Compound subB-17. (Yield: 66%, MS: [M+H]⁺=480)

Compound subB-17 (10 g, 20.8 mmol), Compound amine75 (7 g, 21.9 mmol) and sodium tert-butoxide (2.6 g, 27.1 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-85. (Yield: 66%, MS: [M+H]⁺=815)

Synthesis Example 2-86

5H-benzo[b]carbazole (10 g, 46 mmol), 1-bromo-4-chlorobenzene (9.3 g, 48.3 mmol) and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subC-1. (Yield: 74%, MS: [M+H]⁺=328)

Compound subC-1 (10 g, 30.5 mmol), Compound amine95 (9.5 g, 32 mmol) and sodium tert-butoxide (3.8 g, 39.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-86. (Yield: 61%, MS: [M+H]⁺=587)

Synthesis Example 2-87

Compound subC-1 (10 g, 30.5 mmol), Compound amine55 (12.7 g, 32 mmol) and sodium tert-butoxide (3.8 g, 39.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-87. (Yield: 71%, MS: [M+H]⁺=689)

Synthesis Example 2-88

Compound subC-1 (10 g, 30.5 mmol), Compound amine76 (12.2 g, 32 mmol) and sodium tert-butoxide (3.8 g, 39.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-88. (Yield: 73%, MS: [M+H]⁺=973)

Synthesis Example 2-89

Compound subC-1 (10 g, 30.5 mmol), Compound amine77 (13.1 g, 32 mmol) and sodium tert-butoxide (3.8 g, 39.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-89. (Yield: 66%, MS: [M+H]⁺=702)

Synthesis Example 2-90

5H-benzo[b]carbazole (10 g, 46 mmol), 2-bromo-5-chloro-1,1′-biphenyl (12.9 g, 48.3 mmol) and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subC-2. (Yield: 61%, MS: [M+H]⁺=404)

Compound subC-2 (10 g, 24.8 mmol), Compound amine78 (10 g, 26 mmol) and sodium tert-butoxide (3.1 g, 32.2 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-90. (Yield: 60%, MS: [M+H]⁺=751)

Synthesis Example 2-91

Compound subC-2 (10 g, 24.8 mmol), Compound amine12 (8.4 g, 26 mmol amine78 (10 g, 26 mmol) and sodium tert-butoxide (3.1 g, 32.2 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-91. (Yield: 71%, MS: [M+H]⁺=689)

Synthesis Example 2-92

5H-benzo[b]carbazole (10 g, 46 mmol), 2-chloro-5-bromo-1,1′-biphenyl (12.9 g, 48.3 mmol) and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subC-3. (Yield: 61%, MS: [M+H]⁺=404)

Compound subC-3 (10 g, 24.8 mmol), Compound amine52 (6.4 g, 26 mmol) and sodium tert-butoxide (3.1 g, 32.2 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-92. (Yield: 68%, MS: [M+H]⁺=613)

Synthesis Example 2-93

5H-benzo[b]carbazole (10 g, 46 mmol), 4-bromo-4′-chloro-1,1′-biphenyl (12.9 g, 48.3 mmol) and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subC-4. (Yield: 66%, MS: [M+H]⁺=404)

Compound subC-4 (10 g, 24.8 mmol), Compound amine79 (6.4 g, 26 mmol) and sodium tert-butoxide (3.1 g, 32.2 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.5 g of Compound 2-93. (Yield: 63%, MS: [M+H]⁺=613)

Synthesis Example 2-94

Compound subC-4 (10 g, 24.8 mmol), Compound amine80 (8.7 g, 26 mmol) and sodium tert-butoxide (3.1 g, 32.2 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11 g of Compound 2-94. (Yield: 63%, MS: [M+H]⁺=703)

Synthesis Example 2-95

5H-benzo[b]carbazole (10 g, 46 mmol), 4′-bromo-4-chloro-1,1′:2′,1″-terphenyl (16.6 g, 48.3 mmol) and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subC-5. (Yield: 62%, MS: [M+H]⁺=480)

Compound subC-5 (10 g, 20.8 mmol), Compound amine40 (7 g, 21.9 mmol) and sodium tert-butoxide (2.6 g, 27.1 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10 g of Compound 2-95. (Yield: 64%, MS: [M+H]⁺=751)

Synthesis Example 2-96

5H-benzo[b]carbazole (10 g, 46 mmol), 1-bromo-4-(4-chlorophenyl) naphthalene (15.3 g, 48.3 mmol) and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.4 g of Compound subC-6. (Yield: 74%, MS: [M+H]⁺=454)

Compound subC-6 (10 g, 22 mmol), Compound amine81 (8.6 g, 23.1 mmol) and sodium tert-butoxide (2.8 g, 28.6 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-96. (Yield: 68%, MS: [M+H]⁺=789)

Synthesis Example 2-97

5H-benzo[b]carbazole (10 g, 46 mmol), 1-bromo-3-chlorobenzene (9.3 g, 48.3 mmol) and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9 g of Compound subC-7. (Yield: 60%, MS: [M+H]⁺=328)

Compound subC-7 (10 g, 30.5 mmol), Compound amine82 (11.9 g, 32 mmol) and sodium tert-butoxide (3.8 g, 39.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-97. (Yield: 71%, MS: [M+H]⁺=663)

Synthesis Example 2-98

5H-benzo[b]carbazole (10 g, 46 mmol), 3-bromo-4′-chloro-1,1′-biphenyl (12.9 g, 48.3 mmol) and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare

11.7 g of Compound subC-8. (Yield: 63%, MS: [M+H]⁺=405) Compound subC-8 (10 g, 24.8 mmol), Compound amine40 (8.4 g, 26 mmol) and sodium tert-butoxide (3.1 g, 32.2 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-98. (Yield: 66%, MS: [M+H]⁺=689)

Synthesis Example 2-99

Compound subC-8 (10 g, 24.8 mmol), Compound amine36 (8.7 g, 26 mmol) and sodium tert-butoxide (3.1 g, 32.2 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-99. (Yield: 60%, MS: [M+H]⁺=703)

Synthesis Example 2-100

5H-benzo[b]carbazole (10 g, 46 mmol), 5′-bromo-4-chloro-1,1′:2′,1″-terphenyl (16.6 g, 48.3 mmol) and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.6 g of Compound subC-9. (Yield: 66%, MS: [M+H]⁺=480)

Compound subC-9 (10 g, 20.8 mmol), Compound amine12 (7 g, 21.9 mmol) and sodium tert-butoxide (2.6 g, 27.1 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-100. (Yield: 71%, MS: [M+H]⁺=765)

Synthesis Example 2-101

5H-benzo[b]carbazole (10 g, 46 mmol), 2-bromo-4′-chloro-1,1′-biphenyl (12.9 g, 48.3 mmol) and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subC-10. (Yield: 64%, MS: [M+H]⁺=404)

Compound subC-10 (10 g, 24.8 mmol), Compound amine35 (9.7 g, 26 mmol) and sodium tert-butoxide (3.1 g, 32.2 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-101. (Yield: 66%, MS: [M+H]⁺=739)

Synthesis Example 2-102

5H-benzo[b]carbazole (10 g, 46 mmol), 2-bromo-4′-chloro-1,1′:3′,1″-terphenyl (16.6 g, 48.3 mmol) and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 f Compound subC-11. (Yield: 63%, MS: [M+H]⁺=480)

Compound subC-11 (10 g, 20.8 mmol), Compound amine55 (8.6 g, 21.9 mmol) and sodium tert-butoxide (2.6 g, 27.1 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-102. (Yield: 64%, MS: [M+H]⁺=841)

Synthesis Example 2-103

5H-benzo[b]carbazole (10 g, 46 mmol), 2-bromo-4′-chloro-1,1′:2′,1″-terphenyl (16.6 g, 48.3 mmol) and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subC-12. (Yield: 69%, MS: [M+H]⁺=480)

Compound subC-12 (10 g, 20.8 mmol), Compound amine83 (6.5 g, 21.9 mmol) and sodium tert-butoxide (2.6 g, 27.1 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.4 g of Compound 2-103. (Yield: 74%, MS: [M+H]⁺=739)

Synthesis Example 2-104

5H-benzo[b]carbazole (10 g, 46 mmol), 2′-bromo-4-chloro-1,1′:4′,1″-terphenyl (16.6 g, 48.3 mmol) and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.6 g of Compound subC-13. (Yield: 66%, MS: [M+H]⁺=480)

Compound subC-13 (10 g, 20.8 mmol), Compound amine13 (7.6 g, 21.9 mmol) and sodium tert-butoxide (2.6 g, 27.1 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-104. (Yield: 66%, MS: [M+H]⁺=793)

Synthesis Example 2-105

5H-benzo[b]carbazole (10 g, 46 mmol), 3′-bromo-2-chloro-1,1′-biphenyl (12.9 g, 48.3 mmol) and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subC-14. (Yield: 75%, MS: [M+H]⁺=405)

Compound subC-14 (10 g, 24.8 mmol), Compound amine74 (9.7 g, 26 mmol) and sodium tert-butoxide (3.1 g, 32.2 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-105. (Yield: 72%, MS: [M+H]⁺=739)

Synthesis Example 2-106

5H-benzo[b]carbazole (10 g, 46 mmol), 2′-bromo-2-chloro-1,1′:3′,1″-terphenyl (16.6 g, 48.3 mmol) and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subC-15. (Yield: 64%, MS: [M+H]⁺=480)

Compound subC-15 (10 g, 20.8 mmol), Compound amine63 (8.1 g, 21.9 mmol) and sodium tert-butoxide (2.6 g, 27.1 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11 g of Compound 2-106. (Yield: 65%, MS: [M+H]⁺=815)

Synthesis Example 2-107

7H-benzo[c]carbazole (10 g, 46 mmol), 1-bromo-4-chlorobenzene (9.3 g, 48.3 mmol) and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.8 g of Compound subD-1. (Yield: 72%, MS: [M+H]⁺=328)

Compound subD-1 (10 g, 30.5 mmol), Compound amine63 (11.9 g, 32 mmol) and sodium tert-butoxide (3.8 g, 39.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-107. (Yield: 72%, MS: [M+H]⁺=663)

Synthesis Example 2-108

Compound subD-1 (10 g, 30.5 mmol), Compound amine84 (12.9 g, 32 mmol) and sodium tert-butoxide (3.8 g, 39.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.4 g of Compound 2-108. (Yield: 73%, MS: [M+H]⁺=693)

Synthesis Example 2-109

7H-benzo[c]carbazole (10 g, 46 mmol), 1-(4-bromophenyl)-4-chloronaphthalene (15.3 g, 48.3 mmol) and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subD-2. (Yield: 71%, MS: [M+H]⁺=454)

Compound subD-2 (10 g, 22 mmol), Compound amine85 (8.6 g, 23.1 mmol) and sodium tert-butoxide (2.8 g, 28.6 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.8 g of Compound 2-109. (Yield: 62%, MS: [M+H]⁺=789)

Synthesis Example 2-110

7H-benzo[c]carbazole (10 g, 46 mmol), 1-bromo-4-chloronaphthalene (11.7 g, 48.3 mmol) and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subD-3. (Yield: 71%, MS: [M+H]⁺=378)

Compound subD-3 (10 g, 26.5 mmol), Compound amine86 (12.4 g, 27.8 mmol) and sodium tert-butoxide (3.3 g, 34.4 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.6 g of Compound 2-110. (Yield: 70%, MS: [M+H]⁺=789)

Synthesis Example 2-111

7H-benzo[c]carbazole (10 g, 46 mmol), 4-bromo-4′-chloro-1,1′-biphenyl (12.9 g, 48.3 mmol) and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subD-4. (Yield: 74%, MS: [M+H]⁺=404)

Compound subD-4 (10 g, 24.8 mmol), Compound amine87 (7.7 g, 26 mmol) and sodium tert-butoxide (3.1 g, 32.2 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-111. (Yield: 72%, MS: [M+H]⁺=663)

Synthesis Example 2-112

Compound subD-4 (10 g, 24.8 mmol), Compound amine44 (8.4 g, 26 mmol) and sodium tert-butoxide (3.1 g, 32.2 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-112. (Yield: 75%, MS: [M+H]⁺=689)

Synthesis Example 2-113

Compound subD-4 (10 g, 24.8 mmol), Compound amine88 (6.7 g, 26 mmol) and sodium tert-butoxide (3.1 g, 32.2 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.1 g of Compound 2-113. (Yield: 65%, MS: [M+H]⁺=627)

Synthesis Example 2-114

Compound subD-4 (10 g, 24.8 mmol), Compound amine89 (8.7 g, 26 mmol) and sodium tert-butoxide (3.1 g, 32.2 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-114. (Yield: 65%, MS: [M+H]⁺=702)

Synthesis Example 2-115

7H-benzo[c]carbazole (10 g, 46 mmol), 4-bromo-4′-chloro-1,1′:2′,1″-terphenyl (16.6 g, 48.3 mmol) and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subD-5. (Yield: 71%, MS: [M+H]⁺=480)

Compound subD-5 (10 g, 20.8 mmol), Compound amine90 (7 g, 21.9 mmol) and sodium tert-butoxide (2.6 g, 27.1 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-115. (Yield: 70%, MS: [M+H]⁺=765)

Synthesis Example 2-116

7H-benzo[c]carbazole (10 g, 46 mmol), 4′-bromo-4-chloro-1,1′:3′,1″-terphenyl (16.6 g, 48.3 mmol) and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subD-6. (Yield: 73%, MS: [M+H]⁺=480)

Compound subD-6 (10 g, 20.8 mmol), Compound amine91 (8.1 g, 21.9 mmol) and sodium tert-butoxide (2.6 g, 27.1 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-116. (Yield: 64%, MS: [M+H]⁺=815)

Synthesis Example 2-117

7H-benzo[c]carbazole (10 g, 46 mmol), 2-bromo-4′-chloro-1,1′-biphenyl (12.9 g, 48.3 mmol) and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subD-7. (Yield: 72%, MS: [M+H]⁺=404)

Compound subD-7 (10 g, 24.8 mmol), Compound amine96 (10.3 g, 26 mmol) and sodium tert-butoxide (3.1 g, 32.2 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-117. (Yield: 72%, MS: [M+H]⁺=765)

Synthesis Example 2-118

Compound subD-7 (10 g, 24.8 mmol), Compound amine92 (9.1 g, 26 mmol) and sodium tert-butoxide (3.1 g, 32.2 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-118. (Yield: 68%, MS: [M+H]⁺=719)

Synthesis Example 2-119

7H-benzo[c]carbazole (10 g, 46 mmol), 2-bromo-4′-chloro-1,1′:2′,1″-terphenyl (16.6 g, 48.3 mmol) and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.3 g f Compound subD-8. (Yield: 74%, MS: [M+H]⁺=480)

Compound subD-8 (10 g, 20.8 mmol), Compound amine93 (7 g, 21.9 mmol) and sodium tert-butoxide (2.6 g, 27.1 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.5 g of Compound 2-119. (Yield: 66%, MS: [M+H]⁺=765)

Synthesis Example 2-120

7H-benzo[c]carbazole (10 g, 46 mmol), 3′-bromo-4″-chloro-1,1′:2′,1″-terphenyl (16.6 g, 48.3 mmol) and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.4 g of Compound subD-9. (Yield: 70%, MS: [M+H]⁺=480)

Compound subD-9 (10 g, 20.8 mmol), Compound amine34 (9.2 g, 21.9 mmol) and sodium tert-butoxide (2.6 g, 27.1 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-120. (Yield: 66%, MS: [M+H]⁺=865)

Synthesis Example 2-121

7H-benzo[c]carbazole (10 g, 46 mmol), 2′-bromo-4-chloro-1,1′:3′,1″-terphenyl (16.6 g, 48.3 mmol) and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.4 g of Compound subD-10. (Yield: 70%, MS: [M+H]⁺=480)

Compound subD-10 (10 g, 20.8 mmol), Compound amine91 (8.1 g, 21.9 mmol) and sodium tert-butoxide (2.6 g, 27.1 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-121. (Yield: 70%, MS: [M+H]⁺=815)

Synthesis Example 2-122

7H-benzo[c]carbazole (10 g, 46 mmol), 6′-bromo-4-chloro-1,1′:3′,1″-terphenyl (16.6 g, 48.3 mmol) and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.4 g of Compound subD-11. (Yield: 70%, MS: [M+H]⁺=480)

Compound subD-11 (10 g, 20.8 mmol), Compound amine91 (8.1 g, 21.9 mmol) and sodium tert-butoxide (2.6 g, 27.1 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-122. (Yield: 74%, MS: [M+H]⁺=815)

Synthesis Example 2-123

7H-benzo[c]carbazole (10 g, 46 mmol), 1-bromo-3-chlorobenzene (9.3 g, 48.3 mmol) and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.7 g of Compound subD-12. (Yield: 71%, MS: [M+H]⁺=328)

Compound subD-12 (10 g, 30.5 mmol), Compound amine97 (11.9 g, 32 mmol) and sodium tert-butoxide (3.8 g, 39.7 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-123. (Yield: 67%, MS: [M+H]⁺=663)

Synthesis Example 2-124

7H-benzo[c]carbazole (10 g, 46 mmol), 2-bromo-3′-chloro-1,1′-biphenyl (12.9 g, 48.3 mmol) and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 go f Compound subD-13. (Yield: 68%, MS: [M+H]⁺=404)

Compound subD-13 (10 g, 24.8 mmol), Compound amine43 (10.3 g, 26 mmol) and sodium tert-butoxide (3.1 g, 32.2 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-124. (Yield: 70%, MS: [M+H]⁺=763)

Synthesis Example 2-125

Compound subD-13 (10 g, 24.8 mmol), Compound amine44 (8.4 g, 26 mmol) and sodium tert-butoxide (3.1 g, 32.2 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.4 g of Compound 2-125. (Yield: 67%, MS: [M+H]⁺=689)

Synthesis Example 2-126

7H-benzo[c]carbazole (10 g, 46 mmol), 6′-bromo-3-chloro-1,1′:3′,1″-terphenyl (16.6 g, 48.3 mmol) and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subD-14. (Yield: 65%, MS: [M+H]⁺=480)

Compound subD-14 (10 g, 20.8 mmol), Compound amine44 (7 g, 21.9 mmol) and sodium tert-butoxide (2.6 g, 27.1 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.2 g of Compound 2-126. (Yield: 64%, MS: [M+H]⁺=765)

Synthesis Example 2-127

7H-benzo[c]carbazole (10 g, 46 mmol), 2′-bromo-3″-chloro-1,1′:4′,1″-terphenyl (16.6 g, 48.3 mmol) and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subD-15. (Yield: 72%, MS: [M+H]⁺=480)

Compound subD-15 (10 g, 20.8 mmol), Compound amine98 (10.3 g, 21.9 mmol) and sodium tert-butoxide (2.6 g, 27.1 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.1 g of Compound 2-127. (Yield: 69%, MS: [M+H]⁺=915)

Synthesis Example 2-128

7H-benzo[c]carbazole (10 g, 46 mmol), 2-bromo-2′-chloro-1,1′-biphenyl (12.9 g, 48.3 mmol) and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.7 g of Compound subD-16. (Yield: 63%, MS: [M+H]⁺=404)

Compound subD-16 (10 g, 24.8 mmol), Compound amine96 (10.3 g, 26 mmol) and sodium tert-butoxide (3.1 g, 32.2 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-128. (Yield: 74%, MS: [M+H]⁺=765)

Synthesis Example 2-129

7H-benzo[c]carbazole (10 g, 46 mmol), 3′-bromo-2-chloro-1,1′-biphenyl (12.9 g, 48.3 mmol) and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subD-17. (Yield: 70%, MS: [M+H]⁺=404)

Compound subD-17 (10 g, 24.8 mmol), Compound amine45 (11.6 g, 26 mmol) and sodium tert-butoxide (3.1 g, 32.2 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-129. (Yield: 69%, MS: [M+H]⁺=815)

Synthesis Example 2-130

7H-benzo[c]carbazole (10 g, 46 mmol), 4′-bromo-2-chloro-1,1′-biphenyl (12.9 g, 48.3 mmol) and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added thereto. When the reaction was completed after 3 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 subD-18. (Yield: 66%, MS: [M+H]⁺=404)

Compound subD-18 (10 g, 24.8 mmol), Compound amine94 (10.3 g, 26 mmol) and sodium tert-butoxide (3.1 g, 32.2 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 2 hours, the reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the compound was again completely dissolved in chloroform, washed twice with water, and then the organic layer was separated, treated with anhydrous magnesium sulfate 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 2-130. (Yield: 61%, MS: [M+H]⁺=765)

Example 1

A glass substrate on which a thin film of ITO (indium tin oxide) was coated in a thickness of 1000 Å was put into distilled water containing the detergent dissolved therein and washed by the ultrasonic wave. In this case, the used detergent was a product commercially available from Fisher Co. and the distilled water was one which had been twice filtered by using a filter commercially available from Millipore Co. The ITO was washed for 30 minutes, and ultrasonic washing was then repeated twice for 10 minutes by using distilled water. After the washing with distilled water was completed, the substrate was ultrasonically washed with isopropyl alcohol, acetone, and methanol solvent, and dried, after which it was transported to a plasma cleaner. Then, the substrate was cleaned with oxygen plasma for 5 minutes, and then transferred to a vacuum evaporator.

On the ITO transparent electrode thus prepared, the following Compound HI-1 was formed in a thickness of 1150 Å as a hole injection layer, but the following Compound A-1 was p-doped at a concentration of 1.5 wt. %. The following Compound HT-1 was vacuum deposited on the hole injection layer to form a hole transport layer with a film thickness of 800 Å. Then, 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. Then, the previously prepared Compound 1-1, Compound 2-1, and the following Compound Dp-7 were vacuum-deposited in a weight ratio of 49:49:2 on the EB-1 deposited film to form a red light emitting layer with a film 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. Then, the following Compound ET-1 and the following Compound LiQ were vacuum deposited in a weight ratio of 2:1 on the hole blocking layer to form an electron injection and transport layer with a film thickness of 300 Å. Lithium fluoride (LiF) and aluminum were sequentially deposited to have a thickness of 12 Å and 1,000 Å, respectively, on the electron injection and transport layer, thereby forming a cathode.

In the above-mentioned processes, the deposition rates of the organic materials were maintained at 0.4˜0.7 Å/sec, the deposition rates of lithium fluoride and the aluminum of the cathode were maintained at 0.3 Å/sec and 2 Å/sec, respectively, and the degree of vacuum during the deposition was maintained at 2×10⁻⁷˜5×10⁻⁶ torr, thereby manufacturing an organic light emitting device.

Examples 2 to 340

An organic light emitting device was manufactured in the same manner as in Example 1, except that in the organic light emitting device of Example 1, the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 shown in Table 1 below were co-deposited and used in a weight ratio of 1:1 instead of Compound 1-1 and Compound 2-1 as the first host and second host.

Comparative Examples 1 to 60

An organic light emitting device was manufactured in the same manner as in Example 1, except that in the organic light emitting device of Example 1, the following Comparative Compounds A-1 to A-12 were used instead of Compound 1-1 as the first host and the compound represented by Chemical Formula 2 shown in Table 2 below was used instead of Compound 2-1 as a second host, wherein these two host compounds were co-deposited and used in a weight ratio of 1:1. The specific structures of the Compounds A-1 to A-12 are as follows.

Comparative Examples 61 to 156

An organic light emitting device was manufactured in the same manner as in Example 1, except that in the organic light emitting device of Example 1, the compound represented by Chemical Formula 1 shown in Table 3 below was used instead of Compound 1-1 as the first host, and the following comparative compounds B-1 to B-12 were used instead of Compound 2-1 as the second host, wherein these two host compounds were co-deposited and used in a weight ratio of 1:1. The specific structures of the Compounds B-1 to B-12 are as follows.

Experimental Example

The voltage and efficiency were measured (based on 15 mA/cm²) by applying a current to the organic light emitting devices manufactured in Examples 1 to 340 and Comparative Examples 1 to 156, and the results are shown in Tables 1 to 3 below. The lifetime (T95) was measured based on 7000 nit, and T95 means the time required for the luminance to be reduced to 95% of the initial luminance.

TABLE 1
	The	The			Lifetime	Lumi-
	First	Second	Voltage	Efficiency	T95	nescent
Division	Host	Host	(V)	(cd/A)	(hr)	Color
Example	Compound	Compound	3.74	20.22	207	Red
1	1-1	2-1
Example		Compound	3.76	20.31	207	Red
2		2-27
Example		Compound	3.69	20.34	193	Red
3		2-53
Example		Compound	3.76	20.88	200	Red
4		2-79
Example		Compound	3.74	20.99	207	Red
5		2-105
Example	Compound	Compound	3.71	21.08	190	Red
6	1-2	2-2
Example		Compound	3.71	21.03	201	Red
7		2-28
Example		Compound	3.71	21.12	192	Red
8		2-54
Example		Compound	3.68	20.06	205	Red
9		2-80
Example		Compound	3.72	21.32	206	Red
10		2-106
Example	Compound	Compound	3.45	22.88	237	Red
11	1-3	2-3
Example		Compound	3.45	22.73	241	Red
12		2-29
Example		Compound	3.49	22.73	225	Red
13		2-55
Example		Compound	3.48	22.83	231	Red
14		2-81
Example		Compound	3.51	22.89	233	Red
15		2-107
Example	Compound	Compound	3.47	22.82	223	Red
16	1-4	2-4
Example		Compound	3.53	22.83	251	Red
17		2-30
Example		Compound	3.53	22.56	240	Red
18		2-56
Example		Compound	3.54	22.74	237	Red
19		2-82
Example		Compound	3.52	22.90	250	Red
20		2-108
Example	Compound	Compound	3.60	22.88	237	Red
21	1-5	2-5
Example		Compound	3.53	11.92	241	Red
22		2-31
Example		Compound	3.58	17.20	225	Red
23		2-57
Example		Compound	3.57	12.19	231	Red
24		2-83
Example		Compound	3.56	22.69	233	Red
25		2-109
Example	Compound	Compound	3.53	18.83	223	Red
26	1-6	2-6
Example		Compound	3.57	19.61	251	Red
27		2-32
Example		Compound	3.53	14.53	240	Red
28		2-58
Example		Compound	3.59	21.64	237	Red
29		2-84
Example		Compound	3.58	21.76	250	Red
30		2-110
Example	Compound	Compound	3.53	22.69	270	Red
31	1-7	2-7
Example		Compound	3.46	22.88	256	Red
32		2-33
Example		Compound	3.50	22.70	255	Red
33		2-59
Example		Compound	3.47	22.69	247	Red
34		2-85
Example		Compound	3.48	22.63	261	Red
35		2-111
Example	Compound	Compound	3.54	22.78	258	Red
36	1-8	2-8
Example		Compound	3.49	22.64	261	Red
37		2-34
Example		Compound	3.48	22.74	255	Red
38		2-60
Example		Compound	3.47	22.66	251	Red
39		2-86
Example		Compound	3.49	22.52	247	Red
40		2-112
Example	Compound	Compound	3.53	23.45	270	Red
41	1-9	2-9
Example		Compound	3.46	23.03	256	Red
42		2-35
Example		Compound	3.50	23.14	255	Red
43		2-61
Example		Compound	3.47	23.36	247	Red
44		2-87
Example		Compound	3.48	23.69	261	Red
45		2-113
Example	Compound	Compound	3.49	23.99	308	Red
46	1-10	2-10
Example		Compound	3.45	23.63	300	Red
47		2-36
Example		Compound	3.46	22.80	291	Red
48		2-62
Example		Compound	3.46	23.29	306	Red
49		2-88
Example		Compound	3.46	23.47	300	Red
50		2-114
Example	Compound	Compound	3.45	23.43	284	Red
51	1-11	2-11
Example		Compound	3.47	23.51	291	Red
52		2-37
Example		Compound	3.51	23.66	284	Red
53		2-63
Example		Compound	3.47	23.07	292	Red
54		2-89
Example		Compound	3.53	23.15	288	Red
55		2-115
Example	Compound	Compound	3.54	22.78	234	Red
56	1-12	2-12
Example		Compound	3.49	22.64	242	Red
57		2-38
Example		Compound	3.48	22.74	248	Red
58		2-64
Example		Compound	3.47	22.66	229	Red
59		2-90
Example		Compound	3.49	22.52	224	Red
60		2-116
Example	Compound	Compound	3.61	22.69	225	Red
61	1-13	2-13
Example		Compound	3.61	17.18	230	Red
62		2-39
Example		Compound	3.54	17.66	248	Red
63		2-65
Example		Compound	3.58	17.46	223	Red
64		2-91
Example		Compound	3.53	20.20	248	Red
65		2-117
Example	Compound	Compound	3.53	22.06	234	Red
66	1-14	2-14
Example		Compound	3.61	20.95	242	Red
67		2-40
Example		Compound	3.56	22.11	248	Red
68		2-66
Example		Compound	3.55	14.61	229	Red
69		2-92
Example		Compound	3.52	16.10	224	Red
70		2-118
Example	Compound	Compound	3.71	20.37	192	Red
71	1-15	2-15
Example		Compound	3.71	20.68	204	Red
72		2-41
Example		Compound	3.70	20.61	197	Red
73		2-67
Example		Compound	3.73	21.08	195	Red
74		2-93
Example		Compound	3.76	21.44	207	Red
75		2-119
Example	Compound	Compound	3.64	14.88	227	Red
76	1-16	2-16
Example		Compound	3.59	18.01	218	Red
77		2-42
Example		Compound	3.60	12.80	220	Red
78		2-68
Example		Compound	3.63	22.54	227	Red
79		2-94
Example		Compound	3.65	18.15	227	Red
80		2-120
Example	Compound	Compound	3.62	20.02	225	Red
81	1-17	2-17
Example		Compound	3.67	12.71	224	Red
82		2-43
Example		Compound	3.66	18.04	226	Red
83		2-69
Example		Compound	3.61	22.28	221	Red
84		2-95
Example		Compound	3.65	15.15	219	Red
85		2-121
Example	Compound	Compound	3.54	22.56	244	Red
86	1-18	2-18
Example		Compound	3.46	22.79	235	Red
87		2-44
Example		Compound	3.45	22.66	241	Red
88		2-70
Example		Compound	3.54	22.52	250	Red
89		2-96
Example		Compound	3.54	22.51	237	Red
90		2-122
Example	Compound	Compound	3.50	22.65	235	Red
91	1-19	2-19
Example		Compound	3.53	22.85	234	Red
92		2-45
Example		Compound	3.53	22.89	237	Red
93		2-71
Example		Compound	3.48	22.71	242	Red
94		2-97
Example		Compound	3.53	22.67	247	Red
95		2-123
Example	Compound	Compound	3.58	22.56	244	Red
96	1-20	2-20
Example		Compound	3.56	18.01	235	Red
97		2-46
Example		Compound	3.54	12.80	241	Red
98		2-72
Example		Compound	3.53	22.54	250	Red
99		2-98
Example		Compound	3.52	18.15	237	Red
100		2-124
Example	Compound	Compound	3.60	20.02	235	Red
101	1-21	2-21
Example		Compound	3.57	12.71	234	Red
102		2-47
Example		Compound	3.56	18.04	237	Red
103		2-73
Example		Compound	3.54	22.28	242	Red
104		2-99
Example		Compound	3.58	15.15	247	Red
105		2-125
Example	Compound	Compound	3.49	22.61	237	Red
106	1-22	2-22
Example		Compound	3.51	22.68	244	Red
107		2-48
Example		Compound	3.51	22.81	226	Red
108		2-74
Example		Compound	3.47	22.63	224	Red
109		2-100
Example		Compound	3.46	22.52	223	Red
110		2-126
Example	Compound	Compound	3.51	22.55	246	Red
111	1-23	2-23
Example		Compound	3.46	22.78	230	Red
112		2-49
Example		Compound	3.53	22.69	251	Red
113		2-75
Example		Compound	3.51	22.78	248	Red
114		2-101
Example		Compound	3.46	22.68	243	Red
115		2-127
Example	Compound	Compound	3.49	23.86	272	Red
116	1-24	2-24
Example		Compound	3.51	23.39	247	Red
117		2-50
Example		Compound	3.51	22.90	267	Red
118		2-76
Example		Compound	3.47	23.02	267	Red
119		2-102
Example		Compound	3.46	23.02	252	Red
120		2-128
Example	Compound	Compound	3.54	22.81	312	Red
121	1-25	2-25
Example		Compound	3.46	23.36	290	Red
122		2-51
Example		Compound	3.45	23.36	313	Red
123		2-77
Example		Compound	3.48	23.36	308	Red
124		2-103
Example		Compound	3.52	23.63	318	Red
125		2-129
Example	Compound	Compound	3.50	23.38	315	Red
126	1-26	2-26
Example		Compound	3.54	23.19	284	Red
127		2-52
Example		Compound	3.54	22.88	297	Red
128		2-78
Example		Compound	3.49	23.44	320	Red
129		2-104
Example		Compound	3.52	22.85	311	Red
130		2-130
Example	Compound	Compound	3.54	22.89	284	Red
131	1-27	2-21
Example		Compound	3.53	22.51	286	Red
132		2-49
Example		Compound	3.51	22.86	303	Red
133		2-73
Example		Compound	3.48	22.86	284	Red
134		2-102
Example		Compound	3.54	22.75	317	Red
135		2-130
Example	Compound	Compound	3.63	20.16	216	Red
136	1-28	2-1
Example		Compound	3.65	15.13	213	Red
137		2-27
Example		Compound	3.59	19.04	214	Red
138		2-53
Example		Compound	3.64	11.67	219	Red
139		2-79
Example		Compound	3.61	20.90	214	Red
140		2-105
Example	Compound	Compound	3.50	22.65	240	Red
141	1-29	2-2
Example		Compound	3.54	22.60	250	Red
142		2-28
Example		Compound	3.49	22.53	229	Red
143		2-54
Example		Compound	3.48	22.59	238	Red
144		2-80
Example		Compound	3.50	22.88	233	Red
145		2-106
Example	Compound	Compound	3.53	22.54	230	Red
146	1-30	2-3
Example		Compound	3.51	22.64	231	Red
147		2-29
Example		Compound	3.46	22.56	228	Red
148		2-55
Example		Compound	3.49	22.89	227	Red
149		2-81
Example		Compound	3.50	22.72	243	Red
150		2-107
Example	Compound	Compound	3.61	22.65	240	Red
151	1-31	2-4
Example		Compound	3.60	22.17	250	Red
152		2-30
Example		Compound	3.54	15.76	229	Red
153		2-56
Example		Compound	3.55	16.14	238	Red
154		2-82
Example		Compound	3.58	14.83	233	Red
155		2-108
Example	Compound	Compound	3.52	20.16	230	Red
156	1-32	2-5
Example		Compound	3.56	15.13	231	Red
157		2-31
Example		Compound	3.58	19.04	228	Red
158		2-57
Example		Compound	3.58	11.67	227	Red
159		2-83
Example		Compound	3.56	20.90	243	Red
160		2-109
Example	Compound	Compound	3.57	22.76	229	Red
161	1-33	2-6
Example		Compound	3.56	20.69	242	Red
162		2-32
Example		Compound	3.58	14.71	232	Red
163		2-58
Example		Compound	3.52	15.56	232	Red
164		2-84
Example		Compound	3.52	19.56	245	Red
165		2-110
Example	Compound	Compound	3.52	22.83	318	Red
166	1-34	2-7
Example		Compound	3.46	23.64	287	Red
167		2-33
Example		Compound	3.52	23.12	297	Red
168		2-59
Example		Compound	3.45	23.67	281	Red
169		2-85
Example		Compound	3.49	23.23	298	Red
170		2-111
Example	Compound	Compound	3.49	22.94	295	Red
171	1-35	2-8
Example		Compound	3.45	23.02	289	Red
172		2-34
Example		Compound	3.51	23.04	311	Red
173		2-60
Example		Compound	3.53	22.80	304	Red
174		2-86
Example		Compound	3.53	23.24	288	Red
175		2-112
Example	Compound	Compound	3.47	22.85	293	Red
176	1-36	2-9
Example		Compound	3.46	22.78	309	Red
177		2-35
Example		Compound	3.52	22.74	315	Red
178		2-61
Example		Compound	3.49	22.78	318	Red
179		2-87
Example		Compound	3.49	22.77	309	Red
180		2-113
Example	Compound	Compound	3.53	22.58	233	Red
181	1-37	2-10
Example		Compound	3.54	22.51	251	Red
182		2-36
Example		Compound	3.51	22.60	236	Red
183		2-62
Example		Compound	3.45	22.87	246	Red
184		2-88
Example		Compound	3.45	22.66	228	Red
185		2-114
Example	Compound	Compound	3.49	22.64	289	Red
186	1-38	2-11
Example		Compound	3.49	22.63	299	Red
187		2-37
Example		Compound	3.53	22.52	305	Red
188		2-63
Example		Compound	3.47	22.80	291	Red
189		2-89
Example		Compound	3.50	22.74	285	Red
190		2-115
Example	Compound	Compound	3.55	22.58	233	Red
191	1-39	2-12
Example		Compound	3.56	21.83	251	Red
192		2-38
Example		Compound	3.61	21.20	236	Red
193		2-64
Example		Compound	3.58	16.40	246	Red
194		2-90
Example		Compound	3.55	14.51	228	Red
195		2-116
Example	Compound	Compound	3.54	15.42	240	Red
196	1-40	2-13
Example		Compound	3.55	19.92	244	Red
197		2-39
Example		Compound	3.57	16.08	231	Red
198		2-65
Example		Compound	3.60	20.30	223	Red
199		2-91
Example		Compound	3.54	21.28	248	Red
200		2-117
Example	Compound	Compound	3.66	20.31	226	Red
201	1-41	2-14
Example		Compound	3.64	21.83	211	Red
202		2-40
Example		Compound	3.61	21.20	218	Red
203		2-66
Example		Compound	3.67	16.40	221	Red
204		2-92
Example		Compound	3.67	14.51	218	Red
205		2-118
Example	Compound	Compound	3.64	15.42	228	Red
206	1-42	2-15
Example		Compound	3.64	19.92	219	Red
207		2-41
Example		Compound	3.65	16.08	221	Red
208		2-67
Example		Compound	3.59	20.30	224	Red
209		2-93
Example		Compound	3.65	21.28	223	Red
210		2-119
Example	Compound	Compound	3.52	22.78	286	Red
211	1-43	2-16
Example		Compound	3.54	22.61	312	Red
212		2-42
Example		Compound	3.51	22.54	284	Red
213		2-68
Example		Compound	3.52	22.67	317	Red
214		2-94
Example		Compound	3.48	22.89	319	Red
215		2-120
Example	Compound	Compound	3.66	20.31	226	Red
216	1-44	2-17
Example		Compound	3.64	21.83	211	Red
217		2-43
Example		Compound	3.61	21.20	218	Red
218		2-69
Example		Compound	3.67	16.40	221	Red
219		2-95
Example		Compound	3.67	14.51	218	Red
220		2-121
Example	Compound	Compound	3.64	15.42	228	Red
221	1-45	2-18
Example		Compound	3.64	19.92	219	Red
222		2-44
Example		Compound	3.65	16.08	221	Red
223		2-70
Example		Compound	3.59	20.30	224	Red
224		2-96
Example		Compound	3.65	21.28	223	Red
225		2-122
Example	Compound	Compound	3.70	20.13	197	Red
226	1-46	2-19
Example		Compound	3.76	21.45	198	Red
227		2-45
Example		Compound	3.73	20.08	197	Red
228		2-71
Example		Compound	3.72	21.05	207	Red
229		2-97
Example		Compound	3.71	20.26	192	Red
230		2-123
Example	Compound	Compound	3.72	21.19	197	Red
231	1-47	2-20
Example		Compound	3.66	21.04	207	Red
232		2-46
Example		Compound	3.69	21.10	208	Red
233		2-72
Example		Compound	3.68	21.03	197	Red
234		2-98
Example		Compound	3.74	21.21	201	Red
235		2-124
Example	Compound	Compound	3.72	21.24	198	Red
236	1-48	2-1
Example		Compound	3.74	20.24	202	Red
237		2-17
Example		Compound	3.72	21.41	192	Red
238		2-43
Example		Compound	3.74	20.29	201	Red
239		2-89
Example		Compound	3.77	21.50	208	Red
240		2-105
Example	Compound	Compound	3.72	20.43	192	Red
241	1-49	2-2
Example		Compound	3.72	20.03	204	Red
242		2-28
Example		Compound	3.66	20.48	201	Red
243		2-44
Example		Compound	3.71	20.14	206	Red
244		2-70
Example		Compound	3.78	20.56	198	Red
245		2-106
Example	Compound	Compound	3.60	22.65	225	Red
246	1-50	2-3
Example		Compound	3.56	19.31	238	Red
247		2-29
Example		Compound	3.58	19.06	237	Red
248		2-65
Example		Compound	3.52	19.20	230	Red
249		2-81
Example		Compound	3.57	13.34	237	Red
250		2-107
Example	Compound	Compound	3.62	21.52	216	Red
251	1-51	2-4
Example		Compound	3.62	14.88	226	Red
252		2-30
Example		Compound	3.61	21.55	219	Red
253		2-56
Example		Compound	3.67	13.81	212	Red
254		2-82
Example		Compound	3.63	15.26	217	Red
255		2-108
Example	Compound	Compound	3.60	18.19	226	Red
256	1-52	2-5
Example		Compound	3.63	21.79	219	Red
257		2-31
Example		Compound	3.63	11.73	219	Red
258		2-57
Example		Compound	3.65	13.94	223	Red
259		2-83
Example		Compound	3.66	14.70	220	Red
260		2-109
Example	Compound	Compound	3.51	22.71	239	Red
261	1-53	2-6
Example		Compound	3.53	22.87	233	Red
262		2-32
Example		Compound	3.54	22.76	237	Red
263		2-58
Example		Compound	3.52	22.57	250	Red
264		2-84
Example		Compound	3.52	22.55	250	Red
265		2-110
Example	Compound	Compound	3.54	22.90	320	Red
266	1-54	2-7
Example		Compound	3.49	23.79	285	Red
267		2-33
Example		Compound	3.46	23.66	312	Red
268		2-59
Example		Compound	3.54	23.28	310	Red
269		2-85
Example		Compound	3.46	23.38	290	Red
270		2-111
Example	Compound	Compound	3.46	22.50	290	Red
271	1-55	2-8
Example		Compound	3.49	22.69	316	Red
272		2-34
Example		Compound	3.51	22.64	316	Red
273		2-60
Example		Compound	3.53	22.51	288	Red
274		2-86
Example		Compound	3.45	22.55	281	Red
275		2-112
Example	Compound	Compound	3.73	20.14	202	Red
276	1-56	2-9
Example		Compound	3.68	20.74	192	Red
277		2-35
Example		Compound	3.74	20.67	190	Red
278		2-61
Example		Compound	3.76	20.86	193	Red
279		2-87
Example		Compound	3.70	20.89	206	Red
280		2-113
Example	Compound	Compound	3.61	22.77	223	Red
281	1-57	2-10
Example		Compound	3.53	21.44	251	Red
282		2-36
Example		Compound	3.61	22.34	249	Red
283		2-62
Example		Compound	3.53	18.11	251	Red
284		2-88
Example		Compound	3.59	20.00	245	Red
285		2-114
Example	Compound	Compound	3.61	19.47	230	Red
286	1-58	2-11
Example		Compound	3.58	13.07	229	Red
287		2-37
Example		Compound	3.58	12.18	234	Red
288		2-63
Example		Compound	3.59	15.54	243	Red
289		2-89
Example		Compound	3.57	12.56	246	Red
290		2-115
Example	Compound	Compound	3.47	22.97	318	Red
291	1-59	2-12
Example		Compound	3.50	23.06	280	Red
292		2-38
Example		Compound	3.45	23.76	285	Red
293		2-64
Example		Compound	3.49	23.19	292	Red
294		2-90
Example		Compound	3.54	22.94	290	Red
295		2-116
Example	Compound	Compound	3.48	23.59	292	Red
296	1-60	2-13
Example		Compound	3.49	23.12	295	Red
297		2-39
Example		Compound	3.54	23.16	304	Red
298		2-65
Example		Compound	3.51	23.63	313	Red
299		2-91
Example		Compound	3.47	23.84	301	Red
300		2-117
Example	Compound	Compound	3.70	20.29	198	Red
301	1-61	2-14
Example		Compound	3.74	20.22	198	Red
302		2-40
Example		Compound	3.76	20.36	200	Red
303		2-66
Example		Compound	3.66	21.28	199	Red
304		2-92
Example		Compound	3.72	21.33	199	Red
305		2-118
Example	Compound	Compound	3.70	20.30	208	Red
306	1-62	2-15
Example		Compound	3.76	20.96	194	Red
307		2-41
Example		Compound	3.67	21.33	208	Red
308		2-77
Example		Compound	3.68	21.11	202	Red
309		2-83
Example		Compound	3.65	20.31	194	Red
310		2-119
Example	Compound	Compound	3.62	10.98	220	Red
311	1-63	2-16
Example		Compound	3.59	18.08	228	Red
312		2-42
Example		Compound	3.64	14.42	218	Red
313		2-68
Example		Compound	3.60	17.27	224	Red
314		2-94
Example		Compound	3.61	13.41	222	Red
315		2-120
Example	Compound	Compound	3.48	22.55	313	Red
316	1-64	2-17
Example		Compound	3.49	22.90	289	Red
317		2-43
Example		Compound	3.46	22.73	286	Red
318		2-79
Example		Compound	3.54	22.61	309	Red
319		2-95
Example		Compound	3.48	22.88	288	Red
320		2-121
Example	Compound	Compound	3.52	23.24	302	Red
321	1-65	2-18
Example		Compound	3.54	23.39	317	Red
322		2-44
Example		Compound	3.52	23.05	289	Red
323		2-70
Example		Compound	3.45	23.69	299	Red
324		2-96
Example		Compound	3.48	23.76	283	Red
325		2-122
Example	Compound	Compound	3.67	20.13	199	Red
326	1-66	2-19
Example		Compound	3.67	21.21	196	Red
327		2-45
Example		Compound	3.73	20.57	203	Red
328		2-71
Example		Compound	3.70	20.98	204	Red
329		2-97
Example		Compound	3.69	20.58	196	Red
330		2-123
Example	Compound	Compound	3.49	22.79	295	Red
331	1-67	2-20
Example		Compound	3.50	22.80	305	Red
332		2-66
Example		Compound	3.48	22.77	286	Red
333		2-82
Example		Compound	3.52	22.86	320	Red
334		2-103
Example		Compound	3.46	22.82	280	Red
335		2-127
Example	Compound	Compound	3.46	22.85	288	Red
336	1-68	2-21
Example		Compound	3.48	23.02	305	Red
337		2-57
Example		Compound	3.50	23.70	306	Red
338		2-83
Example		Compound	3.53	23.88	307	Red
339		2-123
Example		Compound	3.48	22.97	291	Red
340		2-130

TABLE 2
					Lifetime
	The First	The Second	Voltage	Efficiency	T95	Luminescent
Division	Host	Host	(V)	(cd/A)	(hr)	Color
Comparative	Compound	Compound	4.13	16.63	129	Red
Example 1	A-1	2-1
Comparative		Compound	4.08	16.45	129	Red
Example 2		2-27
Comparative		Compound	4.17	17.07	124	Red
Example 3		2-53
Comparative		Compound	4.10	16.96	126	Red
Example 4		2-79
Comparative		Compound	4.15	16.56	146	Red
Example 5		2-105
Comparative	Compound	Compound	3.93	17.63	159	Red
Example 6	A-2	2-2
Comparative		Compound	3.95	17.53	147	Red
Example 7		2-28
Comparative		Compound	3.90	16.99	160	Red
Example 8		2-54
Comparative		Compound	3.92	17.44	147	Red
Example 9		2-80
Comparative		Compound	3.91	17.23	163	Red
Example 10		2-106
Comparative	Compound	Compound	3.95	16.63	129	Red
Example 11	A-3	2-3
Comparative		Compound	3.90	16.45	129	Red
Example 12		2-29
Comparative		Compound	3.94	17.07	124	Red
Example 13		2-55
Comparative		Compound	3.88	16.96	126	Red
Example 14		2-81
Comparative		Compound	3.88	16.56	146	Red
Example 15		2-107
Comparative	Compound	Compound	3.91	17.66	165	Red
Example 16	A-4	2-5
Comparative		Compound	3.95	17.40	146	Red
Example 17		2-31
Comparative		Compound	3.92	18.00	169	Red
Example 18		2-57
Comparative		Compound	3.92	17.83	162	Red
Example 19		2-83
Comparative		Compound	3.94	17.68	147	Red
Example 20		2-109
Comparative	Compound	Compound	3.89	17.54	169	Red
Example 21	A-5	2-8
Comparative		Compound	3.95	17.05	163	Red
Example 22		2-34
Comparative		Compound	3.88	17.31	152	Red
Example 23		2-60
Comparative		Compound	3.95	17.67	153	Red
Example 24		2-86
Comparative		Compound	3.93	17.68	162	Red
Example 25		2-112
Comparative	Compound	Compound	3.99	17.66	165	Red
Example 26	A-6	2-10
Comparative		Compound	3.95	17.40	146	Red
Example 27		2-36
Comparative		Compound	3.89	18.00	169	Red
Example 28		2-62
Comparative		Compound	3.91	17.83	162	Red
Example 29		2-88
Comparative		Compound	3.93	17.68	147	Red
Example 30		2-114
Comparative	Compound	Compound	3.90	17.54	169	Red
Example 31	A-7	2-12
Comparative		Compound	3.92	17.05	163	Red
Example 32		2-38
Comparative		Compound	3.90	17.31	152	Red
Example 33		2-64
Comparative		Compound	3.95	17.67	153	Red
Example 34		2-90
Comparative		Compound	3.94	17.68	162	Red
Example 35		2-116
Comparative	Compound	Compound	3.90	17.21	158	Red
Example 36	A-8	2-14
Comparative		Compound	3.93	17.86	156	Red
Example 37		2-40
Comparative		Compound	3.91	17.88	167	Red
Example 38		2-66
Comparative		Compound	3.88	17.67	146	Red
Example 39		2-92
Comparative		Compound	3.92	17.98	154	Red
Example 40		2-118
Comparative	Compound	Compound	3.91	17.73	170	Red
Example 41	A-9	2-17
Comparative		Compound	3.93	17.02	150	Red
Example 42		2-43
Comparative		Compound	3.93	17.14	146	Red
Example 43		2-69
Comparative		Compound	3.94	17.44	169	Red
Example 44		2-95
Comparative		Compound	3.93	17.05	146	Red
Example 45		2-121
Comparative	Compound	Compound	4.14	15.33	120	Red
Example 46	A-10	2-22
Comparative		Compound	4.06	14.58	98	Red
Example 47		2-48
Comparative		Compound	4.07	15.50	113	Red
Example 48		2-74
Comparative		Compound	4.11	15.35	107	Red
Example 49		2-100
Comparative		Compound	4.12	16.04	108	Red
Example 50		2-126
Comparative	Compound	Compound	3.93	16.87	126	Red
Example 51	A-11	2-26
Comparative		Compound	3.90	16.79	129	Red
Example 52		2-52
Comparative		Compound	3.94	16.65	122	Red
Example 53		2-78
Comparative		Compound	3.88	17.03	132	Red
Example 54		2-104
Comparative		Compound	3.92	16.49	143	Red
Example 55		2-130
Comparative	Compound	Compound	3.89	16.47	144	Red
Example 56	A-12	2-21
Comparative		Compound	3.95	16.68	122	Red
Example 57		2-49
Comparative		Compound	3.90	16.75	134	Red
Example 58		2-73
Comparative		Compound	3.91	17.07	128	Red
Example 59		2-102
Comparative		Compound	3.90	17.19	148	Red
Example 60		2-130

TABLE 3
					Lifetime
	The First	TheS econd	Voltage	Efficiency	T95	Luminescent
Division	Host	Host	(V)	(cd/A)	(hr)	Color
Comparative	Compound	Compound	4.05	14.69	109	Red
Example 61	1-1	B-1
Comparative	Compound		4.13	14.62	113	Red
Example 62	1-7
Comparative	Compound		4.16	14.81	113	Red
Example 63	1-16
Comparative	Compound		4.12	15.57	93	Red
Example 64	1-28
Comparative	Compound		4.07	16.11	105	Red
Example 65	1-35
Comparative	Compound		4.06	15.48	111	Red
Example 66	1-43
Comparative	Compound		4.12	16.37	120	Red
Example 67	1-18
Comparative	Compound		4.14	15.22	102	Red
Example 68	1-40
Comparative	Compound	Compound	4.15	16.87	121	Red
Example 69	1-2	B-2
Comparative	Compound		4.09	16.44	131	Red
Example 70	1-10
Comparative	Compound		4.08	16.56	141	Red
Example 71	1-19
Comparative	Compound		4.07	16.82	131	Red
Example 72	1-26
Comparative	Compound		4.09	16.84	122	Red
Example 73	1-31
Comparative	Compound		4.09	16.65	124	Red
Example 74	1-22
Comparative	Compound		4.15	16.77	142	Red
Example 75	1-34
Comparative	Compound		4.05	17.20	145	Red
Example 76	1-41
Comparative	Compound	Compound	3.99	17.06	153	Red
Example 77	1-3	B-3
Comparative	Compound		3.90	17.42	149	Red
Example 78	1-12
Comparative	Compound		3.88	17.12	170	Red
Example 79	1-24
Comparative	Compound		3.91	17.64	151	Red
Example 80	1-37
Comparative	Compound		3.89	17.81	165	Red
Example 81	1-42
Comparative	Compound		3.92	17.98	160	Red
Example 82	1-9
Comparative	Compound		3.88	17.23	162	Red
Example 83	1-18
Comparative	Compound		3.88	17.84	154	Red
Example 84	1-30
Comparative	Compound	Compound	3.90	17.48	166	Red
Example 85	1-4	B-4
Comparative	Compound		3.92	17.70	145	Red
Example 86	1-11
Comparative	Compound		3.92	17.32	160	Red
Example 87	1-23
Comparative	Compound		3.90	17.04	149	Red
Example 88	1-36
Comparative	Compound		3.92	17.96	159	Red
Example 89	1-44
Comparative	Compound		3.90	16.96	151	Red
Example 90	1-16
Comparative	Compound		3.89	17.73	151	Red
Example 91	1-28
Comparative	Compound		3.93	16.94	154	Red
Example 92	1-37
Comparative	Compound	Compound	4.05	16.62	144	Red
Example 93	1-5	B-5
Comparative	Compound		4.06	17.03	147	Red
Example 94	1-14
Comparative	Compound		4.17	16.86	129	Red
Example 95	1-20
Comparative	Compound		4.08	16.62	122	Red
Example 96	1-33
Comparative	Compound		4.17	17.08	125	Red
Example 97	1-45
Comparative	Compound		4.10	16.78	145	Red
Example 98	1-16
Comparative	Compound		4.11	16.86	123	Red
Example 99	1-28
Comparative	Compound		4.12	16.50	144	Red
Example 100	1-39
Comparative	Compound	Compound	3.93	17.14	159	Red
Example 101	1-6	B-6
Comparative	Compound		3.90	17.95	164	Red
Example 102	1-13
Comparative	Compound		3.93	17.23	159	Red
Example 103	1-21
Comparative	Compound		3.88	17.80	159	Red
Example 104	1-32
Comparative	Compound		3.89	17.02	164	Red
Example 105	1-40
Comparative	Compound		3.92	17.03	167	Red
Example 106	1-27
Comparative	Compound		3.91	17.63	149	Red
Example 107	1-36
Comparative	Compound		3.89	17.21	165	Red
Example 108	1-45
Comparative	Compound	Compound	4.13	16.34	91	Red
Example 109	1-7	B-7
Comparative	Compound		4.09	15.04	125	Red
Example 110	1-16
Comparative	Compound		4.09	16.06	103	Red
Example 111	1-25
Comparative	Compound		4.16	14.67	93	Red
Example 112	1-34
Comparative	Compound		4.05	14.92	107	Red
Example 113	1-46
Comparative	Compound		4.14	14.51	121	Red
Example 114	1-10
Comparative	Compound		4.11	16.27	125	Red
Example 115	1-31
Comparative	Compound		4.05	16.52	125	Red
Example 116	1-42
Comparative	Compound	Compound	3.95	16.70	128	Red
Example 117	1-8	B-8
Comparative	Compound		3.91	16.77	122	Red
Example 118	1-17
Comparative	Compound		3.92	16.56	133	Red
Example 119	1-29
Comparative	Compound		3.95	16.88	122	Red
Example 120	1-38
Comparative	Compound		3.91	17.20	138	Red
Example 121	1-12
Comparative	Compound		3.90	17.01	126	Red
Example 122	1-21
Comparative	Compound		3.90	16.53	135	Red
Example 123	1-33
Comparative	Compound		3.91	16.73	141	Red
Example 124	1-45
Comparative	Compound	Compound	3.93	17.64	160	Red
Example 125	1-9	B-9
Comparative	Compound		3.95	17.58	170	Red
Example 126	1-18
Comparative	Compound		3.88	17.84	157	Red
Example 127	1-22
Comparative	Compound		3.94	17.82	163	Red
Example 128	1-30
Comparative	Compound		3.89	17.13	162	Red
Example 129	1-41
Comparative	Compound		3.94	17.18	154	Red
Example 130	1-12
Comparative	Compound		3.89	17.16	160	Red
Example 131	1-26
Comparative	Compound		3.90	17.15	168	Red
Example 132	1-37
Comparative	Compound	Compound	3.88	17.24	160	Red
Example 133	1-1	B-10
Comparative	Compound		3.91	17.49	148	Red
Example 134	1-15
Comparative	Compound		3.95	17.33	169	Red
Example 135	1-26
Comparative	Compound		3.94	17.33	165	Red
Example 136	1-35
Comparative	Compound		3.88	17.74	149	Red
Example 137	1-21
Comparative	Compound		3.90	16.92	159	Red
Example 138	1-30
Comparative	Compound		3.89	17.44	163	Red
Example 139	1-42
Comparative	Compound		3.95	17.18	149	Red
Example 140	1-47
Comparative	Compound	Compound	4.06	16.45	139	Red
Example 141	1-3	B-11
Comparative	Compound		4.16	16.96	140	Red
Example 142	1-14
Comparative	Compound		4.07	17.19	125	Red
Example 143	1-27
Comparative	Compound		4.12	16.58	141	Red
Example 144	1-39
Comparative	Compound		4.17	16.44	135	Red
Example 145	1-47
Comparative	Compound		4.13	16.55	139	Red
Example 146	1-9
Comparative	Compound		4.05	17.01	142	Red
Example 147	1-18
Comparative	Compound		4.06	16.84	148	Red
Example 148	1-31
Comparative	Compound	Compound	3.92	17.10	160	Red
Example 149	1-7	B-12
Comparative	Compound		3.89	17.14	166	Red
Example 150	1-16
Comparative	Compound		3.91	17.35	160	Red
Example 151	1-25
Comparative	Compound		3.94	17.24	160	Red
Example 152	1-34
Comparative	Compound		3.95	17.00	156	Red
Example 153	1-46
Comparative	Compound		3.93	17.93	153	Red
Example 154	1-10
Comparative	Compound		3.93	17.32	151	Red
Example 155	1-31
Comparative	Compound		3.89	17.33	164	Red
Example 156	1-42

When a current was applied to the organic light emitting devices manufactured in Examples 1 to 340 and Comparative Examples 1 to 156, the results of Tables 1 to 3 above were obtained. The red organic light emitting devices of Examples and Comparative Examples used the materials used widely in the prior art, and are structured to use Compound EB-1 as an electron blocking layer and to use Dp-7 as a dopant of the red light emitting layer. As shown in Table 2, when Examples Compounds A-1 to A-12 of Comparative Examples and the compound represented by Chemical Formula 2 of the present disclosure were co-deposited and used as a red light emitting layer, the results usually showed that the driving voltage increased and the efficiency and lifetime decreased as compared with the combination of the present disclosure. As shown in Table 3, even when Compounds B-1 to B-12 of Comparative Examples and the compound represented by Chemical Formula 1 of the present disclosure were co-deposited and used as a red light emitting layer, the results showed that the driving voltage increased and the efficiency and lifespan decreased.

In light of these result, it can be inferred that the reason why the driving voltage is improved and the efficiency and lifespan are increased is because the combination of the compound of Compound Formula 1 as the first host and the compound of Compound Formula 2 as the second host of the present disclosure facilitates energy transfer to the red dopant in the red light emitting layer.

Therefore, it can be confirmed that since the combination of the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 of the present disclosure has a more stable balance in the light emitting layer than the combination with the compounds of Comparative Examples, electrons and holes combine to form excitons, thereby greatly increasing efficiency and lifetime. From these facts, it was confirmed that when the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 of the present disclosure are co-deposited and used as the host of the red light emitting layer, the driving voltage, luminous efficiency and lifespan characteristics of organic light emitting devices can be improved.

DESCRIPTION OF SYMBOLS

• • 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

1. An organic light emitting device comprising: an anode;a cathode; anda light emitting layer between the anode and the cathode,wherein the light emitting layer includes a compound represented by the following Chemical Formula 1 and a compound represented by the following Chemical Formula 2:

2. The organic light emitting device according to claim 1, wherein Ar1 and Ar2 are each independently phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, dibenzofuranyl, dibenzothiophenyl, or triphenylsilyl phenyl,each of which is unsubstituted or substituted with deuterium.

3. The organic light emitting device according to claim 1, wherein L2 and L3 are each independently a single bond, phenylene, biphenyldiyl, or naphthalenediyl,each of which, except for a single bond, is unsubstituted or substituted with deuterium.

4. The organic light emitting device according to claim 1, wherein R1 is each independently hydrogen, deuterium, phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, triphenylenyl, fluoranthenyl, naphthyl phenyl, phenyl naphthyl, dihydroindenyl, dibenzofuranyl, dibenzothiophenyl, benzonaphthofuranyl, or benzonaphthothiophenyl, with the proviso that at least one R1 is deuterium, phenyl substituted with deuterium, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, triphenylenyl, fluoranthenyl, naphthyl phenyl, phenyl naphthyl, dibenzofuranyl, dibenzothiophenyl, benzonaphthofuranyl, or benzonaphthothiophenyl, each of which, except for deuterium and phenyl substituted with deuterium, issubstituted or substituted with deuterium.

5. The organic light emitting device according to claim 1, wherein the compound represented by Chemical Formula 1 is one selected from the following:

6. The organic light emitting device according to claim 1, wherein Ar3 and Ar4 are each independently phenyl, biphenylyl, terphenylyl, quaterphenylyl, triphenylmethyl phenyl, triphenylsilyl phenyl, naphthyl, phenanthrenyl, triphenylenyl, fluoranthenyl, chrysenyl, benzo[c]phenanthrenyl, carbazolyl, phenyl carbazolyl, dimethylfluorenyl, dibenzofuranyl, or dibenzothiophenyl.

7. The organic light emitting device according to claim 1, wherein L4 is phenylene, biphenyldiyl, terphenyldiyl, quarterphenyldiyl, naphthalenediyl, phenylnaphthalenediyl, or phenylnaphthalenediyl substituted with one phenyl.

8. The organic light emitting device according to claim 1, wherein L5 and L6 are each independently a single bond, phenylene, biphenyldiyl, naphthalenediyl, phenylnaphthalenediyl, or carbazolediyl.

9. The organic light emitting device according to claim 1, wherein the compound represented by Chemical Formula 2 is one selected from the following: