KR20230014671A - Organic light emitting device - Google Patents

Abstract

The present invention provides an organic light emitting element with an improved driving voltage, efficiency, and lifespan. The organic light emitting element comprises: a positive pole; a negative pole; and a light emitting layer.

Description

Organic light emitting device {Organic light emitting device}

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

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

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

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

Korean Patent Publication No. 10-2000-0051826

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

The present invention provides the following organic light emitting device:

anode;

cathode; and

Including a light emitting layer between the anode and the cathode,

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

Organic Light-Emitting Elements:

[Formula 1]

In Formula 1,

R ₁ is each independently hydrogen, deuterium, substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted C _2-60 including any one or more selected from the group consisting of N, O and S; Heteroaryl;

R ₂ are each independently hydrogen or deuterium;

Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C _6-60 aryl, or a substituted or unsubstituted C _2-60 hetero including any one or more selected from the group consisting of N, O and S; aryl,

When R ₁ is each independently hydrogen or deuterium, at least one of Ar ₁ and Ar ₂ includes at least one selected from the group consisting of substituted or unsubstituted N, O and S C _2-60 Heteroaryl;

L ₁ and L ₂ are each independently a single bond or a substituted or unsubstituted C _6-60 arylene;

a is an integer from 1 to 7;

b is an integer from 1 to 6;

The compound represented by Formula 1 may not contain deuterium or may contain at least one deuterium,

[Formula 2]

In Formula 2,

A is a benzene ring or naphthalene ring fused with an adjacent ring,

Ar ₃ and Ar ₄ are each independently a substituted or unsubstituted C _6-60 aryl, or a substituted or unsubstituted C _2-60 hetero including any one or more selected from the group consisting of N, O and S; aryl,

L ₃ is a substituted or unsubstituted C _6-60 arylene;

L ₄ and L ₅ are each independently a single bond, a substituted or unsubstituted C _6-60 arylene, or a substituted or unsubstituted C containing any one or more selected from the group consisting of N, O and S; _2-60 heteroarylene.

The organic light emitting device described above may improve efficiency, low driving voltage, and/or lifetime characteristics of the organic light emitting device by including the compound represented by Formula 1 and the compound represented by Formula 2 in the light emitting layer.

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

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

또는

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

or

means a bond connected to another substituent.

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

In the present specification, the number of carbon atoms of the carbonyl group is not particularly limited, but is preferably 1 to 40 carbon atoms. Specifically, it may be a substituent having the following structure, but is not limited thereto.

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

In the present specification, the number of carbon atoms of the imide group is not particularly limited, but is preferably 1 to 25 carbon atoms. Specifically, it may be a substituent having the following structure, but is not limited thereto.

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

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

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

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

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

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

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

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

etc. However, it is not limited thereto.

In the present specification, the heteroaryl group is a heteroaryl group containing one or more of O, N, Si, and S as heterogeneous elements, and the number of carbon atoms is not particularly limited, but preferably has 2 to 60 carbon atoms. According to one embodiment, the heteroaryl group has 6 to 30 carbon atoms. According to one embodiment, the carbon number of the heteroaryl group is 6 to 20. Examples of the heteroaryl group include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazine group, and an acridyl group. , pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyridopyrimidinyl group, pyridopyrazinyl group, pyrazinopyrazinyl group, isoquinoline group, indole group , carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, isoxazolyl group, thiadia A zolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but are not limited thereto.

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

In this specification, the term "deuterated or substituted with deuterium" means that at least one available hydrogen in each formula is replaced with deuterium. Specifically, substituting with deuterium in each chemical formula or definition of a substituent means that at least one of hydrogen-bonding positions in a molecule is substituted with deuterium.

In addition, in the present specification, the term "deuterium substitution rate" means the percentage of the number of deuterium substituted with respect to the total number of hydrogens that may be present in each chemical formula.

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

anode and cathode

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

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

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

hole injection layer

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

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

hole transport layer

The organic light emitting device according to the present invention 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 receives holes from the anode or the hole injection layer and transports the holes to the light emitting layer. As a hole transport material, it is a material that receives holes from the anode or the hole injection layer and transfers them to the light emitting layer, and has hole mobility. Larger materials are suitable.

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

electron blocking layer

The organic light emitting device according to the present invention may include an electron blocking layer between the hole transport layer and the light emitting layer, if necessary. The electron blocking layer is formed on the hole transport layer, and is preferably provided in contact with the light emitting layer to control hole mobility and prevent excessive movement of electrons to increase the probability of hole-electron coupling, thereby increasing the efficiency of the organic light emitting device. means a layer that serves to improve The electron blocking layer includes an electron blocking material, and an example of such an electron blocking material may be an arylamine-based organic material, but is not limited thereto.

light emitting layer

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

Preferably, Chemical Formula 1 may be represented by any one of the following Chemical Formulas 1-1 to 1-11:

In Formula 1-1 to Formula 1-11,

Descriptions of R ₁ , R ₂ , Ar ₁ , Ar ₂ , L ₁ , L ₂ , a and b are as defined in Chemical Formula 1.

Preferably, at least one of R ₁ is deuterium, substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted C _2- including any one or more selected from the group consisting of N, O and S. ₆₀ heteroaryl, and Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C _6-60 aryl, or a substituted or unsubstituted N, O, and S, and any one or more selected from the group consisting of It may be C _2-60 heteroaryl.

More preferably, at least one of R ₁ is deuterium, phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, naphthyl phenyl, phenyl naphthyl, dibenzofuranyl, or dibenzothiophenyl; The phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, naphthyl phenyl, phenyl naphthyl, dibenzofuranyl and dibenzothiophenyl may each independently be unsubstituted or substituted with one or more deuterium atoms. And, Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, dibenzofuranyl, dibenzothiophenyl, or triphenylsilyl phenyl, wherein Ar ₁ and The hydrogens of Ar ₂ may each independently be unsubstituted or substituted with deuterium.

Preferably, R ₁ Each independently contains at least one selected from the group consisting of hydrogen, deuterium, substituted or unsubstituted C _6-20 aryl, or substituted or unsubstituted N, O and S C _2-20 It may be heteroaryl;

More preferably, each R ₁ is independently selected from hydrogen, deuterium, phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, naphthylphenyl, phenyl naphthyl, dibenzofuranyl, or dibenzothio It may be phenyl, and the hydrogens of the phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, naphthyl phenyl, phenyl naphthyl, dibenzofuranyl and dibenzothiophenyl are each independently unsubstituted or deuterium can be replaced with

Most preferably, each R ₁ may independently be hydrogen, deuterium, or any one selected from the group consisting of:

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

More preferably, Ar ₁ and Ar ₂ may each independently be phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, dibenzofuranyl, dibenzothiophenyl or triphenylsilyl phenyl; The hydrogens of Ar ₁ and Ar ₂ may each independently be unsubstituted or substituted with deuterium.

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

Preferably, L ₁ and L ₂ may each independently be a single bond or a substituted or unsubstituted C _6-20 arylene group;

More preferably, L ₁ and L ₂ may each independently be a single bond, phenylene, biphenyldiyl, or naphthalenediyl, and the hydrogens of the phenylene, biphenyldiyl, and naphthalenediyl are each independently unsubstituted. or can be substituted with deuterium.

In addition, the compound represented by Chemical Formula 1 may not contain deuterium or may contain at least one deuterium.

For 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 is 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, Alternatively, it may be 90% or more and 100% or less. The deuterium substitution rate of these compounds is calculated as the number of substituted deuteriums relative to the total number of hydrogens that may exist in the formula. Spectrometer) analysis.

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

.

In the above compounds, the compound represented by '[structural formula] _Dn ' refers to a compound in which n hydrogens of the compound having the corresponding 'structural formula' are substituted with deuterium.

The compound represented by Chemical Formula 1 can be prepared by, for example, a manufacturing method such as the following Reaction Scheme 1, and other compounds can be prepared similarly.

[Scheme 1]

In Reaction Scheme 1, R ₁ , R ₂ , Ar ₁ , Ar ₂ , L ₁ , L ₂ , descriptions of a and b are as defined in Formula 1, X is halogen, and preferably X is chloro or bromo.

Scheme 1 is a Suzuki coupling reaction, which is preferably carried out in the presence of a palladium catalyst and a base, and a reactor for the Suzuki coupling reaction may be modified as known in the art. The manufacturing method may be more specific in Preparation Examples to be described later.

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

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

In Formula 2-1 to Formula 2-4,

Ar ₃ , Ar ₄ and L ₄ to L ₆ are as defined in claim 1.

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

More preferably, Ar ₃ and Ar ₄ are each independently selected from phenyl, biphenylyl, terphenylyl, quaterphenylyl, triphenylmethylphenyl, triphenylsilylphenyl, naphthyl, phenanthrenyl, triphenylenyl, fluoranthenyl, chrysenyl, benzo[c]phenanthrenyl, carbazole, phenyl carbazole, dimethylfluorenyl, dibenzofuranyl, or dibenzothiophenyl.

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

Preferably, L ₃ may be a substituted or unsubstituted C _6-60 arylene;

More preferably, L ₃ may be phenylene, biphenyldiyl, terphenyldiyl, quaterphenyldiyl, naphthalenediyl, phenylnaphthalenediyl, or phenylnaphthalenediyl substituted with one phenyl.

Most preferably, L ₃ can be any one selected from the group consisting of:

Preferably, L ₄ and L ₅ are each independently selected from a single bond, substituted or unsubstituted C _6-20 arylene, or substituted or unsubstituted N, O, and S. It may be a C _2-20 heteroarylene containing

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

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

.

.

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

.

.

In the above compounds, the compound represented by '[structural formula] _Dn ' refers to a compound in which n hydrogens of the compound having the corresponding 'structural formula' are substituted with deuterium.

The compound represented by Chemical Formula 2 can be prepared by, for example, a manufacturing method such as the following Reaction Scheme 2, and other compounds can be prepared similarly.

[Scheme 2]

In Reaction Scheme 2, Ar ₃ , Ar ₄ and L ₄ to L ₆ are as defined in Formula 2, 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 the reactor for the amine substitution reaction can be changed as known in the art. The manufacturing method may be more specific in Preparation Examples to be described later.

Preferably, the weight ratio of the compound represented by Formula 1 and the compound represented by 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 a host. The dopant material is not particularly limited as long as it is a material used in an organic light emitting device. For example, there are aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like. Specifically, aromatic amine derivatives are condensed aromatic ring derivatives having a substituted or unsubstituted arylamino group, such as pyrene, anthracene, chrysene, periplanthene, etc. having an arylamino group, and styrylamine compounds include substituted or unsubstituted arylamine is substituted with at least one arylvinyl group, wherein one or two or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, etc., but is not limited thereto. In addition, metal complexes include, but are not limited to, iridium complexes and platinum complexes.

Preferably, any one from the group consisting of the dopant material may be used, but is not limited thereto:

hole blocking layer

The organic light emitting device according to the present invention may include a hole blocking layer between the light emitting layer and the electron transport layer to be described later, if necessary. The hole blocking layer is formed on the light emitting layer, preferably provided in contact with the light emitting layer, to improve the efficiency of the organic light emitting device by controlling electron mobility and preventing excessive movement of holes to increase the probability of hole-electron coupling layers that play a role. The hole blocking layer includes a hole blocking material, and examples of the hole blocking material include azine derivatives including triazine; triazole derivatives; oxadiazole derivatives; phenanthroline derivatives; A compound having an electron withdrawing group such as a phosphine oxide derivative may be used, but is not limited thereto.

electron transport layer

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

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

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

electron injection layer

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

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

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

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

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

organic light emitting device

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

The organic light emitting device according to the present invention can be manufactured by sequentially stacking the above-described components. At this time, by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation, depositing a metal or a metal oxide having conductivity or an alloy thereof on the substrate to form an anode And, after forming each of the above-described layers thereon, it can be manufactured by depositing a material that can be used as a cathode thereon. In addition to this method, an organic light emitting device may be manufactured by sequentially depositing a cathode material on a substrate to an anode material in the reverse order of the above configuration (WO 2003/012890). In addition, the light emitting layer may be formed by a solution coating method as well as a vacuum deposition method of a host and a dopant. Here, the solution coating method means spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, etc., but is not limited to these.

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

Hereinafter, a preferred embodiment is presented to aid understanding of the present invention. However, the following examples are only provided to more easily understand the present invention, and the content of the present invention is not limited thereby.

Synthesis Example 1-1

(8-chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and compound Trz1 (37 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 28.5 g of compound 1-1_P1. (Yield 67%, MS: [M+H] ⁺ = 700)

Compound 1-1_P1 (15 g, 21.4 mmol) and phenylboronic acid (2.7 g, 22.5 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (8.9 g, 64.3 mmol) was dissolved in 27 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.6 g of Compound 1-1. (Yield 69%, MS: [M+H] ⁺ = 715)

Synthesis Example 1-2

(8-chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and compound Trz2 (42.9 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 31.8 g of compound 1-2_P1. (Yield 66%, MS: [M+H] ⁺ = 792)

Compound 1-2_P1 (15 g, 21.4 mmol) and phenylboronic acid (2.7 g, 22.5 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (8.9 g, 64.3 mmol) was dissolved in 27 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9.6 g of Compound 1-2. (Yield 63%, MS: [M+H] ⁺ = 715)

Synthesis Example 1-3

(8-chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and compound Trz3 (31.2 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.1 g of compound 1-3_P1. (Yield 65%, MS: [M+H] ⁺ = 610)

Compound 1-3_P1 (15 g, 24.6 mmol) and phenylboronic acid (3.1 g, 25.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (10.2 g, 73.8 mmol) was dissolved in 31 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.2 g of compound 1-3. (Yield 70%, MS: [M+H] ⁺ = 652)

Synthesis Example 1-4

(8-chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and compound Trz4 (33.8 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 27.7 g of compound 1-4_P1. (Yield 70%, MS: [M+H] ⁺ = 650)

Compound 1-4_P1 (15 g, 23.1 mmol) and dibenzo[b,d]furan-1-ylboronic acid (5.1 g, 24.2 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (9.6 g, 69.2 mmol) was dissolved in 29 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.8 g of compound 1-4. (Yield 71%, MS: [M+H] ⁺ = 782)

Synthesis Example 1-5

(7-chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and compound Trz5 (44.5 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 31.8 g of compound 1-5_P1. (Yield 64%, MS: [M+H] ⁺ = 818)

Compound 1-5_P1 (15 g, 18.3 mmol) and phenylboronic acid (2.3 g, 19.2 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (7.6 g, 55 mmol) was dissolved in 23 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.3 g of compound 1-5. (Yield 72%, MS: [M+H] ⁺ = 860)

Synthesis Example 1-6

(7-chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and compound Trz6 (28 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.5 g of compound 1-6_P1. (Yield 69%, MS: [M+H] ⁺ = 560)

Compound 1-6_P1 (15 g, 26.8 mmol) and naphthalen-2-ylboronic acid (4.8 g, 28.1 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (11.1 g, 80.3 mmol) was dissolved in 33 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.9 g of compound 1-6. (Yield 68%, MS: [M+H] ⁺ = 652)

Synthesis Example 1-7

(7-chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and compound Trz7 (34.4 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.1 g of compound 1-7_P1. (Yield 60%, MS: [M+H] ⁺ = 660)

Compound 1-7_P1 (15 g, 22.7 mmol) and [1,1'-biphenyl] -3-ylboronic acid (4.7 g, 23.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (9.4 g, 68.2 mmol) was dissolved in 28 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.8 g of compound 1-7. (Yield 67%, MS: [M+H] ⁺ = 778)

Synthesis Example 1-8

(6-chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and compound Trz6 (28 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.8 g of compound 1-8_P1. (Yield 70%, MS: [M+H] ⁺ = 560)

Compound 1-8_P1 (15 g, 26.8 mmol) and naphthalen-1-ylboronic acid (4.8 g, 28.1 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (11.1 g, 80.3 mmol) was dissolved in 33 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12 g of compound 1-8. (Yield 69%, MS: [M+H] ⁺ = 652)

Synthesis Example 1-9

(4-chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and compound Trz8 (33.8 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 25.7 g of compound 1-9_P1. (Yield 65%, MS: [M+H] ⁺ = 650)

Compound 1-9_P1 (15 g, 23.1 mmol) and naphthalen-2-ylboronic acid (4.2 g, 24.2 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (9.6 g, 69.2 mmol) was dissolved in 29 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.8 g of compound 1-9. (Yield 69%, MS: [M+H] ⁺ = 742)

Synthesis Example 1-10

(4-chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and compound Trz3 (31.2 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26 g of compound 1-10_P1. (Yield 70%, MS: [M+H] ⁺ = 610)

Compound 1-10_P1 (15 g, 24.6 mmol) and phenylboronic acid (3.1 g, 25.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (10.2 g, 73.8 mmol) was dissolved in 31 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12 g of compound 1-10. (Yield 75%, MS: [M+H] ⁺ = 652)

Synthesis Example 1-11

Compound 1-10_P1 (15 g, 24.6 mmol) and dibenzo[b,d]furan-1-ylboronic acid (5.5 g, 25.8 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (10.2 g, 73.8 mmol) was dissolved in 31 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12 g of Compound 1-11. (Yield 66%, MS: [M+H] ⁺ = 742)

Synthesis Example 1-12

(8-chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and compound Trz9 (32.9 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.4 g of compound 1-12_P1. (Yield 63%, MS: [M+H] ⁺ = 636)

Compound 1-12_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 stirred and refluxed. Thereafter, potassium carbonate (9.8 g, 70.7 mmol) was dissolved in 29 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.5 g of compound 1-12. (Yield 67%, MS: [M+H] ⁺ = 728)

Synthesis Example 1-13

(3-chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and compound Trz10 (36.1 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 29.2 g of compound 1-13_P1. (Yield 70%, MS: [M+H] ⁺ = 686)

Compound 1-13_P1 (15 g, 21.9 mmol) and phenylboronic acid (2.8 g, 23 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (9.1 g, 65.6 mmol) was dissolved in 27 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10 g of compound 1-13. (Yield 63%, MS: [M+H] ⁺ = 728)

Synthesis Example 1-14

(3-chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and compound Trz11 (37 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26.4 g of compound 1-14_P1. (Yield 62%, MS: [M+H] ⁺ = 700)

Compound 1-14_P1 (15 g, 21.4 mmol) and dibenzo[b,d]thiophen-4-ylboronic acid (5.1 g, 22.5 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (8.9 g, 64.3 mmol) was dissolved in 27 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.6 g of compound 1-14. (Yield 75%, MS: [M+H] ⁺ = 848)

Synthesis Example 1-15

(6-chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and compound Trz12 (34.8 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 28.7 g of compound 1-15_P1. (Yield 71%, MS: [M+H] ⁺ = 666)

Compound 1-15_P1 (15 g, 22.5 mmol) and dibenzo[b,d]thiophen-3-ylboronic acid (5.4 g, 23.6 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (9.3 g, 67.5 mmol) was dissolved in 28 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.5 g of compound 1-15. (Yield 68%, MS: [M+H] ⁺ = 814)

Synthesis Example 1-16

(6-chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and compound Trz13 (37.6 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 32.4 g of compound 1-16_P1. (Yield 75%, MS: [M+H] ⁺ = 710)

Compound 1-16_P1 (15 g, 21.1 mmol) and dibenzo[b,d]thiophen-4-ylboronic acid (5.1 g, 22.2 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (8.8 g, 63.4 mmol) was dissolved in 26 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.3 g of compound 1-16. (Yield 68%, MS: [M+H] ⁺ = 858)

Synthesis Example 1-17

(6-chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and compound Trz14 (34.4 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 28.9 g of compound 1-17_P1. (Yield 72%, MS: [M+H] ⁺ = 660)

Compound 1-17_P1 (15 g, 22.7 mmol) and phenylboronic acid (2.9 g, 23.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (9.4 g, 68.2 mmol) was dissolved in 28 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9.7 g of compound 1-17. (Yield 61%, MS: [M+H] ⁺ = 702)

Synthesis Example 1-18

(4-chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and compound Trz15 (38.6 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 30.5 g of compound 1-18_P1. (Yield 69%, MS: [M+H] ⁺ = 726)

Compound 1-18_P1 (15 g, 20.7 mmol) and phenylboronic acid (2.6 g, 21.7 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (8.6 g, 62 mmol) was dissolved in 26 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.4 g of compound 1-18. (Yield 72%, MS: [M+H] ⁺ = 768)

Synthesis Example 1-19

(3-chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and compound Trz16 (33.8 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 25.7 g of compound 1-19_P1. (Yield 65%, MS: [M+H] ⁺ = 650)

Compound 1-19_P1 (15 g, 23.1 mmol) and phenylboronic acid (3 g, 24.2 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (9.6 g, 69.2 mmol) was dissolved in 29 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.6 g of compound 1-19. (Yield 73%, MS: [M+H] ⁺ = 692)

Synthesis Example 1-20

(4-chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and compound Trz17 (34.8 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 27.1 g of compound 1-20_P1. (Yield 67%, MS: [M+H] ⁺ = 666)

Compound 1-20_P1 (15 g, 22.5 mmol) and phenylboronic acid (2.9 g, 23.6 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (9.3 g, 67.5 mmol) was dissolved in 28 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.5 g of compound 1-20. (Yield 72%, MS: [M+H] ⁺ = 708)

Synthesis Example 1-21

(4-chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and compound Trz18 (34.8 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 28.8 g of compound 1-21_P1. (Yield 69%, MS: [M+H] ⁺ = 686)

Compound 1-21_P1 (15 g, 21.9 mmol) and dibenzo[b,d]thiophen-4-ylboronic acid (5.2 g, 23 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (9.1 g, 65.6 mmol) was dissolved in 27 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.7 g of compound 1-21. (Yield 75%, MS: [M+H] ⁺ = 834)

Synthesis Example 1-22

(8-chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and compound Trz19 (36.1 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26.3 g of compound 1-22_P1. (Yield 65%, MS: [M+H] ⁺ = 666)

Compound 1-22_P1 (15 g, 22.5 mmol) and naphthalen-2-ylboronic acid (4.1 g, 23.6 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (9.3 g, 67.5 mmol) was dissolved in 28 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.6 g of Compound 1-22. (Yield 62%, MS: [M+H] ⁺ = 758)

Synthesis Example 1-23

(7-chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and compound Trz20 (36.1 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 30 g of compound 1-23_P1. (Yield 72%, MS: [M+H] ⁺ = 686)

Compound 1-23_P1 (15 g, 21.9 mmol) and phenylboronic acid (2.8 g, 23 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (9.1 g, 65.6 mmol) was dissolved in 27 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11 g of compound 1-23. (Yield 69%, MS: [M+H] ⁺ = 728)

Synthesis Example 1-24

(3-chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and compound Trz21 (37.6 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 28.9 g of compound 1-24_P1. (Yield 67%, MS: [M+H] ⁺ = 710)

Compound 1-24_P1 (15 g, 21.1 mmol) and phenylboronic acid (2.7 g, 22.2 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (8.8 g, 63.4 mmol) was dissolved in 26 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.7 g of compound 1-24. (Yield 74%, MS: [M+H] ⁺ = 752)

Synthesis Example 1-25

Trifluoromethanesulfonic anhydride (95.9 g, 340 mmol) and Deuterium oxide (34 g, 1699.8 mmol) were added and stirred for 5 hours to form a solution at 0 °C. 1-bromodibenzo[b,d]furan (15 g, 60.7 mmol) was added to 120 ml of 1,2,4-trichlorobenzene and stirred. After that, 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 temperature was raised to 140 °C and stirred while maintaining. After reacting for 20 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated. Then, the organic layer was neutralized with an aqueous solution of potassium carbonate. After washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 5.6 g of compound sub1-1-1. (Yield 37%, MS: [M+H] ⁺ = 251)

Compound sub1-1-1 (15 g, 59.7 mmol) and bis(pinacolato)diboron (16.7 g, 65.7 mmol) were stirred while refluxing in 300 ml of 1,4-dioxane. Then, potassium acetate (8.8 g, 89.6 mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (1 g, 1.8 mmol) and tricyclohexylphosphine (1 g, 3.6 mmol) were added. After reacting for 5 hours, cooling to room temperature and separating the organic layer using chloroform and water, the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.5 g of compound sub1-1-2. (Yield 70%, MS: [M+H] ⁺ = 299)

Compound sub1-1-2 (15 g, 45.1 mmol) and compound Trz22 (23.2 g, 47.4 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.7 g, 135.3 mmol) was dissolved in 56 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 20.8 g of Compound 1-25. (Yield 74%, MS: [M+H] ⁺ = 625)

Synthesis Example 1-26

Trifluoromethanesulfonic anhydride (119.9 g, 424.9 mmol) and Deuterium oxide (42.6 g, 2124.7 mmol) were added and stirred for 5 hours to form a solution at 0 °C. 1-bromodibenzo[b,d]furan (15 g, 60.7 mmol) was added to 120 ml of 1,2,4-trichlorobenzene and stirred. After that, 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 temperature was raised to 140 °C and stirred while maintaining. After reacting for 24 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated. Then, the organic layer was neutralized with an aqueous solution of potassium carbonate. After washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 5.9 g of compound sub1-2-1. (Yield 39%, MS: [M+H] ⁺ = 252)

Compound sub1-2-1 (15 g, 59.5 mmol) and bis(pinacolato)diboron (16.6 g, 65.4 mmol) were stirred while refluxing in 300 ml of 1,4-dioxane. Then, potassium acetate (8.8 g, 89.2 mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (1 g, 1.8 mmol) and tricyclohexylphosphine (1 g, 3.6 mmol) were added. After reacting for 4 hours, cooling to room temperature and separating the organic layer using chloroform and water, the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.2 g of compound sub1-2-2. (Yield 63%, MS: [M+H] ⁺ = 300)

Compound sub1-2-2 (15 g, 50.1 mmol) and compound Trz23 (32.1 g, 52.6 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (20.8 g, 150.4 mmol) was dissolved in 62 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 26.9 g of compound 1-26. (Yield 72%, MS: [M+H] ⁺ = 747)

Synthesis Example 1-27

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 5 hours to form a solution. 1-bromodibenzo[b,d]furan (15 g, 60.7 mmol) was added to 120 ml of 1,2,4-trichlorobenzene and stirred. After that, 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 temperature was raised to 140 °C and stirred while maintaining. After reacting for 36 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated. Then, the organic layer was neutralized with an aqueous solution of potassium carbonate. After washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.1 g of compound sub1-3-1. (Yield 40%, MS: [M+H] ⁺ = 254)

Compound sub1-3-1 (15 g, 59 mmol) and bis(pinacolato)diboron (16.5 g, 64.9 mmol) were stirred while refluxing in 300 ml of 1,4-dioxane. Then, potassium acetate (8.7 g, 88.5 mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (1 g, 1.8 mmol) and tricyclohexylphosphine (1 g, 3.5 mmol) were added. After reacting for 4 hours, cooling to room temperature and separating the organic layer using chloroform and water, the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.6 g of compound sub1-3-2. (Yield 65%, MS: [M+H] ⁺ = 302)

Compound sub1-3-2 (15 g, 50 mmol) and compound Trz24 (320.6 g, 52.5 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (20.7 g, 149.9 mmol) was dissolved in 62 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 23.2 g of compound 1-27. (Yield 74%, MS: [M+H] ⁺ = 628)

Synthesis Example 1-28

(7-chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and compound Trz25 (31.9 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.9 g of compound 1-28_P1. (Yield 66%, MS: [M+H] ⁺ = 621)

Compound 1-28_P1 (15 g, 24.1 mmol) and (phenyl-d5)boronic acid (3.1 g, 25.4 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (10 g, 72.4 mmol) was dissolved in 30 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.1 g of Compound 1-28. (Yield 69%, MS: [M+H] ⁺ = 668)

Synthesis Example 1-29

Trifluoromethanesulfonic anhydride (60.1 g, 213.1 mmol) and Deuterium oxide (21.4 g, 1065.6 mmol) were added and stirred for 5 hours to form a solution at 0 °C. 1-bromo-7-chlorodibenzo[b,d]furan (15 g, 53.3 mmol) was added to 120 ml of 1,2,4-trichlorobenzene and stirred. Thereafter, 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 temperature was raised to 140 °C and stirred while maintaining. . After reacting for 10 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated. Then, the organic layer was neutralized with an aqueous solution of potassium carbonate. After washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.4 g of compound sub3-1-1. (Yield 42%, MS: [M+H] ⁺ = 285)

Compound sub3-1-1 (15 g, 52.5 mmol) and bis(pinacolato)diboron (14.7 g, 57.8 mmol) were stirred while refluxing in 300 ml of 1,4-dioxane. Then, potassium acetate (7.7 g, 78.8 mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.9 g, 1.6 mmol) and tricyclohexylphosphine (0.9 g, 3.2 mmol) were added. After reacting for 6 hours, cooling to room temperature and separating the organic layer using chloroform and water, the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12 g of compound sub3-1-2. (Yield 69%, MS: [M+H] ⁺ = 333)

Compound sub3-1-2 (15 g, 45.1 mmol) and compound Trz5 (33 g, 47.4 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.7 g, 135.3 mmol) was dissolved in 56 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 25.2 g of compound 1-29_P1. (Yield 68%, MS: [M+H] ⁺ = 822)

Compound 1-29_P1 (15 g, 18.2 mmol) and phenylboronic acid (2.3 g, 19.1 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (7.6 g, 54.7 mmol) was dissolved in 23 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.9 g of Compound 1-29. (Yield 69%, MS: [M+H] ⁺ = 864)

Synthesis Example 1-30

Trifluoromethanesulfonic anhydride (45.1 g, 159.8 mmol) and Deuterium oxide (16 g, 799.2 mmol) were added and stirred for 5 hours to form a solution at 0 °C. 1-bromo-7-chlorodibenzo[b,d]furan (15 g, 53.3 mmol) was added to 120 ml of 1,2,4-trichlorobenzene and stirred. Thereafter, 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 temperature was raised to 140 °C and stirred while maintaining. . After reacting for 7 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated. Then, the organic layer was neutralized with an aqueous solution of potassium carbonate. After washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 5.6 g of compound sub3-2-1. (Yield 37%, MS: [M+H] ⁺ = 284)

Compound sub3-2-1 (15 g, 52.7 mmol) and bis(pinacolato)diboron (14.7 g, 58 mmol) were stirred while refluxing in 300 ml of 1,4-dioxane. Then, potassium acetate (7.8 g, 79.1 mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.9 g, 1.6 mmol) and tricyclohexylphosphine (0.9 g, 3.2 mmol) were added. After reacting for 6 hours, cooling to room temperature and separating the organic layer using chloroform and water, the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.1 g of compound sub3-2-2. (Yield 58%, MS: [M+H] ⁺ = 332)

Compound sub3-2-2 (15 g, 45.2 mmol) and compound Trz26 (23.4 g, 47.5 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.8 g, 135.7 mmol) was dissolved in 56 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.7 g of compound 1-30_P1. (Yield 60%, MS: [M+H] ⁺ = 618)

Compound 1-30_P1 (15 g, 24.3 mmol) and phenylboronic acid (3.1 g, 25.5 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (10.1 g, 72.8 mmol) was dissolved in 30 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.6 g of Compound 1-30. (Yield 66%, MS: [M+H] ⁺ = 660)

Synthesis Example 1-31

Trifluoromethanesulfonic anhydride (60.1 g, 213.1 mmol) and Deuterium oxide (21.4 g, 1065.6 mmol) were added and stirred for 5 hours to form a solution at 0 °C. 1-bromo-4-chlorodibenzo[b,d]furan (15 g, 53.3 mmol) was added to 120 ml of 1,2,4-trichlorobenzene and stirred. Thereafter, 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 temperature was raised to 140 °C and stirred while maintaining. . After reacting for 10 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated. Then, the organic layer was neutralized with an aqueous solution of potassium carbonate. After washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.4 g of compound sub5-1-1. (Yield 42%, MS: [M+H] ⁺ = 285)

Compound sub5-1-1 (15 g, 52.5 mmol) and bis(pinacolato)diboron (14.7 g, 57.8 mmol) were stirred while refluxing in 300 ml of 1,4-dioxane. Then, potassium acetate (7.7 g, 78.8 mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.9 g, 1.6 mmol) and tricyclohexylphosphine (0.9 g, 3.2 mmol) were added. After reacting for 6 hours, cooling to room temperature and separating the organic layer using chloroform and water, the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12 g of compound sub5-1-2. (Yield 69%, MS: [M+H] ⁺ = 333)

Compound sub5-1-2 (15 g, 45.1 mmol) and compound Trz27 (21.2 g, 47.4 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.7 g, 135.3 mmol) was dissolved in 56 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.3 g of compound 1-31_P1. (Yield 67%, MS: [M+H] ⁺ = 574)

Compound 1-31_P1 (15 g, 26.1 mmol) and naphthalen-2-ylboronic acid (4.7 g, 27.4 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (10.8 g, 78.4 mmol) was dissolved in 32 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.6 g of Compound 1-31. (Yield 67%, MS: [M+H] ⁺ = 666)

Synthesis Example 1-32

Compound sub1-2-2 (15 g, 50.1 mmol) and compound Trz28 (25.7 g, 52.6 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (20.8 g, 150.4 mmol) was dissolved in 62 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.4 g of Compound 1-32. (Yield 65%, MS: [M+H] ⁺ = 626)

Synthesis Example 1-33

Trifluoromethanesulfonic anhydride (30.1 g, 106.6 mmol) and Deuterium oxide (10.7 g, 532.8 mmol) were added and stirred for 5 hours to form a solution at 0 °C. 1-bromo-8-chlorodibenzo[b,d]furan (15 g, 53.3 mmol) was added to 120 ml of 1,2,4-trichlorobenzene and stirred. After that, 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 temperature was raised to 140 °C and stirred while maintaining. . After reacting for 4 hours, it was cooled to room temperature, and the organic layer and the water layer were separated. Then, the organic layer was neutralized with an aqueous solution of potassium carbonate. After washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.5 g of compound sub2-1-1. (Yield 43%, MS: [M+H] ⁺ = 283)

Compound sub2-1-1 (15 g, 52.9 mmol) and bis(pinacolato)diboron (14.8 g, 58.2 mmol) were stirred while refluxing in 300 ml of 1,4-dioxane. Then, potassium acetate (7.8 g, 79.4 mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.9 g, 1.6 mmol) and tricyclohexylphosphine (0.9 g, 3.2 mmol) were added. After reacting for 5 hours, cooling to room temperature and separating the organic layer using chloroform and water, the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.5 g of compound sub2-1-2. (Yield 66%, MS: [M+H] ⁺ = 331)

Compound sub2-1-2 (15 g, 45.4 mmol) and compound Trz29 (27.9 g, 47.6 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.8 g, 136.1 mmol) was dissolved in 56 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.2 g of compound 1-33_P1. (Yield 69%, MS: [M+H] ⁺ = 709)

Compound 1-33_P1 (15 g, 21.1 mmol) and naphthalen-2-ylboronic acid (3.8 g, 22.2 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (8.8 g, 63.4 mmol) was dissolved in 26 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.7 g of compound 1-33. (Yield 69%, MS: [M+H] ⁺ = 801)

Synthesis Example 1-34

Compound sub1-2-2 (15 g, 50.1 mmol) and compound Trz30 (28.1 g, 52.6 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (20.8 g, 150.4 mmol) was dissolved in 62 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 19.7 g of compound 1-34. (Yield 63%, MS: [M+H] ⁺ = 626)

Synthesis Example 1-35

A solution was prepared by adding trifluoromethanesulfonic anhydride (48 g, 170 mmol) and Deuterium oxide (17 g, 849.9 mmol) and stirring for 5 hours at 0 °C. 1-bromodibenzo[b,d]furan (15 g, 60.7 mmol) was added to 120 ml of 1,2,4-trichlorobenzene and stirred. After that, 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 temperature was raised to 140 °C and stirred while maintaining. After reacting for 8 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated. Then, the organic layer was neutralized with an aqueous solution of potassium carbonate. After washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6 g of compound sub1-4-1. (Yield 40%, MS: [M+H] ⁺ = 249)

Compound sub1-4-1 (15 g, 60.2 mmol) and bis(pinacolato)diboron (16.8 g, 66.2 mmol) were stirred while refluxing in 300 ml of 1,4-dioxane. Then, potassium acetate (8.9 g, 90.3 mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (1 g, 1.8 mmol) and tricyclohexylphosphine (1 g, 3.6 mmol) were added. After reacting for 4 hours, cooling to room temperature and separating the organic layer using chloroform and water, the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.5 g of compound sub1-4-2. (Yield 70%, MS: [M+H] ⁺ = 297)

Compound sub1-4-2 (15 g, 50.6 mmol) and compound Trz31 (29.6 g, 53.2 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (21 g, 151.9 mmol) was dissolved in 63 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 23.4 g of compound 1-35. (Yield 65%, MS: [M+H] ⁺ = 691)

Synthesis Example 1-36

(3-chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and compound Trz32 (33.5 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 28.6 g of compound 1-36_P1. (Yield 73%, MS: [M+H] ⁺ = 645)

Compound 1-36_P1 (15 g, 23.2 mmol) and compound sub1-4-2 (7.2 g, 24.4 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (9.6 g, 69.7 mmol) was dissolved in 29 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.3 g of compound 1-36. (Yield 68%, MS: [M+H] ⁺ = 779)

Synthesis Example 1-37

Compound sub1-4-2 (15 g, 50.6 mmol) and compound Trz33 (32.6 g, 53.2 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (21 g, 151.9 mmol) was dissolved in 63 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 27.6 g of compound 1-37. (Yield 73%, MS: [M+H] ⁺ = 746)

Synthesis Example 1-38

Trifluoromethanesulfonic anhydride (30.1 g, 106.6 mmol) and Deuterium oxide (10.7 g, 532.8 mmol) were added and stirred for 5 hours to form a solution at 0 °C. 1-bromo-4-chlorodibenzo[b,d]furan (15 g, 53.3 mmol) was added to 120 ml of 1,2,4-trichlorobenzene and stirred. Thereafter, 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 temperature was raised to 140 °C and stirred while maintaining. . After reacting for 4 hours, it was cooled to room temperature, and the organic layer and the water layer were separated. Then, the organic layer was neutralized with an aqueous solution of potassium carbonate. After washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6 g of compound sub5-2-1. (Yield 40%, MS: [M+H] ⁺ = 283)

Compound sub5-2-1 (15 g, 52.9 mmol) and bis(pinacolato)diboron (14.8 g, 58.2 mmol) were stirred while refluxing in 300 ml of 1,4-dioxane. Then, potassium acetate (7.8 g, 79.4 mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.9 g, 1.6 mmol) and tricyclohexylphosphine (0.9 g, 3.2 mmol) were added. After reacting for 6 hours, cooling to room temperature and separating the organic layer using chloroform and water, the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9.8 g of compound sub5-2-2. (Yield 56%, MS: [M+H] ⁺ = 331)

Compound sub5-2-2 (15 g, 45.4 mmol) and compound Trz34 (30.5 g, 47.6 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.8 g, 136.1 mmol) was dissolved in 56 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 25.6 g of compound 1-38_P1. (Yield 74%, MS: [M+H] ⁺ = 764)

Compound 1-38_P1 (15 g, 19.6 mmol) and phenyl boronic acid (2.5 g, 20.6 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (8.1 g, 58.9 mmol) was dissolved in 24 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9.8 g of compound 1-38. (Yield 62%, MS: [M+H] ⁺ = 806)

Synthesis Example 1-39

Compound sub1-2-2 (15 g, 50.1 mmol) and compound Trz35 (25.7 g, 52.6 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (20.8 g, 150.4 mmol) was dissolved in 62 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 22.3 g of Compound 1-39. (Yield 71%, MS: [M+H] ⁺ = 626)

Synthesis Example 1-40

Trifluoromethanesulfonic anhydride (30.1 g, 106.6 mmol) and Deuterium oxide (10.7 g, 532.8 mmol) were added and stirred for 5 hours to form a solution at 0 °C. 1-bromo-7-chlorodibenzo[b,d]furan (15 g, 53.3 mmol) was added to 120 ml of 1,2,4-trichlorobenzene and stirred. Thereafter, 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 temperature was raised to 140 °C and stirred while maintaining. . After reacting for 4 hours, it was cooled to room temperature, and the organic layer and the water layer were separated. Then, the organic layer was neutralized with an aqueous solution of potassium carbonate. After washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6 g of compound sub3-3-1. (Yield 40%, MS: [M+H] ⁺ = 283)

Compound sub3-3-1 (15 g, 52.9 mmol) and bis(pinacolato)diboron (14.8 g, 58.2 mmol) were stirred while refluxing in 300 ml of 1,4-dioxane. Then, potassium acetate (7.8 g, 79.4 mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.9 g, 1.6 mmol) and tricyclohexylphosphine (0.9 g, 3.2 mmol) were added. After reacting for 6 hours, cooling to room temperature and separating the organic layer using chloroform and water, the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9.8 g of compound sub3-3-2. (Yield 56%, MS: [M+H] ⁺ = 331)

Compound sub3-3-2 (15 g, 45.4 mmol) and compound Trz36 (21.4 g, 47.6 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.8 g, 136.1 mmol) was dissolved in 56 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.8 g of compound 1-40_P1. (Yield 65%, MS: [M+H] ⁺ = 572)

Compound 1-40_P1 (15 g, 26.2 mmol) and naphthalen-2-ylboronic acid (4.7 g, 27.5 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (10.9 g, 78.7 mmol) was dissolved in 33 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.5 g of compound 1-40. (Yield 66%, MS: [M+H] ⁺ = 664)

Synthesis Example 1-41

Compound 1-11 (10 g, 13.5 mmol), PtO ₂ (0.9 g, 4 mmol), and 67 ml of D ₂ O were added to a shaker tube, and 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 with MgSO ₄ , concentrated, and the sample was purified by silica gel column chromatography to prepare 4.2 g of compound 1-41. (Yield 41%, MS: [M+H] ⁺ = 768)

Synthesis Example 1-42

(4-chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and compound Trz6 (28 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.2 g of compound 1-42_P1. (Yield 71%, MS: [M+H] ⁺ = 561)

Compound 1-42_P1 (15 g, 26.8 mmol) and naphthalen-2-ylboronic acid (4.8 g, 28.2 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (11.1 g, 80.5 mmol) was dissolved in 33 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.3 g of compound 1-42_P2. (Yield 65%, MS: [M+H] ⁺ = 652)

Compound 1-42_P2 (10 g, 15.3 mmol), PtO ₂ (1 g, 4.6 mmol), and 77 ml of D ₂ O were added to a shaker tube, and 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 with MgSO ₄ , concentrated, and the sample was purified by silica gel column to prepare 3.7 g of compound 1-42. (Yield 36%, MS: [M+H] ⁺ = 679)

Synthesis Example 1-43

Compound 1-42_P1 (15 g, 26.8 mmol) and dibenzo[b,d]furan-4-ylboronic acid (4.8 g, 28.1 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (11.1 g, 80.3 mmol) was dissolved in 33 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.7 g of compound 1-43_P1. (Yield 74%, MS: [M+H] ⁺ = 692)

Compound 1-43_P1 (10 g, 14.5 mmol), PtO ₂ (1 g, 4.3 mmol), and 72 ml of D ₂ O were added to a shaker tube, and 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 with MgSO ₄ , concentrated, and the sample was purified by silica gel column chromatography to prepare 5.1 g of compound 1-43. (Yield 49%, MS: [M+H] ⁺ = 716)

Synthesis Example 1-44

(3-chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and compound Trz6 (28 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.8 g of compound 1-44_P1. (Yield 64%, MS: [M+H] ⁺ = 560)

Compound 1-44_P1 (15 g, 26.8 mmol) and dibenzo[b,d]furan-4-ylboronic acid (6 g, 28.1 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (11.1 g, 80.3 mmol) was dissolved in 33 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.2 g of compound 1-44_P2. (Yield 66%, MS: [M+H] ⁺ = 692)

Compound 1-44_P2 (10 g, 14.5 mmol), PtO ₂ (1 g, 4.3 mmol), and 72 ml of D ₂ O were added to a shaker tube, and 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 with MgSO ₄ , concentrated, and the sample was purified by silica gel column chromatography to prepare 3.1 g of compound 1-44. (Yield 30%, MS: [M+H] ⁺ = 717)

Synthesis Example 1-45

(6-chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and compound Trz37 (32.9 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 25.1 g of compound 1-45_P1. (Yield 65%, MS: [M+H] ⁺ = 636)

Compound 1-45_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 stirred and refluxed. Thereafter, potassium carbonate (9.8 g, 70.7 mmol) was dissolved in 29 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.8 g of compound 1-45_P2. (Yield 69%, MS: [M+H] ⁺ = 728)

Compound 1-45_P2 (10 g, 13.7 mmol), PtO ₂ (0.9 g, 4.1 mmol), and 69 ml of D ₂ O were added to a shaker tube, and 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 with MgSO ₄ , concentrated, and the sample was purified by silica gel column chromatography to prepare 4.6 g of compound 1-45. (Yield 44%, MS: [M+H] ⁺ = 756)

Synthesis Example 1-46

(7-chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and compound Trz38 (27.9 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.5 g of compound 1-46_P1. (Yield 72%, MS: [M+H] ⁺ = 560)

Compound 1-46_P1 (15 g, 26.8 mmol) and naphthalen-2-ylboronic acid (4.8 g, 28.1 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (11.1 g, 80.3 mmol) was dissolved in 33 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.2 g of compound 1-46_P2. (Yield 70%, MS: [M+H] ⁺ = 652)

Compound 1-46_P2 (10 g, 15.3 mmol), PtO ₂ (1 g, 4.6 mmol), and 77 ml of D ₂ O 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 with MgSO ₄ , concentrated, and the sample was purified by silica gel column chromatography to prepare 4.5 g of compound 1-46. (Yield 43%, MS: [M+H] ⁺ = 676)

Synthesis Example 1-47

(4-chlorodibenzo[b,d]furan-1-yl)boronic acid (15 g, 60.9 mmol) and compound Trz39 (36.1 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 30.9 g of compound 1-47_P1. (Yield 74%, MS: [M+H] ⁺ = 686)

Compound 1-47_P1 (15 g, 21.9 mmol) and phenylboronic acid (3.9 g, 23 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (9.1 g, 65.6 mmol) was dissolved in 27 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.6 g of compound 1-47_P2. (Yield 73%, MS: [M+H] ⁺ = 728)

Compound 1-47_P2 (10 g, 13.7 mmol), PtO ₂ (0.9 g, 4.1 mmol), and 69 ml of D ₂ O were added to a shaker tube, and 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 with MgSO ₄ , concentrated, and the sample was purified by silica gel column chromatography to prepare 3.7 g of compound 1-47. (Yield 36%, MS: [M+H] ⁺ = 756)

Synthesis Example 2-1

In a nitrogen atmosphere, 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, stirred and refluxed. . After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.3 g of compound subA-1. (Yield 62%, MS: [M+H] ⁺ = 278)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.2 g of Compound 2-1. (Yield 62%, MS: [M+H] ⁺ = 639)

Synthesis Example 2-2

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 17.4 g of Compound 2-2. (Yield 73%, MS: [M+H] ⁺ = 663)

Synthesis Example 2-3

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.3 g of Compound 2-3. (Yield 61%, MS: [M+H] ⁺ = 651)

Synthesis Example 2-4

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.3 g of Compound 2-4. (Yield 61%, MS: [M+H] ⁺ = 653)

Synthesis Example 2-5

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15 g of compound 2-5. (Yield 64%, MS: [M+H] ⁺ = 652)

Synthesis Example 2-6

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.8 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 mixed with Xylene 200 in a nitrogen atmosphere. ml, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.8 g of compound subA-2. (Yield 70%, MS: [M+H] ⁺ = 354)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.7 g of compound 2-7. (Yield 69%, MS: [M+H] ⁺ = 805)

Synthesis Example 2-8

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 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 mixed with Xylene 200 in a nitrogen atmosphere. ml, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.6 g of compound subA-3. (Yield 74%, MS: [M+H] ⁺ = 354)

In a nitrogen atmosphere, 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 and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.4 g of Compound 2-9. (Yield 60%, MS: [M+H] ⁺ = 789)

Synthesis Example 2-10

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.9 g of compound 2-10. (Yield 74%, MS: [M+H] ⁺ = 763)

Synthesis Example 2-11

In a nitrogen atmosphere, 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, stirred and refluxed. . After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.7 g of compound subA-4. (Yield 65%, MS: [M+H] ⁺ = 328)

In a nitrogen atmosphere, 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 and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 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 mixed with Xylene in a nitrogen atmosphere. It was added to 200 ml and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.4 g of compound subA-5. (Yield 73%, MS: [M+H] ⁺ = 354)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.2 g of compound 2-12. (Yield 62%, MS: [M+H] ⁺ = 639)

Synthesis Example 2-13

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.5 g of compound 2-13. (Yield 72%, MS: [M+H] ⁺ = 664)

Synthesis Example 2-14

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.5 g of compound 2-14. (Yield 65%, MS: [M+H] ⁺ = 679)

Synthesis Example 2-15

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.6 g of compound 2-15. (Yield 63%, MS: [M+H] ⁺ = 821)

Synthesis Example 2-16

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 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), sodium tert-butoxide (7.5 g, 77.7 mmol) was added to 200 ml of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.4 g of compound subA-6. (Yield 60%, MS: [M+H] ⁺ = 430)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.5 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 mixed in 200 ml of xylene in a nitrogen atmosphere. added, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.7 g of compound subA-7. (Yield 65%, MS: [M+H] ⁺ = 404)

In a nitrogen atmosphere, 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 and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.1 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), sodium tert- Butoxide (7.5 g, 77.7 mmol) was added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 18.6 g of compound subA-8. (Yield 65%, MS: [M+H] ⁺ = 480)

In a nitrogen atmosphere, 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 and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.5 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), sodium tert-butoxide (7.5 g, 77.7 mmol) was added to 200 ml of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.7 g of compound subA-9. (Yield 61%, MS: [M+H] ⁺ = 430)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.6 g of compound 2-20. (Yield 63%, MS: [M+H] ⁺ = 793)

Synthesis Example 2-21

In a nitrogen atmosphere, 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. Stir and reflux. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 17.4 g of compound subA-10. (Yield 72%, MS: [M+H] ⁺ = 404)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 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 mixed with Xylene in a nitrogen atmosphere. It was added to 200 ml and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.6 g of compound subA-11. (Yield 74%, MS: [M+H] ⁺ = 354)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.9 g of compound 2-22. (Yield 62%, MS: [M+H] ⁺ = 739)

Synthesis Example 2-23

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.6 g of compound 2-23. (Yield 63%, MS: [M+H] ⁺ = 765)

Synthesis Example 2-24

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.4 g of compound 2-24. (Yield 62%, MS: [M+H] ⁺ = 765)

Synthesis Example 2-25

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.6 g of compound 2-25. (Yield 70%, MS: [M+H] ⁺ = 789)

Synthesis Example 2-26

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.5 g of compound 2-26. (Yield 67%, MS: [M+H] ⁺ = 765)

Synthesis Example 2-27

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 16.5 g of compound 2-27. (Yield 74%, MS: [M+H] ⁺ = 789)

Synthesis Example 2-28

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.7 g of compound 2-28. (Yield 60%, MS: [M+H] ⁺ = 689)

Synthesis Example 2-29

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.1 g of compound 2-29. (Yield 61%, MS: [M+H] ⁺ = 821)

Synthesis Example 2-30

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.3 g of compound 2-30. (Yield 71%, MS: [M+H] ⁺ = 765)

Synthesis Example 2-31

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.1 g of compound 2-31. (Yield 66%, MS: [M+H] ⁺ = 703)

Synthesis Example 2-32

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 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), sodium tert-butoxide (7.5 g, 77.7 mmol) was added to 200 ml of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 16.9 g of compound subA-12. (Yield 66%, MS: [M+H] ⁺ = 430)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 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), sodium tert-butoxide (7.5 g, 77.7 mmol) was added to 200 ml of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 16.4 g of compound subA-13. (Yield 64%, MS: [M+H] ⁺ = 430)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.8 g of compound 2-34. (Yield 71%, MS: [M+H] ⁺ = 715)

Synthesis Example 2-35

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 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''-terpheny (21.6 g, 62.8 mmol), sodium tert-butoxide in a nitrogen atmosphere (7.5 g, 77.7 mmol) was added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.7 g of compound subA-14. (Yield 61%, MS: [M+H] ⁺ = 430)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.6 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'-bipheny (16.8 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were mixed with Xylene in a nitrogen atmosphere. It was added to 200 ml and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.3 g of compound subA-15. (Yield 63%, MS: [M+H] ⁺ = 354)

In a nitrogen atmosphere, compound subA-15 (10 g, 2.8 mmol), compound amine35 (1.1 g, 3 mmol), and sodium tert-butoxide (0.4 g, 3.7 mmol) were added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0 g, 0 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 1.3 g of compound 2-37. (Yield 68%, MS: [M+H] ⁺ = 689)

Synthesis Example 2-38

In a nitrogen atmosphere, compound subA-15 (10 g, 2.8 mmol), compound amine36 (1 g, 3 mmol), and sodium tert-butoxide (0.4 g, 3.7 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0 g, 0 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 1.3 g of compound 2-38. (Yield 69%, MS: [M+H] ⁺ = 653)

Synthesis Example 2-39

In a nitrogen atmosphere, compound subA-15 (10 g, 2.8 mmol), compound amine37 (1.4 g, 3 mmol), and sodium tert-butoxide (0.4 g, 3.7 mmol) were added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0 g, 0 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 1.4 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), sodium tert-butoxide (7.5 g, 77.7 mmol) was added to 200 ml of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 18 g of compound subA-16. (Yield 70%, MS: [M+H] ⁺ = 430)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.6 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), sodium tert-butoxide (7.5 g, 77.7 mmol) was added to 200 ml of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.4 g of compound subA-17. (Yield 60%, MS: [M+H] ⁺ = 430)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.7 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), sodium tert-butoxide (7.5 g, 77.7 mmol) was added to 200 ml of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 19 g of compound subA-18. (Yield 74%, MS: [M+H] ⁺ = 430)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 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), sodium tert-butoxide (7.5 g, 77.7 mmol) was added to 200 ml of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 16.7 g of compound subA-19. (Yield 65%, MS: [M+H] ⁺ = 430)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 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 mixed with Xylene in a nitrogen atmosphere. It was added to 200 ml and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.1 g of compound subA-20. (Yield 67%, MS: [M+H] ⁺ = 354)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 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 mixed with Xylene in a nitrogen atmosphere. It was added to 200 ml and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.3 g of compound subA-21. (Yield 63%, MS: [M+H] ⁺ = 354)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 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''-terpheny (21.6 g, 62.8 mmol), sodium tert-butoxide (7.5 g, 77.7 mmol) was added to 200 ml of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 16.4 g of compound subA-22. (Yield 64%, MS: [M+H] ⁺ = 430)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.1 g of compound 2-46. (Yield 61%, MS: [M+H] ⁺ = 715)

Synthesis Example 2-47

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.8 g of compound 2-47. (Yield 64%, MS: [M+H] ⁺ = 765)

Synthesis Example 2-48

In a nitrogen atmosphere, 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, stirred and refluxed. . After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.9 g of compound subA-23. (Yield 72%, MS: [M+H] ⁺ = 278)

In a nitrogen atmosphere, 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 and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.9 g of compound 2-48. (Yield 66%, MS: [M+H] ⁺ = 587)

Synthesis Example 2-49

In a nitrogen atmosphere, 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, stirred and refluxed. . After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9.9 g of compound subA-24. (Yield 60%, MS: [M+H] ⁺ = 278)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 18 g of compound 2-49. (Yield 73%, MS: [M+H] ⁺ = 687)

Synthesis Example 2-50

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 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 mixed with Xylene 200 in a nitrogen atmosphere. ml, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.8 g of compound subA-25. (Yield 75%, MS: [M+H] ⁺ = 354)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 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'-bipheny (16.8 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were mixed with Xylene 200 in a nitrogen atmosphere. ml, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15 g of compound subA-26. (Yield 71%, MS: [M+H] ⁺ = 354)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 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 mixed with Xylene 200 in a nitrogen atmosphere. ml, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.6 g of compound subA-27. (Yield 74%, MS: [M+H] ⁺ = 354)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0 g, 0 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 1.2 g of compound 2-53. (Yield 60%, MS: [M+H] ⁺ = 713)

Synthesis Example 2-54

In a nitrogen atmosphere, 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 and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0 g, 0 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 1 g of compound 2-54. (Yield 60%, MS: [M+H] ⁺ = 613)

Synthesis Example 2-55

In a nitrogen atmosphere, 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 and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 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''-terpheny (21.6 g, 62.8 mmol), sodium tert-butoxide (7.5 g, 77.7 mmol) was added to 200 ml of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.4 g of compound subA-28. (Yield 60%, MS: [M+H] ⁺ = 430)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.6 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), sodium tert-butoxide (7.5 g, 77.7 mmol) was added to 200 ml of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.7 g of compound subA-29. (Yield 61%, MS: [M+H] ⁺ = 430)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13 g of compound 2-57. (Yield 73%, MS: [M+H] ⁺ = 765)

Synthesis Example 2-58

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

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.7 g of compound 2-58. (Yield 61%, MS: [M+H] ⁺ = 739)

Synthesis Example 2-59

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 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 mixed with Xylene in a nitrogen atmosphere. It was added to 200 ml and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.1 g of compound subA-31. (Yield 62%, MS: [M+H] ⁺ = 354)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 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), sodium tert-butoxide (7.5 g, 77.7 mmol) was added to 200 ml of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 17.5 g of compound subA-32. (Yield 68%, MS: [M+H] ⁺ = 430)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.4 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), sodium tert-butoxide in a nitrogen atmosphere (7.5 g, 77.7 mmol) was added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 16.9 g of compound subA-33. (Yield 66%, MS: [M+H] ⁺ = 430)

In a nitrogen atmosphere, compound subA-33 (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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.1 g of compound 2-62. (Yield 61%, MS: [M+H] ⁺ = 715)

Synthesis Example 2-63

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.5 g of compound 2-63. (Yield 65%, MS: [M+H] ⁺ = 789)

Synthesis Example 2-64

In a nitrogen atmosphere, 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 to 200 ml of Xylene. Stir and reflux. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9.5 g of compound subB-1. (Yield 63%, MS: [M+H] ⁺ = 328)

In a nitrogen atmosphere, 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 and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.1 g of compound 2-64. (Yield 70%, MS: [M+H] ⁺ = 613)

Synthesis Example 2-65

In a nitrogen atmosphere, 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 and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.5 g of compound 2-65. (Yield 62%, MS: [M+H] ⁺ = 663)

Synthesis Example 2-66

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.2 g of compound 2-66. (Yield 65%, MS: [M+H] ⁺ = 719)

Synthesis Example 2-67

In a nitrogen atmosphere, 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 and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 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), sodium tert-butoxide (5.7 g, 59.8 mmol) in a nitrogen atmosphere ) was added to 200 ml of Xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.9 g of compound subB-2. (Yield 75%, MS: [M+H] ⁺ = 404)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.2 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), sodium tert-butoxide (5.7 g, 59.8 mmol) in a nitrogen atmosphere ) was added to 200 ml of Xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.4 g of compound subB-3. (Yield 67%, MS: [M+H] ⁺ = 404)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.6 g of compound 2-69. (Yield 68%, MS: [M+H] ⁺ = 687)

Synthesis Example 2-70

11H-benzo[a]carbazole (10 g, 46 mmol), 4-bromo-4'-chloro-1,1'-biphenyl (12.9 g, 48.3 mmol), sodium tert-butoxide (5.7 g, 59.8 mmol) into 200 ml of Xylene, followed by stirring and reflux. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.1 g of compound subB-4. (Yield 65%, MS: [M+H] ⁺ = 404)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.6 g of compound 2-70. (Yield 71%, MS: [M+H] ⁺ = 663)

Synthesis Example 2-71

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.6 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 prepared in a nitrogen atmosphere. It was added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.2 g of compound subB-5. (Yield 73%, MS: [M+H] ⁺ = 454)

In a nitrogen atmosphere, 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 and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.2 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), sodium tert in a nitrogen atmosphere -butoxide (5.7 g, 59.8 mmol) was added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15 g of compound subB-6. (Yield 68%, MS: [M+H] ⁺ = 480)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 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), sodium tert-butoxide (5.7 g, 59.8 mmol) into 200 ml of Xylene, followed by stirring and reflux. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.2 g of compound subB-7. (Yield 71%, MS: [M+H] ⁺ = 404)

In a nitrogen atmosphere, 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 and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.3 g of compound 2-74. (Yield 66%, MS: [M+H] ⁺ = 815)

Synthesis Example 2-75

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 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), Sodium tert-butoxide (5.7 g, 59.8 mmol) was added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.3 g of compound subB-8. (Yield 65%, MS: [M+H] ⁺ = 480)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 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), sodium tert in a nitrogen atmosphere -butoxide (5.7 g, 59.8 mmol) was added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.7 g of compound subB-9. (Yield 71%, MS: [M+H] ⁺ = 480)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 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), sodium tert in nitrogen atmosphere -butoxide (5.7 g, 59.8 mmol) was added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.6 g of compound subB-10. (Yield 66%, MS: [M+H] ⁺ = 480)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.8 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), sodium tert-butoxide (5.7 g, 59.8 mmol) in a nitrogen atmosphere ) was added to 200 ml of Xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.5 g of compound subB-11. (Yield 73%, MS: [M+H] ⁺ = 404)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.3 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), sodium tert-butoxide (5.7 g, 59.8 mmol) into 200 ml of Xylene, followed by stirring and reflux. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.4 g of compound subB-12. (Yield 72%, MS: [M+H] ⁺ = 404)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.1 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), sodium tert in a nitrogen atmosphere -butoxide (5.7 g, 59.8 mmol) was added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.2 g of compound subB-13. (Yield 69%, MS: [M+H] ⁺ = 480)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.1 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), sodium tert in nitrogen atmosphere -butoxide (5.7 g, 59.8 mmol) was added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.7 g of compound subB-14. (Yield 62%, MS: [M+H] ⁺ = 480)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.5 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), sodium tert in nitrogen atmosphere -butoxide (5.7 g, 59.8 mmol) was added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 16.5 g of compound subB-15. (Yield 75%, MS: [M+H] ⁺ = 480)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 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), sodium tert-butoxide (5.7 g, 59.8 mmol) into 200 ml of Xylene, followed by stirring and reflux. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.1 g of compound subB-16. (Yield 65%, MS: [M+H] ⁺ = 404)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.2 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), Sodium tert-butoxide (5.7 g, 59.8 mmol) was added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.6 g of compound subB-17. (Yield 66%, MS: [M+H] ⁺ = 480)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.2 g of compound 2-85. (Yield 66%, MS: [M+H] ⁺ = 815)

Synthesis Example 2-86

In a nitrogen atmosphere, 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. Stir and reflux. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.1 g of compound subC-1. (Yield 74%, MS: [M+H] ⁺ = 328)

In a nitrogen atmosphere, compound subC-1 (10 g, 30.5 mmol), compound amine75 (9.5 g, 32 mmol), and sodium tert-butoxide (3.8 g, 39.7 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.9 g of compound 2-86. (Yield 61%, MS: [M+H] ⁺ = 587)

Synthesis Example 2-87

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.9 g of compound 2-87. (Yield 71%, MS: [M+H] ⁺ = 689)

Synthesis Example 2-88

In a nitrogen atmosphere, 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 and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 21.6 g of compound 2-88. (Yield 73%, MS: [M+H] ⁺ = 973)

Synthesis Example 2-89

In a nitrogen atmosphere, 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 and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.1 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), sodium tert-butoxide (5.7 g, 59.8 mmol) in a nitrogen atmosphere ) was added to 200 ml of Xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.3 g of compound subC-2. (Yield 61%, MS: [M+H] ⁺ = 404)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.1 g of compound 2-90. (Yield 60%, MS: [M+H] ⁺ = 751)

Synthesis Example 2-91

In a nitrogen atmosphere, compound subC-2 (10 g, 24.8 mmol), compound amine12 (8.4 g, 26 mmol), and sodium tert-butoxide (3.1 g, 32.2 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.1 g of compound 2-91. (Yield 71%, MS: [M+H] ⁺ = 689)

Synthesis Example 2-92

5H-benzo[b]carbazole (10 g, 46 mmol), 2-bromo-5-chloro-1,1'-biphenyl (12.9 g, 48.3 mmol), sodium tert-butoxide (5.7 g, 59.8 mmol) in a nitrogen atmosphere ) was added to 200 ml of Xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.3 g of compound subC-3. (Yield 61%, MS: [M+H] ⁺ = 404)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.3 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), sodium tert-butoxide (5.7 g, 59.8 mmol) into 200 ml of Xylene, followed by stirring and reflux. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.2 g of compound subC-4. (Yield 66%, MS: [M+H] ⁺ = 404)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9.5 g of compound 2-93. (Yield 63%, MS: [M+H] ⁺ = 613)

Synthesis Example 2-94

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11 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), sodium tert in a nitrogen atmosphere -butoxide (5.7 g, 59.8 mmol) was added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.7 g of compound subC-5. (Yield 62%, MS: [M+H] ⁺ = 480)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10 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)naphthalen (15.3 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were prepared in a nitrogen atmosphere. It was added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.4 g of compound subC-6. (Yield 74%, MS: [M+H] ⁺ = 454)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.8 g of compound 2-96. (Yield 68%, MS: [M+H] ⁺ = 789)

Synthesis Example 2-97

In a nitrogen atmosphere, 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. Stir and reflux. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9 g of compound subC-7. (Yield 60%, MS: [M+H] ⁺ = 328)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.3 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), sodium tert-butoxide (5.7 g, 59.8 mmol) into 200 ml of Xylene, followed by stirring and reflux. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.7 g of compound subC-8. (Yield 63%, MS: [M+H] ⁺ = 405)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.2 g of compound 2-98. (Yield 66%, MS: [M+H] ⁺ = 689)

Synthesis Example 2-99

In a nitrogen atmosphere, 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 and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 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), sodium tert in nitrogen atmosphere -butoxide (5.7 g, 59.8 mmol) was added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.6 g of compound subC-9. (Yield 66%, MS: [M+H] ⁺ = 480)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.3 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), sodium tert-butoxide (5.7 g, 59.8 mmol) into 200 ml of Xylene, followed by stirring and reflux. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.9 g of compound subC-10. (Yield 64%, MS: [M+H] ⁺ = 404)

In a nitrogen atmosphere, 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 and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 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), sodium tert in a nitrogen atmosphere -butoxide (5.7 g, 59.8 mmol) was added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.9 g of compound subC-11. (Yield 63%, MS: [M+H] ⁺ = 480)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.2 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), sodium tert in nitrogen atmosphere -butoxide (5.7 g, 59.8 mmol) was added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.2 g of compound subC-12. (Yield 69%, MS: [M+H] ⁺ = 480)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.4 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), sodium tert in nitrogen atmosphere -butoxide (5.7 g, 59.8 mmol) was added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.6 g of compound subC-13. (Yield 66%, MS: [M+H] ⁺ = 480

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 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), sodium tert-butoxide (5.7 g, 59.8 mmol) into 200 ml of Xylene, followed by stirring and reflux. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.9 g of compound subC-14. (Yield 75%, MS: [M+H] ⁺ = 405)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.2 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), sodium tert in a nitrogen atmosphere -butoxide (5.7 g, 59.8 mmol) was added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.1 g of compound subC-15. (Yield 64%, MS: [M+H] ⁺ = 480)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11 g of compound 2-106. (Yield 65%, MS: [M+H] ⁺ = 815)

Synthesis Example 2-107

In a nitrogen atmosphere, 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. Stir and reflux. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.8 g of compound subD-1. (Yield 72%, MS: [M+H] ⁺ = 328)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.5 g of compound 2-107. (Yield 72%, MS: [M+H] ⁺ = 663)

Synthesis Example 2-108

In a nitrogen atmosphere, 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 and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.4 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 mixed with Xylene in a nitrogen atmosphere. It was added to 200 ml and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.8 g of compound subD-2. (Yield 71%, MS: [M+H] ⁺ = 454)

In a nitrogen atmosphere, 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 and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.8 g of compound 2-109. (Yield 62%, MS: [M+H] ⁺ = 789)

Synthesis Example 2-110

In a nitrogen atmosphere, 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. Stir and reflux. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.3 g of compound subD-3. (Yield 71%, MS: [M+H] ⁺ = 378)

In a nitrogen atmosphere, 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 and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 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), sodium tert-butoxide (5.7 g, 59.8 mmol) into 200 ml of Xylene, followed by stirring and reflux. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.7 g of compound subD-4. (Yield 74%, MS: [M+H] ⁺ = 404)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.8 g of compound 2-111. (Yield 72%, MS: [M+H] ⁺ = 663)

Synthesis Example 2-112

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.8 g of compound 2-112. (Yield 75%, MS: [M+H] ⁺ = 689)

Synthesis Example 2-113

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.1 g of compound 2-113. (Yield 65%, MS: [M+H] ⁺ = 627)

Synthesis Example 2-114

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.3 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), sodium tert in nitrogen atmosphere -butoxide (5.7 g, 59.8 mmol) was added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.7 g of compound subD-5. (Yield 71%, MS: [M+H] ⁺ = 480)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.1 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), sodium tert in a nitrogen atmosphere -butoxide (5.7 g, 59.8 mmol) was added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 16.1 g of compound subD-6. (Yield 73%, MS: [M+H] ⁺ = 480)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.9 g of compound 2-116. (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), sodium tert-butoxide (5.7 g, 59.8 mmol) into 200 ml of Xylene, followed by stirring and reflux. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.4 g of compound subD-7. (Yield 72%, MS: [M+H] ⁺ = 404)

In a nitrogen atmosphere, compound subD-7 (10 g, 24.8 mmol), compound amine1 (10.3 g, 26 mmol), and sodium tert-butoxide (3.1 g, 32.2 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.6 g of compound 2-117. (Yield 72%, MS: [M+H] ⁺ = 765)

Synthesis Example 2-118

In a nitrogen atmosphere, 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 and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 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), sodium tert in a nitrogen atmosphere -butoxide (5.7 g, 59.8 mmol) was added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 16.3 g of compound subD-8. (Yield 74%, MS: [M+H] ⁺ = 480)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 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), Sodium tert-butoxide (5.7 g, 59.8 mmol) was added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.4 g of compound subD-9. (Yield 70%, MS: [M+H] ⁺ = 480)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.9 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), sodium tert in a nitrogen atmosphere -butoxide (5.7 g, 59.8 mmol) was added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.4 g of compound subD-10. (Yield 70%, MS: [M+H] ⁺ = 480)

In a nitrogen atmosphere, 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 and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.9 g of compound 2-121. (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), sodium tert in a nitrogen atmosphere -butoxide (5.7 g, 59.8 mmol) was added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.4 g of compound subD-11. (Yield 70%, MS: [M+H] ⁺ = 480)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.6 g of compound 2-122. (Yield 74%, MS: [M+H] ⁺ = 815)

Synthesis Example 2-123

In a nitrogen atmosphere, 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. Stir and reflux. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.7 g of compound subD-12. (Yield 71%, MS: [M+H] ⁺ = 328)

In a nitrogen atmosphere, compound subD-12 (10 g, 30.5 mmol), compound amine91 (11.9 g, 32 mmol), and sodium tert-butoxide (3.8 g, 39.7 mmol) were added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.5 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), sodium tert-butoxide (5.7 g, 59.8 mmol) into 200 ml of Xylene, followed by stirring and reflux. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.6 g of compound subD-13. (Yield 68%, MS: [M+H] ⁺ = 404)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.2 g of compound 2-124. (Yield 70%, MS: [M+H] ⁺ = 763)

Synthesis Example 2-125

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.4 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), sodium tert in a nitrogen atmosphere -butoxide (5.7 g, 59.8 mmol) was added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.3 g of compound subD-14. (Yield 65%, MS: [M+H] ⁺ = 480)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 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), Sodium tert-butoxide (5.7 g, 59.8 mmol) was added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.9 g of compound subD-15. (Yield 72%, MS: [M+H] ⁺ = 480)

In a nitrogen atmosphere, compound subD-15 (10 g, 20.8 mmol), compound amine92 (10.3 g, 21.9 mmol), and sodium tert-butoxide (2.6 g, 27.1 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.1 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), sodium tert-butoxide (5.7 g, 59.8 mmol) into 200 ml of Xylene, followed by stirring and reflux. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.7 g of compound subD-16. (Yield 63%, MS: [M+H] ⁺ = 404)

In a nitrogen atmosphere, compound subD-16 (10 g, 24.8 mmol), compound amine1 (10.3 g, 26 mmol), and sodium tert-butoxide (3.1 g, 32.2 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14 g of compound 2-128. (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), sodium tert-butoxide (5.7 g, 59.8 mmol) into 200 ml of Xylene, followed by stirring and reflux. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13 g of compound subD-17. (Yield 70%, MS: [M+H] ⁺ = 404)

In a nitrogen atmosphere, compound subD-17 (10 g, 24.8 mmol), compound amine93 (11.6 g, 26 mmol), and sodium tert-butoxide (3.1 g, 32.2 mmol) were added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.9 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), sodium tert-butoxide (5.7 g, 59.8 mmol) into 200 ml of Xylene, followed by stirring and reflux. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.2 g of compound subD-18. (Yield 66%, MS: [M+H] ⁺ = 404)

In a nitrogen atmosphere, 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, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.5 g of compound 2-130. (Yield 61%, MS: [M+H] ⁺ = 765)

Example 1

A glass substrate coated with ITO (indium tin oxide) to a thickness of 1,000 Å was put in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, a Fischer Co. product was used as the detergent, and distilled water filtered through a second filter of a Millipore Co. product was used as the distilled water. After washing the ITO for 30 minutes, ultrasonic cleaning was performed twice with distilled water for 10 minutes. After washing with distilled water, ultrasonic cleaning was performed with solvents such as isopropyl alcohol, acetone, and methanol, dried, and transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transferred to a vacuum deposition machine.

The following compound HI-1 was formed to a thickness of 1150 Å as a hole injection layer on the prepared ITO transparent electrode, but the following compound A-1 was p-doped at a concentration of 1.5% by weight. The following compound HT-1 was vacuum deposited on the hole injection layer to form a hole transport layer having a thickness of 800 Å. Subsequently, an electron blocking layer was formed by vacuum depositing the following compound EB-1 to a film thickness of 150 Å on the hole transport layer. Then, on the EB-1 deposited film, the previously prepared compounds 1-1, 2-1, and the following compound Dp-7 were vacuum-deposited at a weight ratio of 49:49:2 to form a red light emitting layer having a thickness of 400 Å. A hole blocking layer was formed on the light emitting layer by vacuum depositing the following compound HB-1 to a film thickness of 30 Å. Subsequently, the following compound ET-1 and the following compound LiQ were vacuum deposited at a weight ratio of 2:1 on the hole blocking layer to form an electron injection and transport layer with a thickness of 300 Å. A negative electrode was formed by sequentially depositing lithium fluoride (LiF) to a thickness of 12 Å and aluminum to a thickness of 1,000 Å on the electron injection and transport layer.

In the above process, the deposition rate of the organic material was maintained at 0.4 ~ 0.7 Å/sec, the deposition rate of lithium fluoride on the anode was 0.3 Å/sec, and the deposition rate of aluminum was 2 Å/sec, and the vacuum level during deposition was 2 * 10 Maintaining ^-7 to 5 * 10 ^-6 torr, an organic light emitting device was fabricated.

Examples 2 to 235

In the organic light emitting device of Example 1, the compound represented by Formula 1 and the compound represented by Formula 2 described in Tables 1 to 6 were used instead of Compound 1-1 and Compound 2-1 as the first host and the second host in a weight ratio of 1 An organic light emitting device was manufactured in the same manner as in Example 1, except that co-evaporation was performed with: 1.

Comparative Examples 1 to 60

In the organic light emitting device of Example 1, Comparative Compounds A-1 to A-12 were used instead of Compound 1-1 as the first host, and Chemical Formulas 2 shown in Tables 7 and 8 were used instead of Compound 2-1 as the second host. An organic light emitting device was manufactured in the same manner as in Example 1, except that the compound represented by was co-evaporated at a weight ratio of 1:1. The specific structures of the compounds A-1 to A-12 are as follows.

Comparative Example 61 to Comparative Example 156

In the organic light emitting device of Example 1, a compound represented by Formula 1 described in Tables 9 to 11 was used instead of Compound 1-1 as a first host, and Comparative Compound B-1 was used instead of Compound 2-1 as a second host. to B-12, an organic light emitting device was manufactured in the same manner as in Example 1, except for co-evaporation at a weight ratio of 1:1. Specific structures of the compounds B-1 to B-12 are as follows.

Experimental example

When current was applied to the organic light emitting devices prepared in Examples 1 to 235 and Comparative Examples 1 to 156, voltage and efficiency were measured (15 mA/cm ² standard), and the results are shown in Tables 1 to 156. Table 10 shows. Lifetime T95 was measured based on 7000 nit, and T95 means the time required to decrease from the initial lifespan to 95%.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[Table 7]

[Table 8]

[Table 9]

[Table 10]

[Table 11]

When current was applied to the organic light emitting devices prepared in Examples 1 to 235 and Comparative Examples 1 to 156, the results of Tables 1 to 11 were obtained. The red organic light emitting devices of the above Examples and Comparative Examples used a material widely used in the prior art, and had a structure in which compound EB-1 was used as an electron blocking layer and Dp-7 was used as a dopant of the red light emitting layer. As shown in Tables 7 and 8, when Comparative Examples Compounds A-1 to A-12 and the compound represented by Formula 2 of the present invention are co-deposited and used as a red light emitting layer, the driving voltage is generally higher than the combination of the present invention. As shown in Tables 9 to 11, the driving voltage was As a result, efficiency and lifespan decreased.

Inferred from these results, the reason why the driving voltage is improved and the efficiency and lifespan is increased is that the combination of the compound of Formula 1 as the first host and the compound of Formula 2 as the second host of the present invention is used as a red dopant in the red light emitting layer. It can be inferred that this is because it favors energy transfer.

Therefore, since the combination of the compound represented by Formula 1 and the compound represented by Formula 2 of the present invention achieves a more stable balance in the light emitting layer than the combination with the comparative compound, electrons and holes combine to form excitons, thereby increasing efficiency and lifetime. can confirm that From this, it was confirmed that the driving voltage, luminous efficiency and lifetime characteristics of the organic light emitting device can be improved when the compound represented by Formula 1 and the compound represented by Formula 2 of the present invention are co-deposited and used as a host of the red light emitting layer. .

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

Claims (10)

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

In Formula 1,
R ₁ is each independently hydrogen, deuterium, substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted C _2-60 including any one or more selected from the group consisting of N, O and S; Heteroaryl;
R ₂ are each independently hydrogen or deuterium;
Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C _6-60 aryl, or a substituted or unsubstituted C _2-60 hetero including any one or more selected from the group consisting of N, O and S; aryl,
When R ₁ is each independently hydrogen or deuterium, at least one of Ar ₁ and Ar ₂ includes at least one selected from the group consisting of substituted or unsubstituted N, O and S C _2-60 Heteroaryl;
L ₁ and L ₂ are each independently a single bond or a substituted or unsubstituted C _6-60 arylene;
a is an integer from 1 to 7;
b is an integer from 1 to 6;
The compound represented by Formula 1 may not contain deuterium or may contain at least one deuterium,
[Formula 2]

In Formula 2,
A is a benzene ring or naphthalene ring fused with an adjacent ring,
Ar ₃ and Ar ₄ are each independently a substituted or unsubstituted C _6-60 aryl, or a substituted or unsubstituted C _2-60 hetero including any one or more selected from the group consisting of N, O and S; aryl,
L ₃ is a substituted or unsubstituted C _6-60 arylene;
L ₄ and L ₅ are each independently a single bond, a substituted or unsubstituted C _6-60 arylene, or a substituted or unsubstituted C containing any one or more selected from the group consisting of N, O and S; _2-60 heteroarylene.
According to claim 1,
Chemical Formula 1 is represented by any one of the following Chemical Formulas 1-1 to 1-11,
Organic Light-Emitting Elements:

In Formula 1-1 to Formula 1-11,
Descriptions of R ₁ , R ₂ , Ar ₁ , Ar ₂ , L ₁ , L ₂ , a and b are as defined in claim 1.
According to claim 1,
each R ₁ is independently hydrogen, deuterium, phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, naphthyl phenyl, phenyl naphthyl, dibenzofuranyl, or dibenzothiophenyl;
Hydrogens of the phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, naphthyl phenyl, phenyl naphthyl, dibenzofuranyl and dibenzothiophenyl are each independently unsubstituted or substituted with deuterium,
organic light emitting device.
According to claim 1,
Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, dibenzofuranyl, dibenzothiophenyl, or triphenylsilyl phenyl;
The hydrogens of Ar ₁ and Ar ₂ are each independently unsubstituted or substituted with deuterium,
organic light emitting device.
According to claim 1,
L ₁ and L ₂ are each independently a single bond, phenylene, biphenyldiyl, or naphthalenediyl;
Hydrogens of the phenylene, biphenyldiyl and naphthalenediyl are each independently unsubstituted or substituted with deuterium,
organic light emitting device.
According to claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of
Organic Light-Emitting Elements:

.
According to claim 1, Ar ₃ and Ar ₄ are each independently phenyl, biphenylyl, terphenylyl, quaterphenylyl, triphenylmethyl phenyl, triphenylsilyl phenyl, naphthyl, phenanthrenyl, triphenylenyl , fluoranthenyl, chrysenyl, benzo[c]phenanthrenyl, carbazole, phenyl carbazole, dimethylfluorenyl, dibenzofuranyl, or dibenzothiophenyl,
organic light emitting device.
According to claim 1,
L ₃ is phenylene, biphenyldiyl, terphenyldiyl, quaterphenyldiyl, naphthalenediyl, phenylnaphthalenediyl, or phenylnaphthalenediyl substituted with one phenyl;
organic light emitting device.
According to claim 1,
L ₄ and L ₅ are each independently a single bond, phenylene, biphenyldiyl, naphthalenediyl, phenylnaphthalenediyl, or carbazoldiyl;
organic light emitting device.
According to claim 1,
The compound represented by Formula 2 is any one selected from the group consisting of
Organic Light-Emitting Elements:

.

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