WO2024253479A1 - Organic light-emitting device - Google Patents

Abstract

The present invention provides an organic light-emitting device having improved driving voltage, efficiency, and lifespan.

Description

Organic light emitting diode

Cross-citation with related application(s)

This application claims the benefit of priority to Korean Patent Application No. 10-2023-0073838, filed June 8, 2023, and Korean Patent Application No. 10-2024-0074506, filed June 7, 2024, the entire contents of which are incorporated herein by reference.

The present invention relates to an organic light-emitting device with improved driving voltage, efficiency, and lifespan.

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

Organic light-emitting devices generally have a structure including an anode, a cathode, and an organic layer between the anode and the cathode. The organic layer is often composed of a multilayer structure composed of different materials in order to increase the efficiency and stability of the organic light-emitting device, and may be composed of, for example, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, etc. In the structure of such an organic light-emitting device, when a voltage is applied between two electrodes, holes are injected into the organic layer from the anode and electrons are injected into the organic layer from the cathode, and when the injected holes and electrons meet, excitons are formed, and when these excitons fall back to the ground state, light is emitted.

In the organic light-emitting devices described above, there is a continuous demand for the development of organic light-emitting devices with improved driving voltage, efficiency, and lifespan.

[Prior art literature]

[Patent Document]

(Patent Document 1) Korean Patent Publication No. 10-2000-0051826

The present invention relates to an organic light-emitting device with improved driving voltage, efficiency, and lifespan.

The present invention provides the following organic light-emitting device:

Comprising an anode, a cathode, and a light-emitting layer between the anode and the cathode,

The above light-emitting layer comprises a compound represented by the following chemical formula 1 and a compound represented by the following chemical formula 2.

Organic light emitting diodes:

[Chemical Formula 1]

In the above chemical formula 1,

Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C _6-60 aryl; or a C _2-60 heteroaryl comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S,

L ₁ is a single bond; or a substituted or unsubstituted C _6-60 arylene,

L ₂ and L ₃ are each independently a single bond; a substituted or unsubstituted C _6-60 arylene; or a C _2-60 heteroarylene comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S,

One of R ₁ to R ₇ is connected to a substituent -Ar ₃ , and the others are each independently hydrogen or deuterium,

Ar ₃ is a substituted or unsubstituted C _6-60 aryl; or a C _2-60 heteroaryl comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S,

[Chemical formula 2]

In the above chemical formula 2,

Ar' ₁ is hydrogen; deuterium; substituted or unsubstituted C _6-60 aryl; or C _2-60 heteroaryl comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S,

Ar' ₂ and Ar' ₃ are each independently a substituted or unsubstituted C _6-60 aryl; or a C _2-60 heteroaryl comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S,

L' ₁ to L' ₃ are each independently a single bond; a substituted or unsubstituted C _6-60 arylene; or a C _2-60 heteroarylene comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S,

L' ₄ is a single bond or a substituted or unsubstituted C _6-60 arylene,

R' ₁ is hydrogen or deuterium,

a is an integer from 1 to 8,

-At least one of -L' ₁ -Ar' ₁ and R' ₁ is deuterium,

The deuterium substitution rate of the compound represented by the above chemical formula 2 is 50% or more.

The organic light-emitting device described above can improve efficiency, low driving voltage, and/or lifespan characteristics in the organic light-emitting device by including a compound represented by the chemical formula 1 and a compound represented by the chemical formula 2 in the light-emitting layer.

Figure 1 illustrates 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).

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

Hereinafter, the present invention will be described in more detail to help understand the present invention.

또는

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

or

means a bond connecting to another substituent.

The term "substituted or unsubstituted" as used herein means a group which is unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium; a halogen group; a nitrile group; a nitro group; a hydroxy group; a carbonyl group; an ester group; an imide group; an amino group; a phosphine oxide group; an alkoxy group; an aryloxy group; an alkylthioxy group; an arylthioxy group; an alkylsulfoxy group; an arylsulfoxy group; a silyl group; a boron group; an alkyl group; a cycloalkyl group; an alkenyl group; an aryl group; an aralkyl group; an aralkenyl group; an alkylaryl group; an alkylamine group; an aralkylamine group; a heteroarylamine group; an arylamine group; an arylphosphine group; or a heterocyclic group containing at least one of N, O, and S atoms, or a substituted or unsubstituted group in which two or more of the above-mentioned substituents are linked. For example, the "substituent linked with two or more substituents" can be a biphenyl group. That is, the biphenyl group can be an aryl group, or it can be interpreted as a substituent in which two phenyl groups are connected.

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

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

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

In this specification, the silyl group specifically includes, but is not limited to, 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, etc.

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

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

In the present specification, the alkyl group may be linear or branched, 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 in the alkyl group is 1 to 20. According to another embodiment, the number of carbon atoms in the alkyl group is 1 to 10. According to another embodiment, the number of carbon atoms in the alkyl group is 1 to 6. Specific examples of alkyl groups include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, These include, but are not limited to, 2-methylpentyl, 4-methylhexyl, and 5-methylhexyl.

In the present specification, the alkenyl group may be linear or branched, and the carbon number is not particularly limited, but is preferably 2 to 40. According to one embodiment, the carbon number of the alkenyl group is 2 to 20. According to another embodiment, the carbon number of the alkenyl group is 2 to 10. According to another embodiment, the carbon number of the alkenyl group is 2 to 6. Specific examples include, but are not limited to, 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, and styrenyl.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms. According to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, examples thereof include, but are not limited to, 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.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to one embodiment, the aryl group has 6 to 20 carbon atoms. The monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, or the like, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, or 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 combined with each other to form a spiro structure. When the fluorenyl group is substituted,

It can be, but is not limited to, the following.

In the present specification, a heterocyclic group is a heterocyclic group containing at least one of O, N, Si, and S as a heteroatom, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of heterocyclic groups include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, acridyl group, pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group, carbazole group, benzoxazole group, benzimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, isoxazolyl group, thiadiazolyl group, Examples include, but are not limited to, phenothiazinyl and dibenzofuranyl groups.

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

As used herein, the term “deuterated or deuterium substituted” means that at least one of the substitutable hydrogens in the compound, divalent linking group or monovalent substituent is replaced with deuterium.

Additionally, the term "unsubstituted or substituted with deuterium" or "substituted or unsubstituted with deuterium" means "unsubstituted or substituted with 1 to 9 deuterium atoms". For example, the term "unsubstituted or substituted with deuterium phenanthryl" can be understood to mean "unsubstituted or substituted with 1 to 9 deuterium atoms", considering that the maximum number of hydrogen atoms that can be substituted with deuterium in the phenanthryl structure is 9.

Also, the term "deuterated structure" is meant to encompass compounds of all structures, divalent linkages or monovalent substituents in which at least one hydrogen is replaced by a deuterium. For example, the deuterated structure of phenyl can be understood to refer to monovalent substituents of all structures in which at least one substitutable hydrogen in the phenyl group is replaced by a deuterium, as follows.

In the present specification, the deuterium substitution rate of a compound is calculated as a percentage of the number of substituted deuteriums compared to the total number of hydrogens that can exist in the compound (the sum of the number of hydrogens replaceable with deuterium in the compound and the number of substituted deuteriums). Therefore, the deuterium substitution rate of a compound being "K%" means that K% of the hydrogens replaceable with deuterium in the compound have been replaced with deuterium.

At this time, the above "deuterium substitution rate" or "deuteration degree" can be measured by a commonly known method using MALDI-TOF MS (Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometer), nuclear magnetic resonance spectroscopy (1H NMR), TLC/MS (Thin-Layer Chromatography/Mass Spectrometry), or GC/MS (Gas Chromatography/Mass Spectrometry).

More specifically, when using MALDI-TOF MS, the "deuterium substitution rate" or "deuteration degree" can be obtained by obtaining the number of substituted deuteriums in the compound through MALDI-TOF MS analysis, and then calculating the ratio of the number of substituted deuteriums to the total number of hydrogens that can exist in the compound as a percentage. Therefore, the deuterium substitution rate of a compound being "K%" means that K% of the hydrogens in the compound that can be replaced with deuterium have been replaced with deuterium.

In addition, when using TLC/MS, the "deuterium substitution rate" or "degree of deuteration" can be obtained by calculating the substitution rate based on the maximum value (max. value) of the distribution of molecular weights at the end of the reaction.

In addition, when using nuclear magnetic resonance spectroscopy (1H NMR), the "deuterium substitution rate" or "deuteration degree" can be calculated from the integration amount of the total peak using the integration ratio on 1H NMR.

Meanwhile, in this specification, "deuterium does not exist at a specific position" means that the deuterium substitution rate at that position is 10% or less, and does not mean that the deuterium substitution rate is 0%. In addition, in this specification, "deuterium exists at a specific position" means that the deuterium substitution rate at that position is more than 1%, and does not mean that the deuterium substitution rate at that position is 100%. In this way, the "deuterium substitution rate at a specific position" can be calculated by comparing the 1H NMR spectrum of a compound where deuterium is not substituted with the 1H NMR spectrum of a compound where deuterium is substituted, and confirming the rate at which the integral of each peak decreases for each hydrogen (proton) position.

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

Positive and negative poles

The anode and cathode used in the present invention refer to electrodes used in organic light-emitting devices.

As the above anode material, a material having a high work function is generally preferred so that hole injection into the organic layer can be smooth. Specific examples of the above anode material include, but are not limited to, 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; and conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole, and polyaniline.

The cathode material is preferably a material having a low work function to facilitate electron injection into the organic layer. Specific examples of the cathode material include, but are not limited to, metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; multilayered materials such as LiF/Al or LiO ₂ /Al.

Hole injection layer

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

The above hole injection layer is a layer that injects holes from the electrode, and the hole injection material is preferably a compound that has the ability to transport holes, has an excellent hole injection effect at the anode, an excellent hole injection effect for the light-emitting layer or the light-emitting material, prevents movement of excitons generated in the light-emitting layer to the electron injection layer or the electron injection material, and has excellent thin film forming ability. In addition, it is preferable that the HOMO (highest occupied molecular orbital) 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 hole injection materials include, but are not limited to, metal porphyrins, oligothiophenes, arylamine-based organic compounds, hexanitrilehexaazatriphenylene-based organic compounds, quinacridone-based organic compounds, perylene-based organic compounds, anthraquinones, and conductive polymers of polyaniline and polythiophene-based compounds.

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 when a hole injection layer is present) as needed.

The above 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. A hole transport material that can transport holes from the anode or the hole injection layer and transfer them to the light-emitting layer is suitable, and a material with high mobility for holes is suitable.

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

Electronic barrier layer

The above electron blocking layer is a layer placed between the hole transport layer and the light emitting layer to prevent electrons injected from the cathode from being recombined in the light emitting layer and from passing to the hole transport layer. It is also called an electron suppression layer or electron blocking layer. A material having a lower electron affinity than the electron transport layer is preferable for the electron blocking layer.

luminescent layer

The light-emitting layer used in the present invention refers to a layer that can emit light in the visible light range 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 the chemical formula 1 and the compound represented by the chemical formula 2 are included as hosts.

Preferably, the compound represented by the chemical formula 1 may be represented by any one of the following chemical formulas 1-1 to 1-3:

[Chemical Formula 1-1]

[Chemical Formula 1-2]

[Chemical Formula 1-3]

In the above chemical formulas 1-1 to 1-3,

Ar ₁ to Ar ₃ , L ₁ to L ₃ and R ₁ to R ₇ are as defined in chemical formula 1.

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

More preferably, Ar ₁ and Ar ₂ can each independently be phenyl, biphenylyl, terphenylyl, triphenylsilyl phenyl, naphthyl, phenanthrenyl, dibenzofuranyl, or dibenzothiophenyl, wherein phenyl, biphenylyl, terphenylyl, triphenylsilyl phenyl, naphthyl, phenanthrenyl, dibenzofuranyl, and dibenzothiophenyl can independently be unsubstituted or substituted with one or more deuterium atoms.

More preferably, Ar ₁ and Ar ₂ may each independently be any one selected from the group consisting of: wherein Ar ₁ and Ar ₂ may each independently be unsubstituted or substituted with one or more deuterium atoms:

Preferably, L ₁ is a single bond; or it may be a substituted or unsubstituted C _6-20 arylene,

More preferably, L ₁ may be a single bond, a substituted or unsubstituted phenylene, or a substituted or unsubstituted naphthalenediyl,

Most preferably, L ₁ can be a single bond, phenylene, or naphthalenediyl, wherein each of the phenylene and naphthalenediyl can be independently unsubstituted or substituted with one or more deuterium atoms.

Preferably, L ₂ and L ₃ can each independently be a single bond; or a substituted or unsubstituted C _6-20 arylene; or a C _2-20 heteroarylene comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S,

More preferably, L ₂ and L ₃ may each independently be a single bond, a substituted or unsubstituted phenylene, a substituted or unsubstituted biphenyldiyl, or a substituted or unsubstituted naphthalenediyl,

More preferably, L ₂ and L ₃ may each independently be a single bond, phenylene, biphenyldiyl, or naphthalenediyl, wherein the phenylene, biphenyldiyl and naphthalenediyl may each independently be unsubstituted or substituted with one or more deuterium atoms.

More preferably, L ₂ and L ₃ may each independently be a single bond or one selected from the group consisting of: wherein L ₂ and L ₃ may each independently be unsubstituted or substituted with one or more deuterium atoms:

Preferably, Ar ₃ may be, independently, hydrogen; deuterium; substituted or unsubstituted C _6-20 aryl; or C _2-20 heteroaryl comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S,

More preferably, Ar ₃ can be phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, triphenylenyl, naphthyl phenyl, phenyl naphthyl, fluoranthenyl, dihydroindenyl, dibenzofuranyl, dibenzothiophenyl, benzonaphthofuranyl, or benzonaphthothiophenyl, wherein phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, triphenylenyl, naphthyl phenyl, phenyl naphthyl, fluoranthenyl, dihydroindenyl, dibenzofuranyl, dibenzothiophenyl, benzonaphthofuranyl, and benzonaphthothiophenyl can be unsubstituted or substituted with one or more deuterium.

Preferably, at least one of Ar ₁ to Ar ₃ may be naphthyl, phenyl naphthyl, naphthyl phenyl, phenanthrenyl, fluoranthenyl, dibenzofuranyl, dibenzothiophenyl, benzonaphthofuranyl, or benzonaphthothiophenyl, wherein each of the naphthyl, phenyl naphthyl, naphthyl phenyl, phenanthrenyl, fluoranthenyl, dibenzofuranyl, dibenzothiophenyl, benzonaphthofuranyl, and benzonaphthothiophenyl may independently be unsubstituted or substituted with one or more deuterium atoms.

More preferably, at least one of Ar ₁ to Ar ₃ may be naphthyl, phenyl naphthyl, naphthyl phenyl, fluoranthenyl, dibenzofuranyl, benzonaphthofuranyl, or benzonaphthothiophenyl, wherein each of the naphthyl, phenyl naphthyl, naphthyl phenyl, fluoranthenyl, dibenzofuranyl, benzonaphthofuranyl and benzonaphthothiophenyl may independently be unsubstituted or substituted with one or more deuterium atoms.

Meanwhile, if the number of deuterium substitutions of the compound is to be indicated, it can be indicated by the following chemical formula 1D:

[Chemical Formula 1D]

In the above chemical formula 1D,

Dn means that n hydrogens are replaced with deuterium,

Here, n is an integer greater than or equal to 13,

Ar ₁ to Ar _3d , L _1d to L _3d and R _1d to R _7d represent Ar ₁ to Ar ₃ , L ₁ to L ₃ and R ₁ to R ₇ substituents which are not substituted with deuterium, respectively.

For example, in the chemical formula 1D, n of Dn may be 13 or more, 14 or more, 15 or more, 16 or more, 17 or more, 18 or more, or 19 or more, and 50 or less, 45 or less, 40 or less, 38 or less, 36 or less, 34 or less, 32 or less, 30 or less, 28 or less, 26 or less, 24 or less, 23 or less, 22 or less, 21 or less, or 20 or less.

Representative examples of compounds represented by the chemical formula 1 are as follows:

.

.

The compound represented by the above chemical formula 1 can be manufactured, for example, by a manufacturing method such as the following reaction scheme 1, or by additionally performing a deuterium substitution reaction after performing reaction scheme 1, and the remaining compounds can also be manufactured similarly.

[Reaction Formula 1]

In the above reaction scheme 1, Ar ₁ , Ar ₂ , L ₁ to L ₃ and R ₁ to R ₇ are as defined in the above chemical formula 1, X ₁ is halogen, and preferably X ₁ is chloro or bromo.

The above reaction scheme 1 is a Suzuki coupling reaction, which is preferably performed in the presence of a palladium catalyst and a base, and the reactor for the Suzuki coupling reaction can be changed as known in the art. The above-described deuterium substitution reaction is preferably performed in the presence of D ₂ O, and the reactor, catalyst, solvent, etc. for the deuterium substitution reaction can be changed as appropriate for the desired product as known in the art. The above manufacturing method can be more specifically described in the manufacturing example described below.

In the compound represented by the above chemical formula 2, at least one of -L' ₁ -Ar' ₁ and R' ₁ is deuterium, so that phenanthrenyl of the chemical formula 2 is substituted with at least one hydrogen. Here, the meaning of 'phenanthrenyl is substituted with at least one deuterium' means 'at least one of the nine carbons on which deuterium of the phenanthrenyl of the chemical formula 2 can be substituted has a deuterium, not hydrogen.' More specifically, it means that one of the carbons of the phenanthrenyl included in the compound represented by the above chemical formula 1 is substituted with deuterium, and the deuterium substitution rate at the remaining eight carbons is each more than 1%. The deuterium substitution rate at each carbon of the phenanthrenyl can be obtained by comparing ^{the 1} H NMR spectrum of a compound on which deuterium is not substituted with the ¹ H NMR spectrum of a compound on which deuterium is substituted, as described above.

Preferably, the chemical formula 2 can be represented by any one of the following chemical formulas 2A to 2I.

[Chemical Formula 2A]

[Chemical Formula 2B]

[Chemical Formula 2C]

[Chemical Formula 2D]

[Chemical Formula 2E]

[Chemical Formula 2F]

[Chemical formula 2G]

[chemical formula 2H]

[Chemical Formula 2I]

In the above chemical formulas 2A to 2I,

D is deuterium,

a' is an integer from 0 to 7,

Ar' ₁ to Ar' ₃ , L' ₁ to L' ₄ and R' ₁ are as defined in the chemical formula 2.

Preferably, Ar' ₁ may be a C _2-20 heteroaryl comprising 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,

More preferably, Ar' ₁ can be hydrogen; deuterium; or substituted or unsubstituted C _6-20 aryl.

More preferably, Ar' ₁ can be hydrogen; deuterium; or phenyl which is unsubstituted or substituted with one or more deuterium atoms.

Most preferably, Ar' ₁ may be hydrogen; or deuterium.

Preferably, Ar' ₂ and Ar' ₃ can each independently be a substituted or unsubstituted C _6-20 aryl; or a C _2-20 heteroaryl comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S,

More preferably, Ar' ₂ and Ar' ₃ may each independently be phenyl, biphenylyl, terphenylyl, quarterphenylyl, naphthyl, phenyl naphthyl, naphthyl phenyl, tetrahydronaphthyl, phenanthrenyl, phenyl phenanthrenyl, triphenylenyl, dimethylfluorenyl, diphenylfluorenyl, carbazolyl, phenyl carbazolyl, dibenzofuranyl, dibenzothiophenyl, or phenyl dibenzofuranyl, and said phenyl, biphenylyl, terphenylyl, quarterphenylyl, naphthyl, phenyl naphthyl, naphthyl phenyl, tetrahydronaphthyl, phenanthrenyl, phenyl phenanthrenyl, triphenylenyl, dimethylfluorenyl, diphenylfluorenyl, carbazolyl, phenyl carbazolyl, dibenzofuranyl, dibenzothiophenyl, and phenyl dibenzofuranyl may each independently be unsubstituted or substituted with one or more deuterium, or one or more substituted or unsubstituted C _1-10 alkyl.

More preferably, Ar' ₂ and Ar' ₃ are each independently phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl, phenyl naphthyl, naphthyl phenyl, tetrahydronaphthyl, phenanthrenyl, phenyl phenanthrenyl, triphenylenyl, dimethylfluorenyl, diphenylfluorenyl, carbazolyl, phenyl carbazolyl, dibenzofuranyl, dibenzothiophenyl, phenyl dibenzofuranyl, tetramethyl tetrahydronaphthyl, methyl phenyl, isopropyl phenyl, tertbutyl phenyl, ditertbutyl phenyl, methyl biphenylyl, isopropyl biphenylyl, tertbutyl biphenylyl, dimethyl biphenylyl, diisopropyl biphenylyl, ditertbutyl biphenylyl, methyl terphenylyl, isopropyl terphenylyl, or tertbutyl terphenylyl, wherein said phenyl, biphenylyl, terphenylyl, Quaterphenylyl, naphthyl, phenyl naphthyl, naphthyl phenyl, tetrahydronaphthyl, phenanthrenyl, phenyl phenanthrenyl, triphenylenyl, dimethylfluorenyl, diphenylfluorenyl, carbazolyl, phenyl carbazolyl, dibenzofuranyl, dibenzothiophenyl, phenyl dibenzofuranyl, tetramethyl tetrahydronaphthyl, methyl phenyl, isopropyl phenyl, tertbutyl phenyl, ditertbutyl phenyl, methyl biphenylyl, isopropyl biphenylyl, tertbutyl biphenylyl, dimethyl biphenylyl, diisopropyl biphenylyl, ditertbutyl biphenylyl, methyl terphenylyl, isopropyl terphenylyl, and tertbutyl terphenylyl can each independently be unsubstituted or substituted with one or more deuterium.

Most preferably, Ar' ₂ and Ar' ₃ can each independently be phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, tetrahydronaphthyl, tetramethyltetrahydronaphthyl, phenyl substituted with one or two methyl groups, phenyl substituted with one or two isopropyl groups, phenyl substituted with one or two tertbutyl groups, dibenzofuranyl, or dibenzothiophenyl, wherein said phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, tetrahydronaphthyl, tetramethyltetrahydronaphthyl, phenyl substituted with one or two methyl groups, phenyl substituted with one or two isopropyl groups, phenyl substituted with one or two tertbutyl groups, dibenzofuranyl and dibenzothiophenyl can each independently be unsubstituted or substituted with one or more deuterium groups.

Preferably, L' ₁ to L' ₃ may each independently be a single bond; a substituted or unsubstituted C _6-20 arylene; or a C _2-20 heteroarylene comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S,

More preferably, L' ₁ to L' ₃ may each independently be a single bond, phenylene, biphenylylene, naphthylene, phenyl naphthylene, phenanthrenylene, carbazolylene, phenyl carbazolylene, dibenzofuranylene, phenyl dibenzofuranylene, or dimethylfluorenylene, and wherein phenylene, biphenylylene, naphthylene, phenyl naphthylene, phenanthrenylene, carbazolylene, phenyl carbazolylene, dibenzofuranylene, phenyl dibenzofuranylene, and dimethylfluorenylene may each independently be unsubstituted or substituted with one or more deuterium atoms.

Preferably, L' ₁ is a single bond, and L' ₂ and L' ₃ can each independently be a single bond; a substituted or unsubstituted C _6-20 arylene; or a C _2-20 heteroarylene comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S,

More preferably, L' ₁ is a single bond, and L' ₂ and L' ₃ can each independently be a single bond, phenylene, biphenylylene, naphthylene, phenyl naphthylene, phenanthrenylene, carbazolylene, phenyl carbazolylene, dibenzofuranylene, phenyl dibenzofuranylene, or dimethylfluorenylene, and wherein phenylene, biphenylylene, naphthylene, phenyl naphthylene, phenanthrenylene, carbazolylene, phenyl carbazolylene, dibenzofuranylene, phenyl dibenzofuranylene, and dimethylfluorenylene can each independently be unsubstituted or substituted with one or more deuterium.

Most preferably, L' ₁ is a single bond, and L' ₂ and L' ₃ can each independently be a single bond, phenylene, biphenylylene, naphthylene, or phenyl naphthylene, wherein the phenylene, biphenylylene, naphthylene and phenyl naphthylene can each independently be unsubstituted or substituted with one or more deuterium atoms.

Preferably, L' ₄ may be a single bond or a substituted or unsubstituted C _6-20 arylene,

More preferably, L' ₄ may be a single bond, a substituted or unsubstituted phenylene, a substituted or unsubstituted biphenylylene, or a substituted or unsubstituted naphthylene,

Most preferably, L' ₄ may be a single bond, phenylene, biphenylylene or naphthylene, wherein each of the phenylene, biphenylylene and naphthylene may independently be unsubstituted or substituted with one or more deuterium atoms.

Preferably, the compound represented by chemical formula 2 can be represented by the following chemical formula 2-1:

[Chemical Formula 2-1]

In the above chemical formula 2-1,

Ar' ₁ to Ar' ₃ , L' ₁ to L' ₃ , R' ₁ and a are as defined in the chemical formula 2 above,

R' ₂ is hydrogen; deuterium; or substituted or unsubstituted C _6-60 aryl,

b is an integer from 0 to 4.

Preferably, R' ₂ may be hydrogen; deuterium; or substituted or unsubstituted C _6-20 aryl,

More preferably, R' ₂ can be hydrogen, deuterium, or phenyl which is unsubstituted or substituted with deuterium.

The deuterium substitution rate of the compound represented by the above chemical formula 2 may be 50% to 100%. Specifically, the deuterium substitution rate of the compound may be 50% or more, 60% or more, 70% or more, 75% or more, 80% or more, or 90% or more, but less than or equal to 100%.

For example, the compound represented by the above chemical formula 2 may contain, but is not limited to, 16 to 50 deuterium atoms. More specifically, the compound may contain 16 or more, 17 or more, 18 or more, or 19 or more, and 50 or less, 45 or less, 40 or less, 38 or less, 36 or less, 34 or less, 32 or less, 30 or less, 28 or less, 26 or less, 24 or less, 23 or less, 22 or less, 21 or less, or 20 or less deuterium atoms.

At this time, if the number of deuterium substitutions of the compound is to be indicated, it can be expressed by the following chemical formula 2-D:

[Chemical Formula 2-D]

In the above chemical formula 2-D,

Dn means that the total number of substituted deuterium (D) in the entire compound is n,

The description of R' ₁ and a is as defined in chemical formula 2,

The above n is a value including a,

Ar' _1d to Ar' _3d and L' _1d to L' _4d represent Ar' ₁ to Ar' ₃ and L' ₁ to L' ₄ substituents which are not substituted with deuterium, respectively,

-At least one of -L' _1d -Ar' _1d and R' ₁ is deuterium.

That is, in the chemical formula 2-D, n is the total number of deuteriums substituted in the compound, which is an integer that makes the deuterium substitution rate of the compound 50% or more, and is a value that includes a or a+1, which is the number of deuteriums substituted on phenanthrenyl. The compound represented by the chemical formula 2-D means a compound in which phenanthrenyl is substituted with a or a+1 deuteriums and the entire compound is substituted with n deuteriums. The reason why the number of deuteriums substituted on phenanthrenyl is a or a+1 is because -L' _1d -Ar' _1d can be deuterium.

For example, in the chemical formula 2-D, n of Dn may be 16 or more, 17 or more, 18 or more, or 19 or more, and 50 or less, 45 or less, 40 or less, 38 or less, 36 or less, 34 or less, 32 or less, 30 or less, 28 or less, 26 or less, 24 or less, 23 or less, 22 or less, 21 or less, or 20 or less.

Representative examples of compounds represented by the chemical formula 2 are as follows:

In the above group, D is deuterium,

n1 is an integer from 1 to 9,

n is the total number of deuterium atoms substituted in the compound,

Each of the above compounds has a deuterium substitution rate of 50% or more.

The compound represented by the above chemical formula 2 can be manufactured by a manufacturing method as in the following reaction scheme 2, for example, if it is a compound represented by the above chemical formula 2-D, and the remaining compounds can also be manufactured similarly.

[Reaction Formula 2]

In the above reaction scheme 2, Dn, Ar' _1d to Ar' _3d and L' _1d to L' _4d are as defined in the above chemical formula 2-D, X ₁ ' is halogen, and preferably X ₁ ' is chloro or bromo.

In the above reaction scheme 2, the compound represented by chemical formula 2 is prepared by subjecting each deuterium-substituted reactant to a Suzuki coupling reaction. In reaction scheme 2, the deuterium substitution reaction (step 1) is followed by the Suzuki coupling reaction (step 2). The deuterium substitution reaction is preferably carried out in the presence of D ₂ O, and the reactor, catalyst, solvent, etc. for the deuterium substitution reaction can be changed to suit the desired product as known in the art. The Suzuki coupling reaction is preferably carried out in the presence of a palladium catalyst and a base, and the reactor for the Suzuki coupling reaction can be changed as known in the art. The above manufacturing method can be further specified in the manufacturing examples described below.

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

Meanwhile, the light-emitting layer may additionally include a dopant in addition to the host. The dopant material is not particularly limited as long as it is a material used in an organic light-emitting device. For example, the dopant may include an aromatic amine derivative, a styrylamine compound, a boron complex, a fluoranthene compound, a metal complex, etc. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, such as pyrene, anthracene, chrysene, periflanthene, etc. having an arylamino group, and the styrylamine compound is a compound in which at least one arylvinyl group is substituted in a substituted or unsubstituted arylamine, and one 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, the dopant may include, but is not limited to, styrylamine, styryldiamine, styryltriamine, styryltetraamine, etc. In addition, the metal complex may include, but is not limited to, an iridium complex, a platinum complex, etc.

For example, the dopant material may be one or more compounds selected from the group consisting of, but is not limited to:

.

.

The orthostatic layer

The above hole-blocking layer is a layer placed between the electron transport layer and the light-emitting layer to prevent holes injected from the anode from being recombined in the light-emitting layer and from passing to the electron transport layer. It is also called a hole suppression layer or hole blocking layer. A material with high ionization energy is preferable for the hole-blocking layer.

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 above electron transport layer is a layer that receives electrons from the cathode or the electron injection layer formed on the cathode and transports the electrons to the light-emitting layer, and also suppresses the transfer of holes from the light-emitting layer. As the electron transport material, a material that can well receive electrons from the cathode and transfer them to the light-emitting layer, and a material with high electron mobility is suitable.

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

Electron injection layer

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

The above electron injection layer is a layer that injects electrons from an electrode, has the ability to transport electrons, has an excellent electron injection effect for an electron injection effect from a cathode, a light-emitting layer or a light-emitting material, prevents movement of excitons generated in the light-emitting layer to the hole injection layer, and it is preferable to use a compound having excellent thin film forming ability.

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

As the above metal complex compounds, 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h]quinolinato)beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)(o-cresolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtholato)aluminum, Bis(2-methyl-8-quinolinato)(2-naphtholato)gallium, etc., but are not limited thereto.

Meanwhile, in the present invention, the "electron injection and transport layer" is a layer that performs the roles of both the electron injection layer and the electron transport layer, and materials performing the roles of each layer may be used alone or in combination, but are not limited thereto.

Organic light emitting diode

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

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

Meanwhile, the organic light-emitting device according to the present invention may be a front-emitting type, a back-emitting type, or a double-sided emitting type depending on the material used.

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

Manufacturing Example 1-1

(8-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz1(30 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and the aqueous layer, and distilled off the organic layer. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 25.9 g of compound 1-1_P1. (Yield 67%, MS: [M+H] ⁺ = 636)

Compound 1-1_P1 (15 g, 23.6 mmol) and phenylboronic acid (3.0 g, 24.8 mmol) were added to 300 ml of THF, stirred, and refluxed. Then, potassium carbonate (9.8 g, 70.7 mmol) dissolved in 29 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and the aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.5 g of compound 1-1. (Yield 72%, MS: [M+H] ⁺ = 678)

Manufacturing Example 1-2

(8-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz2(28.4 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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 1-2_P1. (Yield 65%, MS: [M+H] ⁺ = 610)

Compound 1-2_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. Then, potassium carbonate (10.2 g, 73.8 mmol) dissolved in 31 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and the aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.7 g of compound 1-2. (Yield 73%, MS: [M+H] ⁺ = 652)

Manufacturing Example 1-3

(8-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz3(25.2 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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 1-3_P1. (Yield 69%, MS: [M+H] ⁺ = 560)

Compound 1-3_P1 (15 g, 26.8 mmol) and naphthalen-1-ylboronic acid (4.8 g, 28.1 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (11.1 g, 80.3 mmol) dissolved in 33 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.7 g of compound 1-3. (Yield 73%, MS: [M+H] ⁺ = 652)

Manufacturing Example 1-4

(8-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz4(23.5 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 24 g of compound 1-4_P1. (Yield 74%, MS: [M+H] ⁺ = 534)

Compound 1-4_P1 (15 g, 28.1 mmol) and dibenzo[b,d]furan-1-ylboronic acid (6.3 g, 29.5 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (11.7 g, 84.4 mmol) dissolved in 35 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.4 g of compound 1-4. (Yield 66%, MS: [M+H] ⁺ = 666)

Manufacturing Example 1-5

(8-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz5(23.9 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.6 g of compound 1-5_P1. (Yield 72%, MS: [M+H] ⁺ = 540)

Compound 1-5_P1 (15 g, 27.8 mmol) and dibenzo[b,d]thiophen-2-ylboronic acid (6.7 g, 29.2 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (11.5 g, 83.3 mmol) dissolved in 35 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.4 g of compound 1-5. (Yield 65%, MS: [M+H] ⁺ = 688)

Manufacturing Example 1-6

(8-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz6(17.1 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.9 g of compound 1-6_P1. (Yield 68%, MS: [M+H] ⁺ = 434)

Compound 1-6_P1 (15 g, 34.6 mmol) and triphenylen-2-ylboronic acid (9.9 g, 36.3 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (14.3 g, 103.7 mmol) dissolved in 43 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.3 g of compound 1-6. (Yield 66%, MS: [M+H] ⁺ = 626)

Manufacturing Example 1-7

(8-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz7(37 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 30.6 g of compound 1-7_P1. (Yield 72%, MS: [M+H] ⁺ = 700)

Compound 1-7_P1 (15 g, 21.4 mmol) and naphthalen-2-ylboronic acid (3.9 g, 22.5 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (8.9 g, 64.3 mmol) dissolved in 27 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.4 g of compound 1-7. (Yield 67%, MS: [M+H] ⁺ = 792)

Manufacturing Example 1-8

(8-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz8(34.4 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 30.1 g of compound 1-8_P1. (Yield 75%, MS: [M+H] ⁺ = 660)

Compound 1-8_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. Then, potassium carbonate (9.4 g, 68.2 mmol) dissolved in 28 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and the aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 10.7 g of compound 1-8. (Yield 67%, MS: [M+H] ⁺ = 702)

Manufacturing Example 1-9

At 0 ℃, a solution was prepared by adding Trifluoromethanesulfonic anhydride (30.1 g, 106.6 mmol) and Deuterium oxide (10.7 g, 532.8 mmol) and stirring for 5 hours. 1-bromo-8-chlorodibenzo[b,d]furan (15 g, 53.3 mmol) was added to 120 ml of 1,2,4-trichlorobenzene and stirring. 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 stirred while maintaining the temperature at 140 ℃. After 4 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. After that, the organic layer was neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 6.5 g of compound sub1-1-1. (Yield 43%, MS: [M+H] ⁺ = 283)

Compound sub1-1-1 (15 g, 52.9 mmol) and bis (pinacolato) diboron (14.8 g, 58.2 mmol) were stirred and refluxed 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, the mixture was cooled to room temperature, and the organic layer was separated using chloroform and water, and then distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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 sub1-1-2. (Yield 66%, MS: [M+H] ⁺ = 331)

Compound sub1-1-2 (15 g, 45.4 mmol) and compound Trz9 (21.4 g, 47.6 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (18.8 g, 136.1 mmol) dissolved in 56 ml of water was added, and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.5 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 18.2 g of compound 1-9_P1. (Yield 65%, MS: [M+H] ⁺ = 617)

Compound 1-9_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. Then, potassium carbonate (10.1 g, 72.9 mmol) dissolved in 30 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and the aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11 g of compound 1-9. (Yield 69%, MS: [M+H] ⁺ = 659)

Manufacturing Example 1-10

At 0 ℃, a solution was prepared by adding Trifluoromethanesulfonic anhydride (45.1 g, 159.8 mmol) and Deuterium oxide (16 g, 799.2 mmol) and stirring for 5 hours. 1-bromo-8-chlorodibenzo[b,d]furan (15 g, 53.3 mmol) was added to 120 ml of 1,2,4-trichlorobenzene and stirring. 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 stirred while maintaining the temperature at 140 ℃. After 7 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. After that, the organic layer was neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 5.6 g of compound sub1-2-1. (Yield 37%, MS: [M+H] ⁺ = 284)

Compound sub1-2-1 (15 g, 52.7 mmol) and bis (pinacolato) diboron (14.7 g, 58 mmol) were stirred and refluxed 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, the mixture was cooled to room temperature, and the organic layer was separated using chloroform and water, and then the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.1 g of compound sub1-2-2. (Yield 58%, MS: [M+H] ⁺ = 332)

Compound sub1-2-2 (15 g, 45.2 mmol) and compound Trz10 (17.5 g, 47.5 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (18.8 g, 135.7 mmol) dissolved in 56 ml of water was added, and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.5 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 17 g of compound 1-10_P1. (Yield 70%, MS: [M+H] ⁺ = 537)

Compound 1-10_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. Then, potassium carbonate (10.1 g, 72.9 mmol) dissolved in 30 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and the aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11 g of compound 1-10. (Yield 69%, MS: [M+H] ⁺ = 659)

Manufacturing Example 1-11

At 0 ℃, a solution was prepared by adding Trifluoromethanesulfonic anhydride (60.1 g, 213.1 mmol) and Deuterium oxide (21.4 g, 1065.6 mmol) and stirring for 5 hours. 1-bromo-8-chlorodibenzo[b,d]furan (15 g, 53.3 mmol) was added to 120 ml of 1,2,4-trichlorobenzene and stirring. 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 increased to 140 ℃ and maintained while stirring. After 10 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. After that, the organic layer was neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 6.4 g of compound sub1-3-1. (Yield 42%, MS: [M+H] ⁺ = 285)

Compound sub1-3-1 (15 g, 52.5 mmol) and bis (pinacolato) diboron (14.7 g, 57.8 mmol) were stirred and refluxed 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, the mixture was cooled to room temperature, and the organic layer was separated using chloroform and water, and then the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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 sub1-3-2. (Yield 69%, MS: [M+H] ⁺ = 333)

Compound sub1-3-2 (15 g, 45.1 mmol) and compound Trz11 (22.7 g, 47.4 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (18.7 g, 135.3 mmol) dissolved in 56 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 20.2 g of compound 1-11_P1. (Yield 69%, MS: [M+H] ⁺ = 650)

Compound 1-11_P1 (15 g, 23.1 mmol) and phenylboronic acid (2.9 g, 24.2 mmol) were added to 300 ml of THF, stirred, and refluxed. Then, potassium carbonate (9.6 g, 69.2 mmol) dissolved in 29 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and the aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 10.5 g of compound 1-11. (Yield 66%, MS: [M+H] ⁺ = 692)

Manufacturing Example 1-12

Compound sub1-3-2 (15 g, 45.1 mmol) and compound Trz12 (20.3 g, 47.4 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (18.7 g, 135.3 mmol) dissolved in 56 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 20.2 g of compound 1-12_P1. (Yield 75%, MS: [M+H] ⁺ = 599)

Compound 1-12_P1 (15 g, 25 mmol) and phenylboronic acid (3.2 g, 26.3 mmol) were added to 300 ml of THF, stirred, and refluxed. Then, potassium carbonate (10.4 g, 75.1 mmol) dissolved in 31 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.9 g of compound 1-12. (Yield 74%, MS: [M+H] ⁺ = 641)

Manufacturing Example 1-13

Compound 1-6 (10 g, 16 mmol), PtO ₂ (1.1 g, 4.8 mmol), and 80 ml of D ₂ O were added to a shaker tube, sealed, and heated at 250 ° C., 600 psi for 12 h. When the reaction was complete, chloroform was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO ₄ and concentrated, and the sample was purified by silica gel column chromatography to produce 3.9 g of compound 1-13. (Yield 38%, MS: [M + H] ⁺ = 649)

Manufacturing Example 1-14

(7-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz13(25.2 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.1 g of compound 1-14_P1. (Yield 65%, MS: [M+H] ⁺ = 560)

Compound 1-14_P1 (15 g, 26.8 mmol) and phenylboronic acid (3.4 g, 28.1 mmol) were added to 300 ml of THF, stirred, and refluxed. Then, potassium carbonate (11.1 g, 80.3 mmol) dissolved in 33 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and the aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 10.6 g of compound 1-14. (Yield 66%, MS: [M+H] ⁺ = 602)

Manufacturing Example 1-15

(7-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz14(25.2 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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 1-15_P1. (Yield 74%, MS: [M+H] ⁺ = 560)

Compound 1-15_P1 (15 g, 26.8 mmol) and phenylboronic acid (3.4 g, 28.1 mmol) were added to 300 ml of THF, stirred, and refluxed. Then, potassium carbonate (11.1 g, 80.3 mmol) dissolved in 33 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and the aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.6 g of compound 1-15. (Yield 72%, MS: [M+H] ⁺ = 602)

Manufacturing Example 1-16

(7-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz15(25.2 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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 1-16_P1. (Yield 74%, MS: [M+H] ⁺ = 560)

Compound 1-16_P1 (15 g, 26.8 mmol) and phenylboronic acid (3.4 g, 28.1 mmol) were added to 300 ml of THF, stirred, and refluxed. Then, potassium carbonate (11.1 g, 80.3 mmol) dissolved in 33 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and the aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.1 g of compound 1-16. (Yield 75%, MS: [M+H] ⁺ = 602)

Manufacturing Example 1-17

(7-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz16(28.4 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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 1-17_P1. (Yield 68%, MS: [M+H] ⁺ = 610)

Compound 1-17_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. Then, potassium carbonate (10.2 g, 73.8 mmol) dissolved in 31 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and the aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.8 g of compound 1-17. (Yield 74%, MS: [M+H] ⁺ = 652)

Manufacturing Example 1-18

(7-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz17(20.3 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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 1-18_P1. (Yield 74%, MS: [M+H] ⁺ = 484)

Compound 1-18_P1 (15 g, 31 mmol) and naphthalen-2-ylboronic acid (5.6 g, 32.5 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (12.9 g, 93 mmol) dissolved in 39 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.3 g of compound 1-18. (Yield 69%, MS: [M+H] ⁺ = 576)

Manufacturing Example 1-19

(7-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz18(22.9 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 21 g of compound 1-19_P1. (Yield 66%, MS: [M+H] ⁺ = 524)

Compound 1-19_P1 (15 g, 28.6 mmol) and naphthalen-2-ylboronic acid (5.2 g, 30.1 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (11.9 g, 85.9 mmol) dissolved in 36 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.4 g of compound 1-19. (Yield 65%, MS: [M+H] ⁺ = 616)

Manufacturing Example 1-20

(7-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz19(33.6 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 30.3 g of compound 1-20_P1. (Yield 72%, MS: [M+H] ⁺ = 692)

Compound 1-20_P1 (15 g, 21.7 mmol) and dibenzo[b,d]furan-3-ylboronic acid (4.8 g, 22.8 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (9 g, 65 mmol) dissolved in 27 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12 g of compound 1-20. (Yield 67%, MS: [M+H] ⁺ = 824)

Manufacturing Example 1-21

(7-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz20(29.7 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.9 g of compound 1-21_P1. (Yield 67%, MS: [M+H] ⁺ = 586)

Compound 1-21_P1 (15 g, 25.6 mmol) and phenanthren-3-ylboronic acid (6 g, 26.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (10.6 g, 76.8 mmol) dissolved in 32 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.3 g of compound 1-21. (Yield 66%, MS: [M+H] ⁺ = 728)

Manufacturing Example 1-22

(7-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz21(25.8 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.6 g of compound 1-22_P1. (Yield 71%, MS: [M+H] ⁺ = 569)

Compound 1-22_P1 (15 g, 26.4 mmol) and (phenyl-d5)boronic acid (3.5 g, 27.7 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (10.9 g, 79.1 mmol) dissolved in 33 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.7 g of compound 1-22. (Yield 72%, MS: [M+H] ⁺ = 616)

Manufacturing Example 1-23

(7-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz22(20.6 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.2 g of compound 1-23_P1. (Yield 68%, MS: [M+H] ⁺ = 489)

Compound 1-23_P1 (15 g, 30.7 mmol) and naphthalen-2-ylboronic acid (5.5 g, 32.2 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (12.7 g, 92 mmol) dissolved in 38 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.6 g of compound 1-23. (Yield 71%, MS: [M+H] ⁺ = 581)

Manufacturing Example 1-24

At 0 ℃, a solution was prepared by adding Trifluoromethanesulfonic anhydride (30.1 g, 106.6 mmol) and Deuterium oxide (10.7 g, 532.8 mmol) and stirring for 5 hours. 1-bromo-7-chlorodibenzo[b,d]furan (15 g, 53.3 mmol) was added to 120 ml of 1,2,4-trichlorobenzene and stirring was performed. After that, 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 stirred while maintaining the temperature at 140 ℃. After 3 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. After that, the organic layer was neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 6 g of compound sub2-1-1. (Yield 40%, 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 and refluxed 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 4 hours, the mixture was cooled to room temperature, and the organic layer was separated using chloroform and water, and then the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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 sub2-1-2. (Yield 65%, MS: [M+H] ⁺ = 331)

Compound sub2-1-2 (15 g, 45.4 mmol) and compound Trz23 (19 g, 47.6 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (18.8 g, 136.1 mmol) dissolved in 56 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 17.3 g of compound 1-24_P1. (Yield 73%, MS: [M+H] ⁺ = 522)

Compound 1-24_P1 (15 g, 28.7 mmol) and naphthalen-2-ylboronic acid (5.2 g, 30.2 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (11.9 g, 86.2 mmol) dissolved in 36 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.5 g of compound 1-24. (Yield 71%, MS: [M+H] ⁺ = 614)

Manufacturing Example 1-25

At 0 ℃, a solution was prepared by adding Trifluoromethanesulfonic anhydride (60.1 g, 213.1 mmol) and Deuterium oxide (21.4 g, 1065.6 mmol) and stirring for 5 hours. 1-bromo-7-chlorodibenzo[b,d]furan (15 g, 53.3 mmol) was added to 120 ml of 1,2,4-trichlorobenzene and stirring was performed. After that, 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 stirred while maintaining the temperature at 140 ℃. After 10 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. After that, the organic layer was neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 6.7 g of compound sub2-2-1. (Yield 44%, MS: [M+H] ⁺ = 285)

Compound sub2-2-1 (15 g, 52.5 mmol) and bis (pinacolato) diboron (14.7 g, 57.8 mmol) were stirred and refluxed 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, the mixture was cooled to room temperature, and the organic layer was separated using chloroform and water, and then the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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 sub2-2-2. (Yield 67%, MS: [M+H] ⁺ = 333)

Compound sub2-2-2 (15 g, 45.1 mmol) and compound Trz24 (22.7 g, 47.4 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (18.7 g, 135.3 mmol) dissolved in 56 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 19.9 g of compound 1-25_P1. (Yield 68%, MS: [M+H] ⁺ = 650)

Compound 1-25_P1 (15 g, 23.1 mmol) and phenylboronic acid (3 g, 24.2 mmol) were added to 300 ml of THF, stirred, and refluxed. Then, potassium carbonate (9.6 g, 69.2 mmol) dissolved in 29 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.6 g of compound 1-25. (Yield 73%, MS: [M+H] ⁺ = 692)

Manufacturing Example 1-26

Compound 1-16 (10 g, 16.6 mmol), PtO ₂ (1.1 g, 5 mmol), and 83 ml of D ₂ O were added to a shaker tube, sealed, and heated at 250 ° C., 600 psi for 12 hours. When the reaction was complete, chloroform was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO ₄ and concentrated, and the sample was purified by silica gel column chromatography to produce 3.1 g of compound 1-26. (Yield 30%, MS: [M + H] ⁺ = 626)

Manufacturing Example 1-27

Compound 1-18 (10 g, 17.4 mmol), PtO ₂ (1.2 g, 5.2 mmol), and D ₂ O 87 ml were added to a shaker tube, sealed, and heated at 250 ° C., 600 psi for 12 hours. When the reaction was complete, chloroform was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO ₄ and concentrated, and the sample was purified by silica gel column chromatography to produce 3.9 g of compound 1-27. (Yield 38%, MS: [M + H] ⁺ = 598)

Manufacturing Example 1-28

Compound 1-19 (10 g, 16.2 mmol), PtO ₂ (1.1 g, 4.9 mmol), and D ₂ O 81 ml were added to a shaker tube, sealed, and heated at 250 °C, 600 psi for 12 h. When the reaction was complete, chloroform was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO ₄ and concentrated, and the sample was purified by silica gel column chromatography to produce 4.7 g of compound 1-28. (Yield 45%, MS: [M+H] ⁺ = 639)

Manufacturing Example 1-29

(7-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz25(31.2 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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 1-29_P1. (Yield 66%, MS: [M+H] ⁺ = 610)

Compound 1-29_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. Then, potassium carbonate (10.2 g, 73.8 mmol) dissolved in 31 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 10.6 g of compound 1-29_P2. (Yield 66%, MS: [M+H] ⁺ = 652)

Compound 1-29_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, sealed, and heated at 250 ° C., 600 psi for 12 hours. When the reaction was complete, chloroform was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO ₄ and concentrated, and the sample was purified by silica gel column chromatography to produce 4.6 g of compound 1-29. (Yield 44%, MS: [M + H] ⁺ = 678)

Manufacturing Example 1-30

(6-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz4(23.5 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.4 g of compound 1-30_P1. (Yield 72%, MS: [M+H] ⁺ = 534)

Compound 1-30_P1 (15 g, 28.1 mmol) and [1,1'-biphenyl]-4-ylboronic acid (5.8 g, 29.5 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (11.6 g, 84.3 mmol) dissolved in 35 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.4 g of compound 1-30. (Yield 73%, MS: [M+H] ⁺ = 652)

Manufacturing Example 1-31

(6-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz6(17.1 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 17.4 g of compound 1-31_P1. (Yield 66%, MS: [M+H] ⁺ = 434)

Compound 1-31_P1 (15 g, 34.6 mmol) and phenanthren-2-ylboronic acid (8.1 g, 36.3 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (14.3 g, 103.7 mmol) dissolved in 43 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.3 g of compound 1-31. (Yield 67%, MS: [M+H] ⁺ = 576)

Manufacturing Example 1-32

(6-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz13(25.2 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.8 g of compound 1-32_P1. (Yield 73%, MS: [M+H] ⁺ = 560)

Compound 1-32_P1 (15 g, 26.8 mmol) and benzo[b]naphtho[1,2-d]thiophen-5-ylboronic acid (7.8 g, 28.1 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (11.1 g, 80.3 mmol) dissolved in 33 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.4 g of compound 1-32. (Yield 71%, MS: [M+H] ⁺ = 758)

Manufacturing Example 1-33

(6-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz26(22.9 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.7 g of compound 1-33_P1. (Yield 68%, MS: [M+H] ⁺ = 524)

Compound 1-33_P1 (15 g, 28.6 mmol) and phenylboronic acid (3.7 g, 30.1 mmol) were added to 300 ml of THF, stirred, and refluxed. Then, potassium carbonate (11.9 g, 85.9 mmol) dissolved in 36 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and the aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.8 g of compound 1-33. (Yield 73%, MS: [M+H] ⁺ = 566)

Manufacturing Example 1-34

(6-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz27(23.9 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 24 g of compound 1-34_P1. (Yield 73%, MS: [M+H] ⁺ = 540)

Compound 1-34_P1 (15 g, 27.8 mmol) and dibenzo[b,d]furan-4-ylboronic acid (6.2 g, 29.2 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (11.5 g, 83.3 mmol) dissolved in 35 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.9 g of compound 1-34. (Yield 69%, MS: [M+H] ⁺ = 672)

Manufacturing Example 1-35

(6-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz28(25.2 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.8 g of compound 1-35_P1. (Yield 70%, MS: [M+H] ⁺ = 560)

Compound 1-35_P1 (15 g, 26.8 mmol) and naphthalen-2-ylboronic acid (4.8 g, 28.1 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (11.1 g, 80.3 mmol) dissolved in 33 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.9 g of compound 1-35. (Yield 74%, MS: [M+H] ⁺ = 652)

Manufacturing Example 1-36

(6-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz20(29.7 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 23.9 g of compound 1-36_P1. (Yield 67%, MS: [M+H] ⁺ = 586)

Compound 1-36_P1 (15 g, 25.6 mmol) and naphthalen-2-ylboronic acid (4.6 g, 26.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (10.6 g, 76.8 mmol) dissolved in 32 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.8 g of compound 1-36. (Yield 74%, MS: [M+H] ⁺ = 678)

Manufacturing Example 1-37

At 0 ℃, a solution was prepared by adding Trifluoromethanesulfonic anhydride (30.1 g, 106.6 mmol) and Deuterium oxide (10.7 g, 532.8 mmol) and stirring for 5 hours. 1-bromo-6-chlorodibenzo[b,d]furan (15 g, 53.3 mmol) was added to 120 ml of 1,2,4-trichlorobenzene and stirring. After that, the prepared mixed solution of Trifluoromethanesulfonic anhydride and Deuterium oxide was slowly added dropwise to the mixed solution of 1-bromo-6-chlorodibenzo[b,d]furan and 1,2,4-trichlorobenzene and stirred while maintaining the temperature at 140 ℃. After 3 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. After that, the organic layer was neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 6.8 g of compound sub3-1-1. (Yield 45%, MS: [M+H] ⁺ = 283)

Compound sub3-1-1 (15 g, 52.9 mmol) and bis (pinacolato) diboron (14.8 g, 58.2 mmol) were stirred and refluxed 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, the mixture was cooled to room temperature, and the organic layer was separated using chloroform and water, and then the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.1 g of compound sub3-1-2. (Yield 75%, MS: [M+H] ⁺ = 331)

Compound sub3-1-2 (15 g, 45.4 mmol) and compound Trz29 (22.6 g, 47.6 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (18.8 g, 136.1 mmol) dissolved in 56 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 20.4 g of compound 1-37_P1. (Yield 70%, MS: [M+H] ⁺ = 643)

Compound 1-37_P1 (15 g, 23.3 mmol) and (phenyl-d5)boronic acid (3.1 g, 24.5 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (9.7 g, 70 mmol) dissolved in 29 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.7 g of compound 1-37. (Yield 73%, MS: [M+H] ⁺ = 690)

Manufacturing Example 1-38

Compound sub3-1-2 (15 g, 45.4 mmol) and compound Trz30 (21.1 g, 47.6 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (18.8 g, 136.1 mmol) dissolved in 56 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 18 g of compound 1-38_P1. (Yield 65%, MS: [M+H] ⁺ = 612)

Compound 1-38_P1 (15 g, 24.5 mmol) and (phenyl-d5)boronic acid (3.3 g, 25.7 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (10.2 g, 73.5 mmol) dissolved in 30 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.1 g of compound 1-38. (Yield 69%, MS: [M+H] ⁺ = 659)

Manufacturing Example 1-39

At 0 ℃, a solution was prepared by adding Trifluoromethanesulfonic anhydride (60.1 g, 213.1 mmol) and Deuterium oxide (21.4 g, 1065.6 mmol) and stirring for 5 hours. 1-bromo-6-chlorodibenzo[b,d]furan (15 g, 53.3 mmol) was added to 120 ml of 1,2,4-trichlorobenzene and stirring. After that, the prepared mixed solution of Trifluoromethanesulfonic anhydride and Deuterium oxide was slowly added dropwise to the mixed solution of 1-bromo-6-chlorodibenzo[b,d]furan and 1,2,4-trichlorobenzene and stirred while maintaining the temperature at 140 ℃. After 10 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. After that, the organic layer was neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 6.5 g of compound sub3-2-1. (Yield 43%, MS: [M+H] ⁺ = 285)

Compound sub3-2-1 (15 g, 52.5 mmol) and bis (pinacolato) diboron (14.7 g, 57.8 mmol) were stirred and refluxed 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 5 hours, the mixture was cooled to room temperature, and the organic layer was separated using chloroform and water, and then the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.1 g of compound sub3-2-2. (Yield 75%, MS: [M+H] ⁺ = 333)

Compound sub3-2-2 (15 g, 45.1 mmol) and compound Trz31 (19.1 g, 47.4 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (18.7 g, 135.3 mmol) dissolved in 56 ml of water was added, and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.5 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 19.1 g of compound 1-39_P1. (Yield 74%, MS: [M+H] ⁺ = 573)

Compound 1-39_P1 (15 g, 26.2 mmol) and benzo[b]naphtho[1,2-d]thiophen-5-ylboronic acid (7.6 g, 27.5 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (10.9 g, 78.5 mmol) dissolved in 33 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.7 g of compound 1-39. (Yield 68%, MS: [M+H] ⁺ = 771)

Manufacturing Example 1-40

At 0 ℃, a solution was prepared by adding Trifluoromethanesulfonic anhydride (60.1 g, 213.1 mmol) and Deuterium oxide (21.4 g, 1065.6 mmol) and stirring for 5 hours. 1-bromo-6-chlorodibenzo[b,d]furan (15 g, 53.3 mmol) was added to 120 ml of 1,2,4-trichlorobenzene and stirring. After that, the prepared mixed solution of Trifluoromethanesulfonic anhydride and Deuterium oxide was slowly added dropwise to the mixed solution of 1-bromo-6-chlorodibenzo[b,d]furan and 1,2,4-trichlorobenzene and stirred while maintaining the temperature at 140 ℃. After 10 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. After that, the organic layer was neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 6.4 g of compound sub3-3-1. (Yield 42%, MS: [M+H] ⁺ = 285)

Compound sub3-3-1 (15 g, 52.5 mmol) and bis (pinacolato) diboron (14.7 g, 57.8 mmol) were stirred and refluxed 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, the mixture was cooled to room temperature, and the organic layer was separated using chloroform and water, and then distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.8 g of compound sub3-3-2. (Yield 62%, MS: [M+H] ⁺ = 333)

Compound sub3-3-2 (15 g, 45.1 mmol) and compound Trz32 (17.9 g, 47.4 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (18.7 g, 135.3 mmol) dissolved in 56 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 18 g of compound 1-40_P1. (Yield 73%, MS: [M+H] ⁺ = 549)

Compound 1-40_P1 (15 g, 27.4 mmol) and dibenzo[b,d]furan-4-ylboronic acid (6.1 g, 28.7 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (11.3 g, 82.1 mmol) dissolved in 34 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.3 g of compound 1-40. (Yield 66%, MS: [M+H] ⁺ = 681)

Manufacturing Example 1-41

Compound sub3-3-2 (15 g, 45.1 mmol) and compound Trz33 (18.9 g, 47.4 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (18.7 g, 135.3 mmol) dissolved in 56 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 19 g of compound 1-41_P1. (Yield 74%, MS: [M+H] ⁺ = 569)

Compound 1-41_P1 (15 g, 26.4 mmol) and naphthalen-2-ylboronic acid (4.8 g, 27.7 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (10.9 g, 79.1 mmol) dissolved in 33 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.5 g of compound 1-41. (Yield 72%, MS: [M+H] ⁺ = 661)

Manufacturing Example 1-42

(6-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz5(23.9 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.3 g of compound 1-42_P1. (Yield 71%, MS: [M+H] ⁺ = 540)

Compound 1-42_P1 (15 g, 23.3 mmol) and (phenyl-d5)boronic acid (3.1 g, 24.5 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (9.7 g, 70 mmol) dissolved in 29 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.3 g of compound 1-42_P2. (Yield 70%, MS: [M+H] ⁺ = 690)

Compound 1-42_P2 (10 g, 14.9 mmol), PtO ₂ (1 g, 4.5 mmol), and 74 ml of D ₂ O were added to a shaker tube, sealed, and heated at 250 ° C., 600 psi for 12 hours. When the reaction was complete, chloroform was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO ₄ and concentrated, and the sample was purified by silica gel column chromatography to produce 3.8 g of compound 1-42. (Yield 37%, MS: [M + H] ⁺ = 695)

Manufacturing Example 1-43

(4-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz34(30 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26.7 g of compound 1-43_P1. (Yield 69%, MS: [M+H] ⁺ = 636)

Compound 1-43_P1 (15 g, 23.6 mmol) and naphthalen-2-ylboronic acid (4.3 g, 24.8 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (9.8 g, 70.7 mmol) dissolved in 29 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.7 g of compound 1-43. (Yield 74%, MS: [M+H] ⁺ = 728)

Manufacturing Example 1-44

(4-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz17(20.3 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 19.1 g of compound 1-44_P1. (Yield 65%, MS: [M+H] ⁺ = 484)

Compound 1-44_P1 (15 g, 31 mmol) and phenanthren-9-ylboronic acid (7.2 g, 32.6 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (12.9 g, 93.1 mmol) dissolved in 39 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.2 g of compound 1-44. (Yield 73%, MS: [M+H] ⁺ = 626)

Manufacturing Example 1-45

Compound 1-44_P1 (15 g, 31 mmol) and fluoranthen-3-ylboronic acid (8 g, 32.6 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (12.9 g, 93.1 mmol) dissolved in 39 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.3 g of compound 1-45. (Yield 66%, MS: [M+H] ⁺ = 650)

Manufacturing Example 1-46

Compound 1-44_P1 (15 g, 31 mmol) and dibenzo[b,d]furan-1-ylboronic acid (6.9 g, 32.6 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (12.9 g, 93.1 mmol) dissolved in 39 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.8 g of compound 1-46. (Yield 72%, MS: [M+H] ⁺ = 616)

Manufacturing Example 1-47

(4-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz13(25.2 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 25.5 g of compound 1-47_P1. (Yield 75%, MS: [M+H] ⁺ = 560)

Compound 1-47_P1 (15 g, 26.8 mmol) and benzo[b]naphtho[2,1-d]thiophen-8-ylboronic acid (7.8 g, 28.1 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (11.1 g, 80.3 mmol) dissolved in 33 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.4 g of compound 1-47. (Yield 66%, MS: [M+H] ⁺ = 758)

Manufacturing Example 1-48

(4-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz35(28.4 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 27.4 g of compound 1-48_P1. (Yield 74%, MS: [M+H] ⁺ = 610)

Compound 1-48_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. Then, potassium carbonate (10.2 g, 73.8 mmol) dissolved in 31 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and the aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 10.6 g of compound 1-48. (Yield 66%, MS: [M+H] ⁺ = 652)

Manufacturing Example 1-49

(4-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz36(31.6 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 27.7 g of compound 1-49_P1. (Yield 74%, MS: [M+H] ⁺ = 616)

Compound 1-49_P1 (15 g, 24.3 mmol) and naphthalen-2-ylboronic acid (4.4 g, 25.6 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (10.1 g, 73 mmol) dissolved in 30 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.4 g of compound 1-49. (Yield 72%, MS: [M+H] ⁺ = 708)

Manufacturing Example 1-50

(4-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz37(28 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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 1-50_P1. (Yield 71%, MS: [M+H] ⁺ = 560)

Compound 1-50_P1 (15 g, 26.8 mmol) and naphthalen-2-ylboronic acid (4.8 g, 28.1 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (11.1 g, 80.3 mmol) dissolved in 33 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.5 g of compound 1-50. (Yield 66%, MS: [M+H] ⁺ = 652)

Manufacturing Example 1-51

(4-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz38(23.2 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.5 g of compound 1-51_P1. (Yield 67%, MS: [M+H] ⁺ = 529)

Compound 1-51_P1 (15 g, 28.4 mmol) and ([1,1'-biphenyl]-4-yl-d9)boronic acid (6.2 g, 29.8 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (11.8 g, 85.1 mmol) dissolved in 35 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.3 g of compound 1-51. (Yield 66%, MS: [M+H] ⁺ = 656)

Manufacturing Example 1-52

At 0 ℃, a solution was prepared by adding Trifluoromethanesulfonic anhydride (30.1 g, 106.6 mmol) and Deuterium oxide (10.7 g, 532.8 mmol) and stirring for 5 hours. 1-bromo-4-chlorodibenzo[b,d]furan (15 g, 53.3 mmol) was added to 120 ml of 1,2,4-trichlorobenzene and stirring. After that, 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 stirred while maintaining the temperature at 140 ℃. After 3 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. After that, the organic layer was neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 6.5 g of compound sub4-1-1. (Yield 43%, MS: [M+H] ⁺ = 283)

Compound sub4-1-1 (15 g, 52.9 mmol) and bis (pinacolato) diboron (14.8 g, 58.2 mmol) were stirred and refluxed 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, the mixture was cooled to room temperature, and the organic layer was separated using chloroform and water, and then the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.8 g of compound sub4-1-2. (Yield 62%, MS: [M+H] ⁺ = 331)

Compound sub4-1-2 (15 g, 45.4 mmol) and compound Trz40 (20.2 g, 47.6 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (18.8 g, 136.1 mmol) dissolved in 56 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 19.9 g of compound 1-52_P1. (Yield 74%, MS: [M+H] ⁺ = 594)

Compound 1-52_P1 (15 g, 25.3 mmol) and phenylboronic acid (3.2 g, 26.6 mmol) were added to 300 ml of THF, stirred, and refluxed. Then, potassium carbonate (10.5 g, 75.9 mmol) dissolved in 31 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and the aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.7 g of compound 1-52. (Yield 73%, MS: [M+H] ⁺ = 635)

Manufacturing Example 1-53

At 0 ℃, a solution was prepared by adding Trifluoromethanesulfonic anhydride (60.1 g, 213.1 mmol) and Deuterium oxide (21.4 g, 1065.6 mmol) and stirring for 5 hours. 1-bromo-4-chlorodibenzo[b,d]furan (15 g, 53.3 mmol) was added to 120 ml of 1,2,4-trichlorobenzene and stirring. After that, 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 increased to 140 ℃ and maintained while stirring. After 10 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. After that, the organic layer was neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 5.3 g of compound sub4-2-1. (Yield 35%, MS: [M+H] ⁺ = 285)

Compound sub4-2-1 (15 g, 52.5 mmol) and bis (pinacolato) diboron (14.7 g, 57.8 mmol) were stirred and refluxed 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, the mixture was cooled to room temperature, and the organic layer was separated using chloroform and water, and then the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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 sub4-2-2. (Yield 63%, MS: [M+H] ⁺ = 333)

Compound sub4-2-2 (15 g, 45.1 mmol) and compound Trz41 (15.8 g, 47.4 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (18.7 g, 135.3 mmol) dissolved in 56 ml of water was added, and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.5 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 16.6 g of compound 1-53_P1. (Yield 75%, MS: [M+H] ⁺ = 493)

Compound 1-53_P1 (15 g, 30.4 mmol) and dibenzo[b,d]furan-1-ylboronic acid (6.8 g, 31.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (12.6 g, 91.3 mmol) dissolved in 38 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.1 g of compound 1-53. (Yield 69%, MS: [M+H] ⁺ = 625)

Manufacturing Example 1-54

Compound sub4-2-2 (15 g, 45.1 mmol) and compound Trz42 (21.2 g, 47.4 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (18.7 g, 135.3 mmol) dissolved in 56 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 18.4 g of compound 1-54_P1. (Yield 71%, MS: [M+H] ⁺ = 574)

Compound 1-54_P1 (15 g, 26.1 mmol) and naphthalen-2-ylboronic acid (4.7 g, 27.4 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (10.8 g, 78.4 mmol) dissolved in 32 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.6 g of compound 1-54. (Yield 67%, MS: [M+H] ⁺ = 666)

Manufacturing Example 1-55

At 0 ℃, a solution was prepared by adding Trifluoromethanesulfonic anhydride (90.2 g, 319.7 mmol) and Deuterium oxide (32 g, 1598.4 mmol) and stirring for 5 hours. 1-bromo-4-chlorodibenzo[b,d]furan (15 g, 53.3 mmol) was added to 120 ml of 1,2,4-trichlorobenzene and stirring. After that, 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 stirred while heating to 140 ℃. After 18 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. After that, the organic layer was neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 5.8 g of compound sub4-3-1. (Yield 38%, MS: [M+H] ⁺ = 287)

Compound sub4-3-1 (15 g, 52.2 mmol) and bis (pinacolato) diboron (14.6 g, 57.4 mmol) were stirred and refluxed in 300 ml of 1,4-dioxane. Then, potassium acetate (7.7 g, 78.2 mmol) was added, and after sufficient stirring, bis (dibenzylideneacetone) palladium (0) (0.9 g, 1.6 mmol) and tricyclohexylphosphine (0.9 g, 3.1 mmol) were added. After reacting for 6 hours, the mixture was cooled to room temperature, and the organic layer was separated using chloroform and water, and then the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.9 g of compound sub4-3-2. (Yield 74%, MS: [M+H] ⁺ = 335)

Compound sub4-3-2 (15 g, 44.8 mmol) and compound Trz41 (15.7 g, 47.1 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (18.6 g, 134.5 mmol) dissolved in 56 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 4 hours of reaction, it was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.2 g of compound 1-55_P1. (Yield 73%, MS: [M+H] ⁺ = 495)

Compound 1-55_P1 (15 g, 30.3 mmol) and fluoranthen-3-ylboronic acid (7.8 g, 31.8 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (12.6 g, 90.9 mmol) dissolved in 38 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 15 g of compound 1-55. (Yield 75%, MS: [M+H] ⁺ = 661)

Manufacturing Example 1-56

Compound 1-44 (10 g, 16 mmol), PtO ₂ (1.1 g, 4.8 mmol), and 80 ml of D ₂ O were added to a shaker tube, sealed, and heated at 250 ° C., 600 psi for 12 hours. When the reaction was complete, chloroform was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO ₄ and concentrated, and the sample was purified by silica gel column chromatography to produce 3.9 g of compound 1-56. (Yield 38%, MS: [M + H] ⁺ = 650)

Manufacturing Example 1-57

(3-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz6(17.1 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 19 g of compound 1-57_P1. (Yield 72%, MS: [M+H] ⁺ = 434)

Compound 1-57_P1 (15 g, 34.6 mmol) and phenanthren-3-ylboronic acid (8.1 g, 36.3 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (14.3 g, 103.7 mmol) dissolved in 43 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.1 g of compound 1-57. (Yield 71%, MS: [M+H] ⁺ = 576)

Manufacturing Example 1-58

Compound 1-57_P1 (15 g, 34.6 mmol) and naphtho[2,3-b]benzofuran-1-ylboronic acid (9.5 g, 36.3 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (14.3 g, 103.7 mmol) dissolved in 43 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 16 g of compound 1-58. (Yield 75%, MS: [M+H] ⁺ = 616)

Manufacturing Example 1-59

(3-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz42(26.8 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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 1-59_P1. (Yield 74%, MS: [M+H] ⁺ = 586)

Compound 1-59_P1 (15 g, 25.6 mmol) and phenylboronic acid (3.3 g, 26.9 mmol) were added to 300 ml of THF, stirred, and refluxed. Then, potassium carbonate (10.6 g, 76.8 mmol) dissolved in 32 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and the aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 10.6 g of compound 1-59. (Yield 66%, MS: [M+H] ⁺ = 628)

Manufacturing Example 1-60

(3-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz13(25.2 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 25.2 g of compound 1-60_P1. (Yield 74%, MS: [M+H] ⁺ = 560)

Compound 1-60_P1 (15 g, 26.8 mmol) and naphtho[2,1-b]benzofuran-6-ylboronic acid (7.4 g, 28.1 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (11.1 g, 80.3 mmol) dissolved in 33 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.5 g of compound 1-60. (Yield 73%, MS: [M+H] ⁺ = 742)

Manufacturing Example 1-61

(3-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz43(33.2 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 29.6 g of compound 1-61_P1. (Yield 71%, MS: [M+H] ⁺ = 686)

Compound 1-61_P1 (15 g, 21.9 mmol) and phenylboronic acid (2.8 g, 23 mmol) were added to 300 ml of THF, stirred, and refluxed. Then, potassium carbonate (9.1 g, 65.6 mmol) dissolved in 27 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.3 g of compound 1-61. (Yield 68%, MS: [M+H] ⁺ = 758)

Manufacturing Example 1-62

(3-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz44(23.5 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 22.7 g of compound 1-62_P1. (Yield 70%, MS: [M+H] ⁺ = 534)

Compound 1-62_P1 (15 g, 28.1 mmol) and dibenzo[b,d]furan-4-ylboronic acid (6.3 g, 29.5 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (11.6 g, 84.3 mmol) dissolved in 35 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.9 g of compound 1-62. (Yield 69%, MS: [M+H] ⁺ = 666)

Manufacturing Example 1-63

(3-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz45(22.9 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.3 g of compound 1-63_P1. (Yield 67%, MS: [M+H] ⁺ = 524)

Compound 1-63_P1 (15 g, 28.6 mmol) and naphthalen-2-ylboronic acid (5.2 g, 30.1 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (11.9 g, 85.9 mmol) dissolved in 36 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.7 g of compound 1-63. (Yield 72%, MS: [M+H] ⁺ = 616)

Manufacturing Example 1-64

(3-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz46(30 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 25.5 g of compound 1-64_P1. (Yield 66%, MS: [M+H] ⁺ = 636)

Compound 1-64_P1 (15 g, 23.6 mmol) and phenylboronic acid (3 g, 24.8 mmol) were added to 300 ml of THF, stirred, and refluxed. Then, potassium carbonate (9.8 g, 70.7 mmol) dissolved in 29 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and the aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 10.7 g of compound 1-64. (Yield 67%, MS: [M+H] ⁺ = 678)

Manufacturing Example 1-65

(3-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz47(32.9 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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 1-65_P1. (Yield 68%, MS: [M+H] ⁺ = 636)

Compound 1-65_P1 (15 g, 23.6 mmol) and phenylboronic acid (3 g, 24.8 mmol) were added to 300 ml of THF, stirred, and refluxed. Then, potassium carbonate (9.8 g, 70.7 mmol) dissolved in 29 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and the aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 10.5 g of compound 1-65. (Yield 66%, MS: [M+H] ⁺ = 678)

Manufacturing Example 1-66

(3-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz48(32.9 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 25.9 g of compound 1-66_P1. (Yield 67%, MS: [M+H] ⁺ = 636)

Compound 1-66_P1 (15 g, 23.6 mmol) and dibenzo[b,d]furan-1-ylboronic acid (5.2 g, 24.8 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (9.8 g, 70.7 mmol) dissolved in 29 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.1 g of compound 1-66. (Yield 67%, MS: [M+H] ⁺ = 768)

Manufacturing Example 1-67

At 0 ℃, a solution was prepared by adding Trifluoromethanesulfonic anhydride (30.1 g, 106.6 mmol) and Deuterium oxide (10.7 g, 532.8 mmol) and stirring for 5 hours. 1-bromo-3-chlorodibenzo[b,d]furan (15 g, 53.3 mmol) was added to 120 ml of 1,2,4-trichlorobenzene and stirring. After that, the prepared mixed solution of Trifluoromethanesulfonic anhydride and Deuterium oxide was slowly added dropwise to the mixed solution of 1-bromo-3-chlorodibenzo[b,d]furan and 1,2,4-trichlorobenzene and stirred while maintaining the temperature at 140 ℃. After 4 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. After that, the organic layer was neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 6 g of compound sub5-1-1. (Yield 40%, MS: [M+H] ⁺ = 283)

Compound sub5-1-1 (15 g, 52.9 mmol) and bis (pinacolato) diboron (14.8 g, 58.2 mmol) were stirred and refluxed 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, the mixture was cooled to room temperature, and the organic layer was separated using chloroform and water, and then the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.8 g of compound sub5-1-2. (Yield 56%, MS: [M+H] ⁺ = 331)

Compound sub5-1-2 (15 g, 45.4 mmol) and compound Trz49 (27.3 g, 47.6 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (18.8 g, 136.1 mmol) dissolved in 56 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 21.8 g of compound 1-67_P1. (Yield 69%, MS: [M+H] ⁺ = 698)

Compound 1-67_P1 (15 g, 21.5 mmol) and phenylboronic acid (2.8 g, 22.6 mmol) were added to 300 ml of THF, stirred, and refluxed. Then, potassium carbonate (8.9 g, 64.5 mmol) dissolved in 27 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and the aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.6 g of compound 1-67. (Yield 73%, MS: [M+H] ⁺ = 739)

Manufacturing Example 1-68

At 0 ℃, a solution was prepared by adding Trifluoromethanesulfonic anhydride (60.1 g, 213.1 mmol) and Deuterium oxide (21.4 g, 1065.6 mmol) and stirring for 5 hours. 1-bromo-3-chlorodibenzo[b,d]furan (15 g, 53.3 mmol) was added to 120 ml of 1,2,4-trichlorobenzene and stirring was performed. After that, the prepared mixed solution of Trifluoromethanesulfonic anhydride and Deuterium oxide was slowly added dropwise to the mixed solution of 1-bromo-3-chlorodibenzo[b,d]furan and 1,2,4-trichlorobenzene and stirred while maintaining the temperature at 140 ℃. After 10 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. After that, the organic layer was neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 6.2 g of compound sub5-2-1. (Yield 41%, MS: [M+H] ⁺ = 285)

Compound sub5-2-1 (15 g, 52.9 mmol) and bis (pinacolato) diboron (14.8 g, 58.2 mmol) were stirred and refluxed 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, the mixture was cooled to room temperature, and the organic layer was separated using chloroform and water, and then the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.8 g of compound sub5-2-2. (Yield 62%, MS: [M+H] ⁺ = 331)

Compound sub5-2-2 (15 g, 45.1 mmol) and compound Trz50 (13.2 g, 47.4 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (18.7 g, 135.3 mmol) dissolved in 56 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.1 g of compound 1-68_P1. (Yield 65%, MS: [M+H] ⁺ = 448)

Compound 1-68_P1 (15 g, 33.5 mmol) and naphtho[2,3-b]benzofuran-1-ylboronic acid (9.2 g, 35.2 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (13.9 g, 100.5 mmol) dissolved in 42 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 15.6 g of compound 1-68. (Yield 74%, MS: [M+H] ⁺ = 630)

Manufacturing Example 1-69

At 0 ℃, a solution was prepared by adding Trifluoromethanesulfonic anhydride (75.2 g, 266.4 mmol) and Deuterium oxide (26.7 g, 1332 mmol) and stirring for 5 hours. 1-bromo-3-chlorodibenzo[b,d]furan (15 g, 53.3 mmol) was added to 120 ml of 1,2,4-trichlorobenzene and stirring. After that, the prepared mixed solution of Trifluoromethanesulfonic anhydride and Deuterium oxide was slowly added dropwise to the mixed solution of 1-bromo-3-chlorodibenzo[b,d]furan and 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 12 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. After that, the organic layer was neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 5.6 g of ub5-3-1. (Yield 37%, MS: [M+H] ⁺ = 286)

Compound sub5-3-1 (15 g, 52.3 mmol) and bis (pinacolato) diboron (14.6 g, 57.6 mmol) were stirred and refluxed in 300 ml of 1,4-dioxane. Then, potassium acetate (7.7 g, 78.5 mmol) was added, and after sufficient stirring, bis (dibenzylideneacetone) palladium (0) (0.9 g, 1.6 mmol) and tricyclohexylphosphine (0.9 g, 3.1 mmol) were added. After reacting for 6 hours, the mixture was cooled to room temperature, and the organic layer was separated using chloroform and water, and then the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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 sub5-3-2. (Yield 69%, MS: [M+H] ⁺ = 334)

Compound sub5-3-2 (15 g, 45 mmol) and compound Trz44 (17.4 g, 47.2 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (18.6 g, 134.9 mmol) dissolved in 56 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 17.2 g of compound 1-69_P1. (Yield 71%, MS: [M+H] ⁺ = 539)

Compound 1-69_P1 (15 g, 27.8 mmol) and naphthalen-2-ylboronic acid (5 g, 29.2 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (11.5 g, 83.5 mmol) dissolved in 35 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.3 g of compound 1-69. (Yield 70%, MS: [M+H] ⁺ = 631)

Manufacturing Example 1-70

(3-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz14(25.2 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 22.8 g of compound 1-70_P1. (Yield 67%, MS: [M+H] ⁺ = 560)

Compound 1-70_P1 (15 g, 26.8 mmol) and phenylboronic acid (3.4 g, 28.1 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (11.1 g, 80.3 mmol) dissolved in 33 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 10.9 g of compound 1-70_P2. (Yield 68%, MS: [M+H] ⁺ = 602)

Compound 1-70_P2 (10 g, 16.6 mmol), PtO ₂ (1.1 g, 5 mmol), and 83 ml of D ₂ O were added to a shaker tube, sealed, and heated at 250 ° C., 600 psi for 12 hours. When the reaction was complete, chloroform was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO ₄ and concentrated, and the sample was purified by silica gel column chromatography to produce 4 g of compound 1-70. (Yield 39%, MS: [M + H] ⁺ = 626)

Manufacturing Example 1-71

(3-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz17(20.3 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 21.2 g of compound 1-71_P1. (Yield 72%, MS: [M+H] ⁺ = 484)

Compound 1-71_P1 (15 g, 31 mmol) and naphtho[2,3-b]benzofuran-4-ylboronic acid (8.5 g, 32.5 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (12.9 g, 93 mmol) dissolved in 39 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.2 g of compound 1-71_P2. (Yield 69%, MS: [M+H] ⁺ = 666)

Compound 1-71_P2 (10 g, 15 mmol), PtO ₂ (1 g, 4.5 mmol), and 75 ml of D ₂ O were added to a shaker tube, sealed, and heated at 250 ° C., 600 psi for 12 hours. When the reaction was complete, chloroform was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO ₄ and concentrated, and the sample was purified by silica gel column chromatography to produce 3.8 g of compound 1-71. (Yield 37%, MS: [M + H] ⁺ = 690)

Manufacturing Example 1-72

Compound 1-59 (10 g, 15.9 mmol), PtO ₂ (1.1 g, 4.8 mmol), and 80 ml of D ₂ O were added to a shaker tube, sealed, and heated at 250 ° C., 600 psi for 12 hours. When the reaction was complete, chloroform was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO ₄ and concentrated, and the sample was purified by silica gel column chromatography to produce 4 g of compound 1-72. (Yield 39%, MS: [M + H] ⁺ = 653)

Manufacturing Example 1-73

(2-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz51(28.4 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.8 g of compound 1-73_P1. (Yield 67%, MS: [M+H] ⁺ = 610)

Compound 1-73_P1 (15 g, 24.6 mmol) and naphthalen-2-ylboronic acid (4.4 g, 25.8 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (10.2 g, 73.8 mmol) dissolved in 31 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.1 g of compound 1-73. (Yield 70%, MS: [M+H] ⁺ = 702)

Manufacturing Example 1-74

(2-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz52(23.5 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 23.4 g of compound 1-74_P1. (Yield 72%, MS: [M+H] ⁺ = 534)

Compound 1-74_P1 (15 g, 28.1 mmol) and [1,1'-biphenyl]-4-ylboronic acid (5.8 g, 29.5 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (11.6 g, 84.3 mmol) dissolved in 35 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.1 g of compound 1-74. (Yield 66%, MS: [M+H] ⁺ = 652)

Manufacturing Example 1-75

(2-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz53(22 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.1 g of compound 1-75_P1. (Yield 65%, MS: [M+H] ⁺ = 510)

Compound 1-75_P1 (15 g, 29.4 mmol) and (4-(naphthalen-1-yl)phenyl)boronic acid (7.7 g, 30.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (12.2 g, 88.2 mmol) dissolved in 37 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.9 g of compound 1-75. (Yield 65%, MS: [M+H] ⁺ = 678)

Manufacturing Example 1-76

(2-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz54(23.5 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23 g of compound 1-76_P1. (Yield 71%, MS: [M+H] ⁺ = 534)

Compound 1-76_P1 (15 g, 28.1 mmol) and dibenzo[b,d]thiophen-1-ylboronic acid (6.7 g, 29.5 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (11.6 g, 84.3 mmol) dissolved in 35 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.4 g of compound 1-76. (Yield 70%, MS: [M+H] ⁺ = 682)

Manufacturing Example 1-77

(2-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz55(28.4 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 26.7 g of compound 1-77_P1. (Yield 72%, MS: [M+H] ⁺ = 610)

Compound 1-77_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. Then, potassium carbonate (10.2 g, 73.8 mmol) dissolved in 31 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and the aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.8 g of compound 1-77. (Yield 74%, MS: [M+H] ⁺ = 652)

Manufacturing Example 1-78

(2-chlorodibenzo[b,d]furan-1-yl)boronic acid(15 g, 60.9 mmol) and compound Trz56(30.6 g, 63.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate(25.2 g, 182.6 mmol) dissolved in 76 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.3 g, 0.6 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 27 g of compound 1-78_P1. (Yield 74%, MS: [M+H] ⁺ = 600)

Compound 1-78_P1 (15 g, 25 mmol) and phenylboronic acid (3.2 g, 26.2 mmol) were added to 300 ml of THF, stirred, and refluxed. Then, potassium carbonate (10.4 g, 75 mmol) dissolved in 31 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and the aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.5 g of compound 1-78. (Yield 72%, MS: [M+H] ⁺ = 642)

Manufacturing Example 1-79

At 0 ℃, a solution was prepared by adding Trifluoromethanesulfonic anhydride (60.1 g, 213.1 mmol) and Deuterium oxide (21.4 g, 1065.6 mmol) and stirring for 5 hours. 1-bromo-2-chlorodibenzo[b,d]furan (15 g, 53.3 mmol) was added to 120 ml of 1,2,4-trichlorobenzene and stirring. After that, the prepared mixed solution of Trifluoromethanesulfonic anhydride and Deuterium oxide was slowly added dropwise to the mixed solution of 1-bromo-2-chlorodibenzo[b,d]furan and 1,2,4-trichlorobenzene, and stirred while maintaining the temperature at 140 ℃. After 10 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. After that, the organic layer was neutralized with potassium carbonate aqueous solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 6.1 g of compound sub6-1-1. (Yield 40%, MS: [M+H] ⁺ = 285)

Compound sub6-1-1 (15 g, 52.5 mmol) and bis (pinacolato) diboron (14.7 g, 57.8 mmol) were stirred and refluxed 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 5 hours, the mixture was cooled to room temperature, and the organic layer was separated using chloroform and water, and then the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.5 g of compound sub6-1-2. (Yield 60%, MS: [M+H] ⁺ = 333)

Compound sub6-1-2 (15 g, 45.1 mmol) and compound Trz57 (21.3 g, 47.4 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (18.7 g, 135.3 mmol) dissolved in 56 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 18.1 g of compound 1-79_P1. (Yield 65%, MS: [M+H] ⁺ = 619)

Compound 1-79_P1 (15 g, 24.2 mmol) and phenylboronic acid (3.1 g, 25.4 mmol) were added to 300 ml of THF, stirred, and refluxed. Then, potassium carbonate (10 g, 72.7 mmol) dissolved in 30 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and the aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11 g of compound 1-79. (Yield 69%, MS: [M+H] ⁺ = 661)

Manufacturing Example 1-80

Compound 1-78 (10 g, 15.6 mmol), PtO ₂ (1.1 g, 4.7 mmol), and D ₂ O 78 ml were added to a shaker tube, sealed, and heated at 250 ° C., 600 psi for 12 hours. When the reaction was complete, chloroform was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO ₄ and concentrated, and the sample was purified by silica gel column chromatography to produce 4.3 g of compound 1-80. (Yield 42%, MS: [M + H] ⁺ = 665)

Manufacturing Example 2-1

Compound amine1 (10 g, 20.7 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (15 g, 746.9 mmol) was added to trifluoromethanesulfonic anhydride (52.7 g, 186.7 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 8 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 5 g of compound 2-1 (yield 48%, MS: [M+H]+= 501).

Compound 2-1 (15 g, 30 mmol) and phenanthren-9-ylboronic acid_D4 (7.1 g, 31.5 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (12.4 g, 90 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.7 g of compound 2-1-D22 (yield 76%, MS: [M+H]+= 647).

Manufacturing Example 2-2

Compound amine2 (10 g, 19.7 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (14.2 g, 708.6 mmol) was added to trifluoromethanesulfonic anhydride (33.3 g, 118.1 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 4 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 5.1 g of compound 2-2 (yield 50%, MS: [M+H]+= 518).

Compound 2-2 (15 g, 29 mmol) and phenanthren-9-ylboronic acid_D9 (7 g, 30.5 mmol) were added to 300 ml of THF, stirred, and refluxed. Then, potassium carbonate (12 g, 87 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and the aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.5 g of compound 2-2-D18. (Yield 75%, MS: [M+H]+= 669)

Manufacturing Example 2-3

Compound amine3 (10 g, 19.2 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (13.8 g, 689.6 mmol) was added to trifluoromethanesulfonic anhydride (48.6 g, 172.4 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 8 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 5 g of compound 2-3 (yield 48%, MS: [M+H]+= 542).

Compound 2-3 (15 g, 27.7 mmol) and phenanthren-9-ylboronic acid_D7 (6.7 g, 29.1 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (11.5 g, 83.2 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.5 g of compound 2-3-D26 (yield 60%, MS: [M+H]+= 691).

Manufacturing Example 2-4

Compound amine4 (10 g, 16.7 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (12.1 g, 601.9 mmol) was added to trifluoromethanesulfonic anhydride (42.5 g, 150.5 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 8 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.3 g of compound 2-4 (yield 41%, MS: [M+H]+= 621).

Compound 2-4 (15 g, 24.2 mmol) and phenanthren-9-ylboronic acid_D6 (5.8 g, 25.4 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (10 g, 72.6 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.9 g of compound 2-4-D28 (yield 75%, MS: [M+H]+= 769).

Manufacturing Example 2-5

Compound amine5 (10 g, 18.8 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (13.6 g, 676.6 mmol) was added to trifluoromethanesulfonic anhydride (63.6 g, 225.5 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 15 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 5.2 g of compound 2-5 (yield 50%, MS: [M+H]+= 559).

Compound 2-5 (15 g, 26.9 mmol) and phenanthren-9-ylboronic acid_D9 (6.5 g, 28.2 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (11.1 g, 80.6 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.1 g of compound 2-5-D35 (yield 74%, MS: [M+H]+= 710).

Manufacturing Example 2-6

Compound amine6 (10 g, 17.1 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (12.3 g, 616.3 mmol) was added to trifluoromethanesulfonic anhydride (43.5 g, 154.1 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and stirred while maintaining the temperature. After 8 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.7 g of compound 2-6 (yield 45%, MS: [M+H]+= 609).

Compound 2-6 (15 g, 24.7 mmol) and phenanthren-9-ylboronic acid_D2 (5.8 g, 25.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (10.2 g, 74 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.9 g of compound 2-6-D26 (yield 75%, MS: [M+H]+= 753).

Manufacturing Example 2-7

Compound amine7 (10 g, 17.1 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (12.3 g, 616.3 mmol) was added to trifluoromethanesulfonic anhydride (58 g, 205.4 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 15 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.8 g of compound 2-7 (yield 46%, MS: [M+H]+= 615).

Compound 2-7 (15 g, 24.4 mmol) and phenanthren-9-ylboronic acid_D9 (5.9 g, 25.6 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (10.1 g, 73.3 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.4 g of compound 2-7-D39 (yield 61%, MS: [M+H]+= 766).

Manufacturing Example 2-8

Compound amine8 (10 g, 18.4 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (13.3 g, 661.5 mmol) was added to trifluoromethanesulfonic anhydride (31.1 g, 110.3 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 4 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.8 g of compound 2-8 (yield 47%, MS: [M+H]+= 563).

Compound 2-8 (15 g, 26.8 mmol) and phenanthren-9-ylboronic acid_D6 (6.4 g, 28.1 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (11.1 g, 80.3 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.1 g of compound 2-8-D25 (yield 69%, MS: [M+H]+= 711).

Manufacturing Example 2-9

Compound amine9 (10 g, 19.4 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (14 g, 697.5 mmol) was added to trifluoromethanesulfonic anhydride (32.8 g, 116.2 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 4 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.4 g of compound 2-9 (yield 43%, MS: [M+H]+= 534).

Compound 2-9 (15 g, 28.3 mmol) and phenanthren-9-ylboronic acid_D5 (6.7 g, 29.7 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (11.7 g, 84.9 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 15.3 g of compound 2-9-D23 (yield 80%, MS: [M+H]+= 681).

Manufacturing Example 2-10

Compound amine10 (10 g, 17.9 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (12.9 g, 645 mmol) was added to trifluoromethanesulfonic anhydride (45.5 g, 161.3 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 8 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.4 g of compound 2-10 (yield 42%, MS: [M+H]+= 580).

Compound 2-10 (15 g, 25.9 mmol) and phenanthren-9-ylboronic acid_D8 (6.3 g, 27.2 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (10.7 g, 77.7 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.6 g of compound 2-10-D29 (yield 67%, MS: [M+H]+= 730).

Manufacturing Example 2-11

Compound amine11 (10 g, 16.4 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (11.9 g, 591.9 mmol) was added to trifluoromethanesulfonic anhydride (27.8 g, 98.7 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and stirred while maintaining the temperature. After 4 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.9 g of compound 2-11 (yield 48%, MS: [M+H]+= 623).

Compound 2-11 (15 g, 24.1 mmol) and phenanthren-9-ylboronic acid_D7 (5.8 g, 25.3 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (10 g, 72.3 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 4 hours of reaction, it was cooled to room temperature, the organic layer and aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.5 g of compound 2-11-D21 (yield 62%, MS: [M+H]+= 772).

Manufacturing Example 2-12

Compound amine12 (10 g, 17.9 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (12.9 g, 645 mmol) was added to trifluoromethanesulfonic anhydride (45.5 g, 161.3 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 8 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 5.1 g of compound 2-12 (yield 49%, MS: [M+H]+= 581).

Compound 2-12 (15 g, 25.9 mmol) and phenanthren-9-ylboronic acid_D5 (6.2 g, 27.1 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (10.7 g, 77.6 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.5 g of compound 2-12-D27 (yield 61%, MS: [M+H]+= 728).

Manufacturing Example 2-13

Compound amine13 (10 g, 18.8 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (13.6 g, 676.6 mmol) was added to trifluoromethanesulfonic anhydride (47.7 g, 169.1 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 8 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 5.1 g of compound 2-13 (yield 49%, MS: [M+H]+= 553).

Compound 2-13 (15 g, 27.2 mmol) and phenanthren-9-ylboronic acid_D9 (6.6 g, 28.5 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (11.3 g, 81.5 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 15.1 g of compound 2-13-D29 (yield 79%, MS: [M+H]+= 704).

Manufacturing Example 2-14

Compound amine14 (10 g, 17.1 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (12.3 g, 616.3 mmol) was added to trifluoromethanesulfonic anhydride (43.5 g, 154.1 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and stirred while maintaining the temperature. After 8 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.5 g of compound 2-14 (yield 43%, MS: [M+H]+= 608).

Compound 2-14 (15 g, 24.7 mmol) and phenanthren-9-ylboronic acid_D7 (5.9 g, 25.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (10.2 g, 74.1 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12 g of compound 2-14-D30 (yield 64%, MS: [M+H]+= 757).

Manufacturing Example 2-15

Compound amine15 (10 g, 16.7 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (12.1 g, 601.9 mmol) was added to trifluoromethanesulfonic anhydride (28.3 g, 100.3 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 4 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.4 g of compound 2-15 (yield 43%, MS: [M+H]+= 614).

Compound 2-15 (15 g, 24.5 mmol) and phenanthren-9-ylboronic acid_D4 (5.8 g, 25.7 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (10.1 g, 73.4 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.7 g of compound 2-15-D19 (yield 74%, MS: [M+H]+= 760).

Manufacturing Example 2-16

Compound amine16 (10 g, 16.1 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (11.6 g, 580.4 mmol) was added to trifluoromethanesulfonic anhydride (27.3 g, 96.7 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 4 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 5 g of compound 2-16 (yield 49%, MS: [M+H]+= 639).

Compound 2-16 (15 g, 23.5 mmol) and phenanthren-9-ylboronic acid_D8 (5.7 g, 24.7 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (9.8 g, 70.6 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.5 g of compound 2-16-D27 (yield 62%, MS: [M+H]+= 789).

Manufacturing Example 2-17

Compound amine 17 (10 g, 18.4 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (13.3 g, 664 mmol) was added to trifluoromethanesulfonic anhydride (46.8 g, 166 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 8 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 5.1 g of compound 2-17 (yield 49%, MS: [M+H]+= 570).

Compound 2-17 (15 g, 26.4 mmol) and phenanthren-9-ylboronic acid_D1 (6.2 g, 27.7 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (10.9 g, 79.1 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.1 g of compound 2-17-D28 (yield 75%, MS: [M+H]+= 713).

Manufacturing Example 2-18

Compound amine18 (10 g, 23.2 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (16.7 g, 833.4 mmol) was added to trifluoromethanesulfonic anhydride (58.8 g, 208.4 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and stirred while maintaining it. After 8 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.3 g of compound 2-18 (yield 41%, MS: [M+H]+= 449).

Compound 2-18 (15 g, 33.5 mmol) and phenanthren-9-ylboronic acid_D8 (8.1 g, 35.2 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (13.9 g, 100.5 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 15.8 g of compound 2-18-D24 (yield 79%, MS: [M+H]+= 599).

Manufacturing Example 2-19

Compound amine19 (10 g, 17.9 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (12.9 g, 645 mmol) was added to trifluoromethanesulfonic anhydride (45.5 g, 161.3 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 8 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.3 g of compound 2-19 (yield 41%, MS: [M+H]+= 581).

Compound 2-19 (15 g, 25.9 mmol) and phenanthren-9-ylboronic acid_D4 (6.1 g, 27.1 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (10.7 g, 77.6 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.2 g of compound 2-19-D26 (yield 65%, MS: [M+H]+= 727).

Manufacturing Example 2-20

Compound amine20 (10 g, 17.9 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (12.9 g, 645 mmol) was added to trifluoromethanesulfonic anhydride (30.3 g, 107.5 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 4 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.9 g of compound 2-20 (yield 48%, MS: [M+H]+= 572).

Compound 2-20 (15 g, 26.3 mmol) and phenanthren-9-ylboronic acid_D9 (6.4 g, 27.6 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (10.9 g, 78.8 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.7 g of compound 2-20-D22 (yield 72%, MS: [M+H]+= 723).

Manufacturing Example 2-21

Compound amine21 (10 g, 17.9 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (12.9 g, 645 mmol) was added to trifluoromethanesulfonic anhydride (60.7 g, 215 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and stirred while maintaining the temperature. After 15 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 5.3 g of compound 2-21 (yield 50%, MS: [M+H]+= 587).

Compound 2-21 (15 g, 25.6 mmol) and phenanthren-9-ylboronic acid_D9 (6.2 g, 26.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (10.6 g, 76.8 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.2 g of compound 2-21-D37 (yield 70%, MS: [M+H]+= 738).

Manufacturing Example 2-22

Compound amine22 (10 g, 17.1 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (12.3 g, 616.3 mmol) was added to trifluoromethanesulfonic anhydride (29 g, 102.7 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 4 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.2 g of compound 2-22 (yield 41%, MS: [M+H]+= 600).

Compound 2-22 (15 g, 25 mmol) and phenanthren-9-ylboronic acid_D5 (6 g, 26.3 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (10.4 g, 75.1 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.3 g of compound 2-22-D20 (yield 71%, MS: [M+H]+= 747).

Manufacturing Example 2-23

Compound amine23 (10 g, 16.7 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (12.1 g, 601.9 mmol) was added to trifluoromethanesulfonic anhydride (28.3 g, 100.3 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 4 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 5.1 g of compound 2-23 (yield 50%, MS: [M+H]+= 613).

Compound 2-23 (15 g, 24.5 mmol) and phenanthren-9-ylboronic acid_D7 (5.9 g, 25.7 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (10.2 g, 73.5 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.5 g of compound 2-23-D21 (yield 67%, MS: [M+H]+= 762).

Manufacturing Example 2-24

Compound amine24 (10 g, 17.1 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (12.3 g, 616.3 mmol) was added to trifluoromethanesulfonic anhydride (43.5 g, 154.1 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and stirred while maintaining the temperature. After 8 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 5 g of compound 2-24 (yield 48%, MS: [M+H]+= 604).

Compound 2-24 (15 g, 24.9 mmol) and phenanthren-9-ylboronic acid_D3 (5.9 g, 26.1 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (10.3 g, 74.6 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.3 g of compound 2-24-D22 (yield 66%, MS: [M+H]+= 749).

Manufacturing Example 2-25

Compound amine25 (10 g, 16.2 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (11.7 g, 582.3 mmol) was added to trifluoromethanesulfonic anhydride (27.4 g, 97 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and stirred while maintaining the temperature. After 4 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 5 g of compound 2-25 (yield 49%, MS: [M+H]+= 637).

Compound 2-25 (15 g, 23.6 mmol) and phenanthren-9-ylboronic acid_D9 (5.7 g, 24.8 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (9.8 g, 70.7 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.1 g of compound 2-25-D27 (yield 65%, MS: [M+H]+= 788).

Manufacturing Example 2-26

Compound amine26 (10 g, 18.4 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (13.3 g, 661.5 mmol) was added to trifluoromethanesulfonic anhydride (31.1 g, 110.3 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 4 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.4 g of compound 2-26 (yield 43%, MS: [M+H]+= 563).

Compound 2-26 (15 g, 26.7 mmol) and phenanthren-9-ylboronic acid_D7 (6.4 g, 28 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (11.1 g, 80 mmol) dissolved in 100 ml of water was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12 g of compound 2-26-D25 (yield 63%, MS: [M+H]+= 712).

Manufacturing Example 2-27

Compound amine27 (10 g, 19.7 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (14.2 g, 708.6 mmol) was added to trifluoromethanesulfonic anhydride (50 g, 177.1 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 8 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 5 g of compound 2-27 (yield 48%, MS: [M+H]+= 529).

Compound 2-27 (15 g, 28.4 mmol) and phenanthren-9-ylboronic acid_D8 (6.9 g, 29.8 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (11.8 g, 85.2 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.1 g of compound 2-27-D28 (yield 63%, MS: [M+H]+= 679).

Manufacturing Example 2-28

Compound amine28 (10 g, 19.7 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (14.2 g, 708.6 mmol) was added to trifluoromethanesulfonic anhydride (66.6 g, 236.2 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 15 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 5.2 g of compound 2-28 (yield 49%, MS: [M+H]+= 535).

Compound 2-28 (15 g, 28.1 mmol) and phenanthren-9-ylboronic acid_D9 (6.8 g, 29.5 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (11.6 g, 84.3 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.5 g of compound 2-28-D35 (yield 65%, MS: [M+H]+= 686).

Manufacturing Example 2-29

Compound amine29 (10 g, 17.9 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (12.9 g, 645 mmol) was added to trifluoromethanesulfonic anhydride (30.3 g, 107.5 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and stirred while maintaining the temperature. After 4 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.2 g of compound 2-29 (yield 41%, MS: [M+H]+= 573).

Compound 2-29 (15 g, 26.2 mmol) and phenanthren-9-ylboronic acid_D9 (6.4 g, 27.5 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (10.9 g, 78.7 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.4 g of compound 2-29-D23 (yield 60%, MS: [M+H]+= 724).

Manufacturing Example 2-30

Compound amine30 (10 g, 16.4 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (11.9 g, 591.9 mmol) was added to trifluoromethanesulfonic anhydride (41.8 g, 148 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 8 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 5.2 g of compound 2-30 (yield 50%, MS: [M+H]+= 628).

Compound 2-30 (15 g, 23.9 mmol) and phenanthren-9-ylboronic acid_D3 (5.7 g, 25.1 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (9.9 g, 71.7 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.3 g of compound 2-30-D22 (yield 61%, MS: [M+H]+= 773).

Manufacturing Example 2-31

Compound amine31 (10 g, 17.1 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (12.3 g, 616.3 mmol) was added to trifluoromethanesulfonic anhydride (43.5 g, 154.1 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and stirred while maintaining the temperature. After 8 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.8 g of compound 2-31 (yield 46%, MS: [M+H]+= 607).

Compound 2-31 (15 g, 24.7 mmol) and phenanthren-9-ylboronic acid_D9 (6 g, 26 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (10.3 g, 74.2 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.6 g of compound 2-31-D31 (yield 78%, MS: [M+H]+= 758).

Manufacturing Example 2-32

Compound amine32 (10 g, 18.8 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (13.6 g, 676.6 mmol) was added to trifluoromethanesulfonic anhydride (47.7 g, 169.1 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 8 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.3 g of compound 2-32 (yield 42%, MS: [M+H]+= 552).

Compound 2-32 (15 g, 27.2 mmol) and phenanthren-9-ylboronic acid_D5 (6.5 g, 28.6 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (11.3 g, 81.7 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.5 g of compound 2-32-D24 (yield 71%, MS: [M+H]+= 699).

Manufacturing Example 2-33

Compound amine33 (10 g, 18.6 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (13.4 g, 669 mmol) was added to trifluoromethanesulfonic anhydride (31.5 g, 111.5 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 4 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.5 g of compound 2-33 (yield 44%, MS: [M+H]+= 551).

Compound 2-33 (15 g, 27.3 mmol) and phenanthren-9-ylboronic acid_D7 (6.6 g, 28.6 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (11.3 g, 81.8 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.3 g of compound 2-33-D19 (yield 75%, MS: [M+H]+= 700).

Manufacturing Example 2-34

Compound amine34 (10 g, 16.3 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (11.7 g, 586.1 mmol) was added to trifluoromethanesulfonic anhydride (41.3 g, 146.5 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and stirred while maintaining the temperature. After 8 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.5 g of compound 2-34 (yield 44%, MS: [M+H]+= 635).

Compound 2-34 (15 g, 23.7 mmol) and phenanthren-9-ylboronic acid_D3 (5.6 g, 24.8 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (9.8 g, 71 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.7 g of compound 2-34-D23 (yield 69%, MS: [M+H]+= 780).

Manufacturing Example 2-35

Compound amine35 (10 g, 17.8 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (12.8 g, 640.4 mmol) was added to trifluoromethanesulfonic anhydride (45.2 g, 160.1 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 8 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.7 g of compound 2-35 (yield 46%, MS: [M+H]+= 581).

Compound 2-35 (15 g, 25.9 mmol) and phenanthren-9-ylboronic acid_D7 (6.2 g, 27.1 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (10.7 g, 77.6 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.3 g of compound 2-35-D25 (yield 60%, MS: [M+H]+= 730).

Manufacturing Example 2-36

Compound amine36 (10 g, 21.7 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (15.7 g, 782.6 mmol) was added to trifluoromethanesulfonic anhydride (36.8 g, 130.4 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and stirred while maintaining the temperature. After 4 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.1 g of compound 2-36 (yield 40%, MS: [M+H]+= 472).

Compound 2-36 (15 g, 31.8 mmol) and phenanthren-9-ylboronic acid_D9 (7.7 g, 33.4 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (13.2 g, 95.5 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.5 g of compound 2-36-D20 (yield 63%, MS: [M+H]+= 623).

Manufacturing Example 2-37

Compound amine37 (10 g, 19.7 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (14.2 g, 708.6 mmol) was added to trifluoromethanesulfonic anhydride (50 g, 177.1 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and stirred while maintaining the temperature. After 8 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 5 g of compound 2-37 (yield 48%, MS: [M+H]+= 527).

Compound 2-37 (15 g, 28.5 mmol) and phenanthren-9-ylboronic acid_D9 (6.9 g, 29.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (11.8 g, 85.4 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.2 g of compound 2-37-D28 (yield 74%, MS: [M+H]+= 678).

Manufacturing Example 2-38

Compound amine38 (10 g, 17.9 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (12.9 g, 642.7 mmol) was added to trifluoromethanesulfonic anhydride (30.2 g, 107.1 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 4 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 5 g of compound 2-38 (yield 49%, MS: [M+H]+= 575).

Compound 2-38 (15 g, 26.1 mmol) and phenanthren-9-ylboronic acid_D6 (6.3 g, 27.4 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (10.8 g, 78.4 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.4 g of compound 2-38-D20 (yield 66%, MS: [M+H]+= 721).

Manufacturing Example 2-39

Compound amine39 (10 g, 16.4 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (11.9 g, 591.9 mmol) was added to trifluoromethanesulfonic anhydride (41.8 g, 148 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 8 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.9 g of compound 2-39 (yield 48%, MS: [M+H]+= 628).

Compound 2-39 (15 g, 23.9 mmol) and phenanthren-9-ylboronic acid_D2 (5.6 g, 25.1 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (9.9 g, 71.7 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.2 g of compound 39-D21 (yield 66%, MS: [M+H]+= 772).

Manufacturing Example 2-40

Compound amine40 (10 g, 17.9 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (12.9 g, 645 mmol) was added to trifluoromethanesulfonic anhydride (30.3 g, 107.5 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 4 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 5 g of compound 2-40 (yield 49%, MS: [M+H]+= 574).

Compound 2-40 (15 g, 26.2 mmol) and phenanthren-9-ylboronic acid_D5 (6.2 g, 27.5 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (10.9 g, 78.5 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.4 g of compound 2-40-D20 (yield 66%, MS: [M+H]+= 721).

Manufacturing Example 2-41

Compound amine41 (10 g, 17.1 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (12.3 g, 616.3 mmol) was added to trifluoromethanesulfonic anhydride (29 g, 102.7 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 4 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.1 g of compound 2-41 (yield 40%, MS: [M+H]+= 597).

Compound 2-41 (15 g, 25.2 mmol) and phenanthren-9-ylboronic acid_D9 (6.1 g, 26.4 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (10.4 g, 75.5 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.9 g of compound 2-41-D21 (yield 74%, MS: [M+H]+= 748).

Manufacturing Example 2-42

Compound amine42 (10 g, 17.9 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (12.9 g, 645 mmol) was added to trifluoromethanesulfonic anhydride (60.7 g, 215 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 15 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.6 g of compound 2-42 (yield 44%, MS: [M+H]+= 587).

Compound 2-42 (15 g, 25.6 mmol) and phenanthren-9-ylboronic acid_D9 (6.2 g, 26.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (10.6 g, 76.8 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.6 g of compound 2-42-D37 (yield 72%, MS: [M+H]+= 738).

Manufacturing Example 2-43

Compound amine43 (10 g, 17.1 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (12.3 g, 616.3 mmol) was added to trifluoromethanesulfonic anhydride (29 g, 102.7 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 4 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.2 g of compound 2-43 (yield 41%, MS: [M+H]+= 600).

Compound 2-43 (15 g, 25 mmol) and phenanthren-9-ylboronic acid_D6 (6 g, 26.3 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (10.4 g, 75.1 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.5 g of compound 2-43-D21 (yield 72%, MS: [M+H]+= 748).

Manufacturing Example 2-44

Compound amine44 (10 g, 17.1 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (12.3 g, 616.3 mmol) was added to trifluoromethanesulfonic anhydride (29 g, 102.7 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and stirred while maintaining the temperature. After 4 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.6 g of compound 2-44 (yield 45%, MS: [M+H]+= 598).

Compound 2-44 (15 g, 25.1 mmol) and phenanthren-9-ylboronic acid_D8 (6.1 g, 26.4 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (10.4 g, 75.4 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.3 g of compound 2-44-D21 (yield 76%, MS: [M+H]+= 748).

Manufacturing Example 2-45

Compound amine45 (10 g, 16.7 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (12.1 g, 601.9 mmol) was added to trifluoromethanesulfonic anhydride (42.5 g, 150.5 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 8 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 5.1 g of compound 2-45 (yield 49%, MS: [M+H]+= 621).

Compound 2-45 (15 g, 24.2 mmol) and phenanthren-9-ylboronic acid_D2 (5.7 g, 25.4 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (10 g, 72.6 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.2 g of compound 2-45-D24 (yield 66%, MS: [M+H]+= 765).

Manufacturing Example 2-46

Compound amine46 (10 g, 18.6 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (13.4 g, 669 mmol) was added to trifluoromethanesulfonic anhydride (31.5 g, 111.5 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 4 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 5 g of compound 2-46 (yield 49%, MS: [M+H]+= 549).

Compound 2-46 (15 g, 27.4 mmol) and phenanthren-9-ylboronic acid_D9 (6.6 g, 28.7 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (11.3 g, 82.1 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14 g of compound 2-46-D19 (yield 73%, MS: [M+H]+= 700).

Manufacturing Example 2-47

Compound amine47 (10 g, 18.7 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (13.4 g, 671.5 mmol) was added to trifluoromethanesulfonic anhydride (31.6 g, 111.9 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and stirred while maintaining the temperature. After 4 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.3 g of compound 2-47 (yield 42%, MS: [M+H]+= 552).

Compound 2-47 (15 g, 27.2 mmol) and phenanthren-9-ylboronic acid_D6 (6.5 g, 28.6 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (11.3 g, 81.7 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.3 g of compound 2-47-D21 (yield 75%, MS: [M+H]+= 700).

Manufacturing Example 2-48

Compound amine48 (10 g, 20.6 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (14.8 g, 740.6 mmol) was added to trifluoromethanesulfonic anhydride (52.2 g, 185.2 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 8 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.4 g of compound 2-48 (yield 42%, MS: [M+H]+= 505).

Compound 2-48 (15 g, 29.8 mmol) and phenanthren-9-ylboronic acid_D2 (7 g, 31.2 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (12.3 g, 89.3 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.6 g of compound 2-48-D20 (yield 60%, MS: [M+H]+= 649).

Manufacturing Example 2-49

Compound amine 49 (10 g, 19.7 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (14.2 g, 708.6 mmol) was added to trifluoromethanesulfonic anhydride (33.3 g, 118.1 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and stirred while maintaining the temperature. After 4 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.2 g of compound 2-49 (yield 41%, MS: [M+H]+= 520).

Compound 2-49 (15 g, 28.9 mmol) and phenanthren-9-ylboronic acid_D9 (7 g, 30.3 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (12 g, 86.7 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.2 g of compound 2-49-D20 (yield 68%, MS: [M+H]+= 671).

Manufacturing Example 2-50

Compound amine50 (10 g, 17.9 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (12.9 g, 645 mmol) was added to trifluoromethanesulfonic anhydride (45.5 g, 161.3 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 8 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 5.2 g of compound 2-50 (yield 50%, MS: [M+H]+= 578).

Compound 2-50 (15 g, 26 mmol) and phenanthren-9-ylboronic acid_D1 (6.1 g, 27.3 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (10.8 g, 78 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 15 g of compound 2-50-D20 (yield 80%, MS: [M+H]+= 721).

Manufacturing Example 2-51

Compound amine51 (10 g, 19.7 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (14.2 g, 708.6 mmol) was added to trifluoromethanesulfonic anhydride (33.3 g, 118.1 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 4 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.5 g of compound 2-51 (yield 44%, MS: [M+H]+= 521).

Compound 2-51 (15 g, 28.8 mmol) and phenanthren-9-ylboronic acid_D9 (7 g, 30.3 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (12 g, 86.5 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 15.5 g of compound 2-51-D21 (yield 80%, MS: [M+H]+= 672).

Manufacturing Example 2-52

Compound amine52 (10 g, 17.9 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (12.9 g, 645 mmol) was added to trifluoromethanesulfonic anhydride (60.7 g, 215 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and stirred while maintaining the temperature. After 15 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 5.3 g of compound 2-52 (yield 50%, MS: [M+H]+= 587).

Compound 2-52 (15 g, 25.6 mmol) and phenanthren-9-ylboronic acid_D9 (6.2 g, 26.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (10.6 g, 76.8 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.9 g of compound 2-52-D37 (yield 79%, MS: [M+H]+= 738).

Manufacturing Example 2-53

Compound amine53 (10 g, 18.8 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (13.6 g, 676.6 mmol) was added to trifluoromethanesulfonic anhydride (31.8 g, 112.8 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and stirred while maintaining it. After 4 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.8 g of compound 2-53 (yield 47%, MS: [M+H]+= 545).

Compound 2-53 (15 g, 27.6 mmol) and phenanthren-9-ylboronic acid_D7 (6.6 g, 28.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (11.4 g, 82.7 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.1 g of compound 2-53-D19 (yield 74%, MS: [M+H]+= 694).

Manufacturing Example 2-54

Compound amine54 (10 g, 18.4 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (13.3 g, 664 mmol) was added to trifluoromethanesulfonic anhydride (31.2 g, 110.7 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 4 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.9 g of compound 2-54 (yield 48%, MS: [M+H]+= 559).

Compound 2-54 (15 g, 26.9 mmol) and phenanthren-9-ylboronic acid_D9 (6.5 g, 28.2 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (11.1 g, 80.6 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.1 g of compound 2-54-D25 (yield 74%, MS: [M+H]+= 710).

Manufacturing Example 2-55

Compound amine55 (10 g, 18.6 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (13.4 g, 669 mmol) was added to trifluoromethanesulfonic anhydride (47.2 g, 167.3 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and stirred while maintaining the temperature. After 8 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.9 g of compound 2-55 (yield 47%, MS: [M+H]+= 559).

Compound 2-55 (15 g, 26.9 mmol) and phenanthren-9-ylboronic acid_D3 (6.4 g, 28.2 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (11.1 g, 80.6 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.3 g of compound 2-55-D23 (yield 60%, MS: [M+H]+= 704).

Manufacturing Example 2-56

Compound amine56 (10 g, 17.9 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (12.9 g, 645 mmol) was added to trifluoromethanesulfonic anhydride (30.3 g, 107.5 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 4 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.1 g of compound 2-56 (yield 40%, MS: [M+H]+= 571).

Compound 2-56 (15 g, 26.3 mmol) and phenanthren-9-ylboronic acid_D9 (6.4 g, 27.6 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (10.9 g, 78.9 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.4 g of compound 2-56-D21 (yield 60%, MS: [M+H]+= 722).

Manufacturing Example 2-57

Compound amine57 (10 g, 17.9 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (12.9 g, 645 mmol) was added to trifluoromethanesulfonic anhydride (45.5 g, 161.3 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 8 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.6 g of compound 2-57 (yield 44%, MS: [M+H]+= 579).

Compound 2-57 (15 g, 25.9 mmol) and phenanthren-9-ylboronic acid_D9 (6.3 g, 27.2 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (10.8 g, 77.8 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.7 g of compound 2-57-D29 (yield 62%, MS: [M+H]+= 730).

Manufacturing Example 2-58

Compound amine58 (10 g, 16.4 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (11.9 g, 591.9 mmol) was added to trifluoromethanesulfonic anhydride (41.8 g, 148 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and stirred while maintaining the temperature. After 8 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.1 g of compound 2-58 (yield 40%, MS: [M+H]+= 631).

Compound 2-58 (15 g, 23.8 mmol) and phenanthren-9-ylboronic acid_D5 (5.7 g, 25 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (9.9 g, 71.4 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.2 g of compound 2-58-D27 (yield 77%, MS: [M+H]+= 778).

Manufacturing Example 2-59

Compound amine59 (10 g, 17.9 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (12.9 g, 645 mmol) was added to trifluoromethanesulfonic anhydride (45.5 g, 161.3 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 8 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.3 g of compound 2-59 (yield 41%, MS: [M+H]+= 582).

Compound 2-59 (15 g, 25.8 mmol) and phenanthren-9-ylboronic acid_D1 (6 g, 27.1 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (10.7 g, 77.4 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours of reaction, it was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.2 g of compound 2-59-D24 (yield 60%, MS: [M+H]+= 725).

Manufacturing Example 2-60

Compound amine60 (10 g, 17.9 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (12.9 g, 645 mmol) was added to trifluoromethanesulfonic anhydride (30.3 g, 107.5 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 4 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.7 g of compound 2-60 (yield 46%, MS: [M+H]+= 572).

Compound 2-60 (15 g, 26.3 mmol) and phenanthren-9-ylboronic acid_D7 (6.3 g, 27.6 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (10.9 g, 78.8 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.2 g of compound 2-60-D20 (yield 75%, MS: [M+H]+= 721).

Manufacturing Example 2-61

Compound amine61 (10 g, 17.1 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (12.3 g, 616.3 mmol) was added to trifluoromethanesulfonic anhydride (43.5 g, 154.1 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and stirred while maintaining the temperature. After 8 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.2 g of compound 2-61 (yield 41%, MS: [M+H]+= 605).

Compound 2-61 (15 g, 24.8 mmol) and phenanthren-9-ylboronic acid_D5 (5.9 g, 26.1 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (10.3 g, 74.5 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.6 g of compound 2-61-D25 (yield 62%, MS: [M+H]+= 752).

Manufacturing Example 2-62

Compound amine62 (10 g, 16.7 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (12.1 g, 601.9 mmol) was added to trifluoromethanesulfonic anhydride (42.5 g, 150.5 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 8 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.6 g of compound 2-62 (yield 45%, MS: [M+H]+= 617).

Compound 2-62 (15 g, 24.3 mmol) and phenanthren-9-ylboronic acid_D3 (5.8 g, 25.6 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (10.1 g, 73 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.2 g of compound 2-62-D21 (yield 71%, MS: [M+H]+= 762).

Manufacturing Example 2-63

Compound amine63 (10 g, 19.2 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (13.8 g, 689.5 mmol) was added to trifluoromethanesulfonic anhydride (48.6 g, 172.4 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 8 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.8 g of compound 2-63 (yield 46%, MS: [M+H]+= 545).

Compound 2-63 (15 g, 27.6 mmol) and phenanthren-9-ylboronic acid_D8 (6.7 g, 28.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (11.4 g, 82.7 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.2 g of compound 2-63-D30 (yield 69%, MS: [M+H]+= 695).

Manufacturing Example 2-64

Compound amine64 (10 g, 19.7 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (14.2 g, 708.6 mmol) was added to trifluoromethanesulfonic anhydride (33.3 g, 118.1 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 4 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.8 g of compound 2-64 (yield 47%, MS: [M+H]+= 520).

Compound 2-64 (15 g, 28.9 mmol) and phenanthren-9-ylboronic acid_D9 (7 g, 30.3 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (12 g, 86.7 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.1 g of compound 2-64-D20 (yield 73%, MS: [M+H]+= 671).

Manufacturing Example 2-65

Compound amine65 (10 g, 16.4 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (11.9 g, 591.9 mmol) was added to trifluoromethanesulfonic anhydride (41.8 g, 148 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 8 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.4 g of compound 2-65 (yield 42%, MS: [M+H]+= 634).

Compound 2-65 (15 g, 23.7 mmol) and phenanthren-9-ylboronic acid_D3 (5.6 g, 24.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (9.8 g, 71.1 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.6 g of compound 2-65-D28 (yield 79%, MS: [M+H]+= 779).

Manufacturing Example 2-66

Compound amine66 (10 g, 17.9 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (12.9 g, 645 mmol) was added to trifluoromethanesulfonic anhydride (60.7 g, 215 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 15 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.5 g of compound 2-66 (yield 43%, MS: [M+H]+= 587).

Compound 2-66 (15 g, 25.6 mmol) and phenanthren-9-ylboronic acid_D9 (6.2 g, 26.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (10.6 g, 76.8 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.2 g of compound 2-66-D37 (yield 70%, MS: [M+H]+= 738).

Manufacturing Example 2-67

Compound amine67 (10 g, 17.1 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (12.3 g, 616.3 mmol) was added to trifluoromethanesulfonic anhydride (43.5 g, 154.1 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and stirred while maintaining the temperature. After 8 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.7 g of compound 2-67 (yield 45%, MS: [M+H]+= 608).

Compound 2-67 (15 g, 24.7 mmol) and phenanthren-9-ylboronic acid_D6 (5.9 g, 25.9 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (10.2 g, 74.1 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.9 g of compound 2-67-D29 (yield 69%, MS: [M+H]+= 756).

Manufacturing Example 2-68

Compound amine68 (10 g, 18.8 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (13.6 g, 676.6 mmol) was added to trifluoromethanesulfonic anhydride (47.7 g, 169.1 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 8 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.5 g of compound 2-68 (yield 43%, MS: [M+H]+= 553).

Compound 2-68 (15 g, 27.2 mmol) and phenanthren-9-ylboronic acid_D9 (6.6 g, 28.5 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (11.3 g, 81.5 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.2 g of compound 2-68-D29 (yield 69%, MS: [M+H]+= 704).

Manufacturing Example 2-69

Compound amine69 (10 g, 16.3 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (11.7 g, 586.1 mmol) was added to trifluoromethanesulfonic anhydride (41.3 g, 146.5 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and stirred while maintaining the temperature. After 8 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.3 g of compound 2-69 (yield 42%, MS: [M+H]+= 636).

Compound 2-69 (15 g, 23.6 mmol) and phenanthren-9-ylboronic acid_D2 (5.6 g, 24.8 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (9.8 g, 70.8 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 5 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12 g of compound 2-69-D23 (yield 65%, MS: [M+H]+= 780).

Manufacturing Example 2-70

Compound amine 70 (10 g, 19.2 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (13.8 g, 689.6 mmol) was added to trifluoromethanesulfonic anhydride (48.6 g, 172.4 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 8 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.1 g of compound 2-70 (yield 40%, MS: [M+H]+= 541).

Compound 2-70 (15 g, 27.7 mmol) and phenanthren-9-ylboronic acid_D5 (6.6 g, 29.1 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (11.5 g, 83 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 4 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.1 g of compound 2-70-D25 (yield 74%, MS: [M+H]+= 690).

Manufacturing Example 2-71

Compound amine 71 (10 g, 16.1 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (11.6 g, 580.4 mmol) was added to trifluoromethanesulfonic anhydride (27.3 g, 96.7 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and stirred while maintaining the temperature. After 4 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.8 g of compound 2-71 (yield 47%, MS: [M+H]+= 640).

Compound 2-71 (15 g, 23.5 mmol) and phenanthren-9-ylboronic acid_D7 (5.6 g, 24.6 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (9.7 g, 70.4 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.2 g of compound 2-71-D26 (yield 77%, MS: [M+H]+= 789).

Manufacturing Example 2-72

Compound amine72 (10 g, 19.7 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (14.2 g, 708.6 mmol) was added to trifluoromethanesulfonic anhydride (33.3 g, 118.1 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and maintained while stirring. After 4 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 4.2 g of compound 2-72 (yield 41%, MS: [M+H]+= 523).

Compound 2-72 (15 g, 28.7 mmol) and phenanthren-9-ylboronic acid_D9 (7 g, 30.2 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (11.9 g, 86.2 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.9 g of compound 2-72-D23 (yield 77%, MS: [M+H]+= 674).

Manufacturing Example 2-73

Compound amine 73 (20 g, 37.6 mmol) was added to 200 ml of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (14.2 g, 708.6 mmol) was added to trifluoromethanesulfonic anhydride (66.6 g, 236.2 mmol) at 0 ℃ and stirred for 10 hours to prepare a solution. After that, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the temperature was increased to 140 ℃ and stirred while maintaining the temperature. After 4 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer were separated. Thereafter, the organic layer was neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, 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 2-73 (yield 53%, MS: [M+H]+= 544).

Compound 2-73 (15 g, 27.6 mmol) and phenanthren-9-ylboronic acid_D9 (7 g, 29.0 mmol) were added to 300 ml of THF, stirred and refluxed. Then, potassium carbonate (12 g, 86.5 mmol) dissolved in 100 ml of water was added, stirred sufficiently, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 3 hours of reaction, the mixture was cooled to room temperature, separated from the organic layer and aqueous layer, and distilled. This was dissolved in chloroform again, washed twice with water, separated from the organic layer, added anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 9.6 g of compound 2-73-D21 (yield 75%, MS: [M+H]+= 674).

Example 1

A glass substrate coated with a 1000 Å thick ITO (indium tin oxide) film was placed in distilled water containing a detergent and cleaned ultrasonically. The detergent used was a Fischer Co. product, and the distilled water used was distilled water that had been filtered twice through a Millipore Co. filter. 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 a solvent of isopropyl alcohol, acetone, and methanol, and after drying, the substrate was transported to a plasma cleaner. In addition, the substrate was cleaned for 5 minutes using oxygen plasma and then transported to a vacuum deposition machine.

On the ITO transparent electrode thus prepared, a hole injection layer of the following compound HI-1 was formed with a thickness of 1150 Å, and p-doped with the following compound A-1 at a concentration of 1.5 wt%. On the hole injection layer, the following compound HT-1 was vacuum-deposited to form a hole transport layer with a film thickness of 800 Å. Subsequently, the following compound EB-1 was vacuum-deposited to a film thickness of 150 Å on the hole transport layer to form an electron blocking layer. Subsequently, on the EB-1 deposited film, the following compound 1-1 as a first host, the following compound 2-1-D22 as a second host, and the following compound Dp-7 as a dopant were vacuum-deposited at a weight ratio of 49:49:2 to form a red emitting layer with a thickness of 400 Å. The following compound HB-1 was vacuum-deposited to a film thickness of 30 Å on the emitting layer to form a hole blocking layer. Next, on the hole-blocking layer, the following compound ET-1 and the following compound LiQ were vacuum-deposited at a weight ratio of 2:1 to form an electron injection and transport layer with a thickness of 300 Å. On the electron injection and transport layer, lithium fluoride (LiF) was sequentially deposited with a thickness of 12 Å and aluminum was sequentially deposited with a thickness of 1000 Å to form a cathode.

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

Examples 2 to 245

An organic light-emitting device was manufactured in the same manner as in Example 1, except that instead of compound 1 in the organic light-emitting device of Example 1, a compound represented by the chemical formula 1 as a first host and a compound represented by the chemical formula 2 as a second host were co-deposited at a weight ratio of 1:1, as described in Tables 1 to 6 below.

Comparative examples 1 to 60

An organic light-emitting device was manufactured in the same manner as in Example 1, except that instead of compound 1 in the organic light-emitting device of Example 1, comparative compounds A-1 to A-12 as a first host and a compound represented by the chemical formula 2 as a second host were co-deposited at a weight ratio of 1:1 as described in Tables 7 and 8 below. Compounds A-1 to A-12 in Tables 7 and 8 below are as follows.

Comparative examples 61 to 268

An organic light-emitting device was manufactured in the same manner as in Example 1, except that instead of compound 1 in the organic light-emitting device of Example 1, a compound represented by the chemical formula 1 as a first host and a comparative compound described in Tables 9 to 13 as a second host were co-deposited at a weight ratio of 1:1 as described in Tables 9 to 14 below. The second host compounds of Tables 9 to 14 below are as follows.

Experimental example

When current was applied to the organic light-emitting devices manufactured in Examples 1 to 245 and Comparative Examples 1 to 268, the voltage and efficiency were measured (based on 15 mA/cm ² ), and the results are shown in Tables 1 to 14 below. The lifespan, T95, was measured based on 6000 nit, and T95 means the time required for the initial lifespan to decrease by 95%.

When current was applied to the organic light-emitting devices manufactured by Examples 1 to 245 and Comparative Examples 1 to 268, the results shown in Tables 1 to 14 were obtained. The red organic light-emitting device of Example 1 used a material that has been widely used in the past, and has a structure that uses compound EB-1 as an electron blocking layer and Dp-7 as a dopant of a red light-emitting layer. As shown in Tables 7 to 8, when Comparative Examples A-1 to A-12 and the compound of Chemical Formula 2 of the present invention were co-deposited and used as a red light-emitting layer, the driving voltage generally increased and the efficiency and lifespan decreased compared to the combination of the present invention. As shown in Tables 9 to 14, when the comparative compound and the compound of Chemical Formula 1 of the present invention were co-deposited and used as a red light-emitting layer, the driving voltage increased and the efficiency and lifespan decreased.

From this, when using a combination of a compound represented by chemical formula 1 as a first host of the present invention and a compound represented by chemical formula 2 as a second host, it was confirmed that energy transfer to the red dopant in the red emitting layer was excellently achieved, creating a more stable balance within the emitting layer than the combination of the comparative example, and effectively forming excitons by combining electrons and holes, thereby significantly increasing the efficiency and lifespan. In addition, it was inferred that deuterium substitution for the compound of the present invention contributed to molecular stability, thereby further improving the lifespan characteristics. In conclusion, it was confirmed that when the compound represented by chemical formula 1 of the present invention and the compound represented by chemical formula 2 were combined and co-deposited and used as a host for a red emitting layer, the driving voltage, luminous efficiency, and lifespan characteristics of the organic light-emitting device could be improved.

[Explanation of symbols]

1: Substrate 2: Anode

3: 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 (12)

Bipolar; cathode; and Including a light-emitting layer between the anode and cathode, The above light-emitting layer comprises a compound represented by the following chemical formula 1 and a compound represented by the following chemical formula 2. Organic light emitting diodes: [Chemical Formula 1]

In the above chemical formula 1, Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C _6-60 aryl; or a C _2-60 heteroaryl comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S, L ₁ is a single bond; or a substituted or unsubstituted C _6-60 arylene, L ₂ and L ₃ are each independently a single bond; a substituted or unsubstituted C _6-60 arylene; or a C _2-60 heteroarylene comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S, One of R ₁ to R ₇ is connected to a substituent -Ar ₃ , and the others are each independently hydrogen or deuterium, Ar ₃ is a substituted or unsubstituted C _6-60 aryl; or a C _2-60 heteroaryl comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S, [Chemical formula 2]

In the above chemical formula 2, Ar' ₁ is hydrogen; deuterium; substituted or unsubstituted C _6-60 aryl; or C _2-60 heteroaryl comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S, Ar' ₂ and Ar' ₃ are each independently a substituted or unsubstituted C _6-60 aryl; or a C _2-60 heteroaryl comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S, L' ₁ to L' ₃ are each independently a single bond; a substituted or unsubstituted C _6-60 arylene; or a C _2-60 heteroarylene comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S, L' ₄ is a single bond or a substituted or unsubstituted C _6-60 arylene, R' ₁ is hydrogen or deuterium, a is an integer from 1 to 8, -At least one of -L' ₁ -Ar' ₁ and R' ₁ is deuterium, The deuterium substitution rate of the compound represented by the above chemical formula 2 is 50% or more. In the first paragraph, Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, terphenylyl, triphenylsilyl phenyl, naphthyl, phenanthrenyl, dibenzofuranyl, or dibenzothiophenyl, The above phenyl, biphenylyl, terphenylyl, triphenylsilyl phenyl, naphthyl, phenanthrenyl, dibenzofuranyl, and dibenzothiophenyl are each independently unsubstituted or substituted with one or more deuterium. Organic light emitting diode. In the first paragraph, L ₁ is a single bond, a substituted or unsubstituted phenylene, or a substituted or unsubstituted naphthalenediyl, Organic light emitting diode. In the first paragraph, L ₂ and L ₃ are each independently a single bond, a substituted or unsubstituted phenylene, a substituted or unsubstituted biphenyldiyl, or a substituted or unsubstituted naphthalenediyl, Organic light emitting diode. In the first paragraph, Ar ₃ is phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, triphenylenyl, naphthylphenyl, phenyl naphthyl, fluoranthenyl, dihydroindenyl, dibenzofuranyl, dibenzothiophenyl, benzonaphthofuranyl, or benzonaphthothiophenyl, The above phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, triphenylenyl, naphthyl phenyl, phenyl naphthyl, fluoranthenyl, dihydroindenyl, dibenzofuranyl, dibenzothiophenyl, benzonaphthofuranyl, and benzonaphthothiophenyl are unsubstituted or substituted with one or more deuterium atoms. Organic light emitting diode. In the first paragraph, At least one of Ar ₁ to Ar ₃ is naphthyl, phenyl naphthyl, naphthyl phenyl, phenanthrenyl, fluoranthenyl, dibenzofuranyl, dibenzothiophenyl, benzonaphthofuranyl, or benzonaphthothiophenyl, The above naphthyl, phenyl naphthyl, naphthyl phenyl, phenanthrenyl, fluoranthenyl, dibenzofuranyl, dibenzothiophenyl, benzonaphthofuranyl and benzonaphthothiophenyl are each independently unsubstituted or substituted with one or more deuterium atoms. Organic light emitting diode. In the first paragraph, The compound represented by the above chemical formula 1 is one selected from the group consisting of: Organic light emitting diodes:

. In the first paragraph, Ar' ₁ is hydrogen, deuterium, or phenyl which is unsubstituted or substituted with one or more deuterium atoms, Organic light emitting diode. In the first paragraph, Ar' ₂ and Ar' ₃ are each independently phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl, phenyl naphthyl, naphthyl phenyl, tetrahydronaphthyl, phenanthrenyl, phenyl phenanthrenyl, triphenylenyl, dimethylfluorenyl, diphenylfluorenyl, carbazolyl, phenyl carbazolyl, dibenzofuranyl, dibenzothiophenyl, or phenyl dibenzofuranyl, The above phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl, phenyl naphthyl, naphthyl phenyl, tetrahydronaphthyl, phenanthrenyl, phenyl phenanthrenyl, triphenylenyl, dimethylfluorenyl, diphenylfluorenyl, carbazolyl, phenyl carbazolyl, dibenzofuranyl, dibenzothiophenyl, and phenyl dibenzofuranyl are each independently unsubstituted or substituted with one or more deuterium, or one or more C _1-10 alkyl. Organic light emitting diode. In the first paragraph, L' ₁ to L' ₃ are each independently a single bond, phenylene, biphenylylene, naphthylene, phenyl naphthylene, phenanthrenylene, carbazolylene, phenyl carbazolylene, dibenzofuranylene, phenyl dibenzofuranylene, or dimethylfluorenylene, The above phenylene, biphenylylene, naphthylene, phenyl naphthylene, phenanthrenylene, carbazolylene, phenyl carbazolylene, dibenzofuranylene, phenyl dibenzofuranylene, and dimethylfluorenylene are each independently unsubstituted or substituted with one or more deuterium atoms. Organic light emitting diode. In the first paragraph, L' ₄ is a single bond, a substituted or unsubstituted phenylene, a substituted or unsubstituted biphenylylene, or a substituted or unsubstituted naphthylene, Organic light emitting diode. In the first paragraph, The compound represented by the above chemical formula 2 is one selected from the group consisting of: In the group below, D is deuterium, n1 is an integer from 1 to 9, n is the total number of deuterium atoms substituted in the compound, Each compound in the group below has a deuterium substitution rate of 50% or more. Organic light emitting diodes:

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