KR20230107135A - Organic light emitting device - Google Patents

Abstract

The present invention provides an organic light emitting device with improved driving voltage, efficiency and lifetime.

Description

Organic light emitting device {Organic light emitting device}

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

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

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

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

Korean Patent Publication No. 10-2000-0051826

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

The present invention provides the following organic light emitting device:

anode; cathode; And a light emitting layer between the anode and the cathode,

The light emitting layer may include a compound represented by Chemical Formula 1; and

Including a compound represented by Formula 2 below,

Organic Light-Emitting Elements:

[Formula 1]

In Formula 1,

Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C _6-60 aryl; Or a C _2-60 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O and S, but Ar ₁ and Ar ₂ one of which is substituted or unsubstituted C _6-60 aryl, and at least one of Ar ₁ and Ar ₂ is benzo[c]phenanthrenyl, chrysenyl, fluoranthenyl, or benzonaphthofuranyl, wherein the benzo[c]phenanthrenyl, chrysenyl, fluoranthenyl, or benzonaphthofuranil is unsubstituted or substituted with one or more deuterium;

L ₁ to L ₃ are each independently a single bond; or a substituted or unsubstituted C _6-60 arylene;

R ₁ is hydrogen; heavy hydrogen; Substituted or unsubstituted C _6-60 aryl; Or a C _2-60 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O and S,

a is an integer from 0 to 7;

[Formula 2]

In Formula 2,

X' is O or S;

Any one of R' ₁ to R' ₁₀ is connected to the following Formula 2A, the others are hydrogen or deuterium,

[Formula 2A]

In Formula 2A

L' ₁ to L' ₃ are each independently a single bond; or a substituted or unsubstituted C _6-60 arylene;

Ar' ₁ and Ar' ₂ are each independently phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, dimethylfluorenyl, spirobifluorenyl, dibenzofuranyl, dibenzothiophenyl, or phenyl carbazolyl, wherein Ar' ₁ and Ar' ₂ are each independently unsubstituted or substituted.

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

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

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

또는

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

or

means a bond connected to another substituent.

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

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

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

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

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

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

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

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

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

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

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

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

etc. However, it is not limited thereto.

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

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

Meanwhile, in the present specification, when the number of deuterium substitutions of a specific compound is to be indicated, it may be expressed as '[structural formula] _Dn '. Here, 'Dn' means that n hydrogens of the compound represented by the 'structural formula' are replaced with deuterium.

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

anode and cathode

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

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

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

hole injection layer

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

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

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

hole transport layer

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

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

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

electron blocking layer

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

The electron blocking layer is a layer placed between the hole transport layer and the light emitting layer to prevent electrons injected from the cathode from passing to the hole transport layer without recombination in the light emitting layer, and is also called an electron blocking layer or an electron blocking layer. A material having a smaller electron affinity than the electron transport layer is preferable for the electron blocking layer.

light emitting layer

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

Preferably, the compound represented by Chemical Formula 1 may be represented by any of the following Chemical Formulas 1-1 to 1-3:

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In Formulas 1-1 to 1-3,

Ar ₁ , Ar ₂ and L ₁ to L ₃ are as defined in Formula 1,

R ₁ is deuterium; Substituted or unsubstituted C _6-60 aryl; Or a C _2-60 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O and S.

Preferably, Ar ₁ and Ar ₂ are each independently substituted or unsubstituted C _6-20 aryl; Or a C _2-20 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O and S, but Ar ₁ and Ar ₂ one of which is substituted or unsubstituted C _6-20 aryl, and at least one of Ar ₁ and Ar ₂ is substituted or unsubstituted benzo[c]phenanthrenyl, substituted or unsubstituted chrysenyl, substituted or unsubstituted fluoranthenyl, or substituted or unsubstituted benzonaph. It may be tofuranil;

More preferably, Ar ₁ and Ar ₂ are each independently selected from phenyl, triphenylsilyl phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, chrysenyl, benzo[c]phenanthrenyl, fluoran tenyl, dibenzofuranyl, dibenzothiophenyl, or benzonaphthofuranyl, wherein Ar ₁ and Ar ₂ are each independently unsubstituted or substituted with one or more deuterium atoms, but one of Ar ₁ and Ar ₂ is phenyl, triphenylsilyl phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, chrysenyl, or fluoranthenyl, the phenyl, triphenylsilyl phenyl, biphenylyl, terphenylyl, naphthyl Tyl, phenanthrenyl, chrysenyl, or fluoranthenyl may be unsubstituted or substituted with at least one deuterium, and at least one of Ar ₁ and Ar ₂ is benzo[c]phenanthrenyl, chrysenyl, fluoranthenyl , or benzonaphthofuranil, and the benzo[c]phenanthrenyl, chrysenyl, fluoranthenyl, or benzonaphthofuranil may be unsubstituted or substituted with at least one deuterium.

Most preferably, Ar ₁ and Ar ₂ are each independently triphenylsilyl or any one selected from the group consisting of Ar 1 and Ar 2 , wherein one of Ar ₁ and Ar ₂ is phenyl, phenyl substituted with 5 deuterium atoms, tri phenylsilyl phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, chrysenyl, or fluoranthenyl, and at least one of Ar ₁ and Ar ₂ is benzo[c]phenanthrenyl, chrysenyl, fluoran tenyl, or benzonaphthofuranil:

.

.

Preferably, L ₁ to L ₃ are each independently a single bond; Or it may be a substituted or unsubstituted C _6-20 arylene,

More preferably, L ₁ to L ₃ may each independently be a single bond, phenylene, biphenyldiyl, naphthalenediyl, phenyl naphthalenediyl, or naphthyl naphthalenediyl, wherein the phenylene, biphenyldiyl, naphthalene diyl, phenyl naphthalenediyl, or naphthyl naphthalenediyl may each independently be unsubstituted or substituted with one or more deuterium atoms;

Most preferably, L ₁ to L ₃ may each independently be a single bond or any one selected from the group consisting of, and hydrogen of each linker in the following group may be independently substituted with deuterium:

.

.

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

More preferably, each R ₁ is independently selected from hydrogen, deuterium, phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, triphenylenyl, naphthyl phenyl, phenyl naphthyl, fluoranthenyl, di It may be benzofuranil, dibenzothiophenyl, benzonaphthofuranil, or benzonaphthothiophenyl, and the above phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, triphenylenyl, naphthyl phenyl, Phenyl naphthyl, fluoranthenyl, dibenzofuranyl, dibenzothiophenyl, benzonaphthofuranil and benzonaphthothiophenyl may each independently be unsubstituted or substituted with at least one deuterium.

Preferably, a can be 0 or 1. More preferably, a may be 1.

On the other hand, when the number of deuterium substitutions of the compound is desired, it can be represented by the following formula 1D:

[Formula 1D]

In Formula 1D,

Dn means that n hydrogen atoms have been replaced by deuterium;

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

Ar _1d , Ar _2d , and L _1d to L _3d represent Ar ₁ , Ar ₂ , and L ₁ to L ₃ substituents not substituted with deuterium, respectively;

R _1d is C _6-60 aryl unsubstituted with deuterium, substituted or unsubstituted; Or a C _2-60 heteroaryl containing at least one selected from the group consisting of N, O and S unsubstituted, substituted or unsubstituted with deuterium,

a is an integer from 0 to 7;

For example, in Formula 1D, n of Dn is 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 the compound represented by Formula 1 are as follows:

.

.

Among the compounds represented by Formula 1, when R ₁ is hydrogen or deuterium, it can be prepared by, for example, a manufacturing method such as the following Reaction Scheme 1-1, and when R ₁ is not hydrogen or deuterium, as an example, the following Reaction Scheme 1- It can be prepared by the same preparation method as in 2, and other compounds can be prepared similarly.

[Scheme 1-1]

[Scheme 1-2]

In Reaction Schemes 1-1 and 1-2, Ar ₁ , Ar ₂ and L ₁ to L ₃ are as defined in Formula 1, Z ₁ to Z ₃ are halogen, preferably Z ₁ to Z ₃ are chloro or bromo.

Schemes 1-1 and 1-2 are Suzuki coupling reactions, which are preferably carried out in the presence of a palladium catalyst and a base, and the reactor for the Suzuki coupling reaction can be changed as known in the art. The manufacturing method may be more specific in Preparation Examples to be described later.

Preferably, Formula 2A may be linked to any one of R' ₁ , R' ₂ , R' ₄ , R' ₅ , and R' ₈ to R' ₁₀ in Formula 2 above.

Preferably, L' ₁ to L' ₃ are each independently a single bond; Or it may be a substituted or unsubstituted C _6-20 arylene,

More preferably, L' ₁ to L' ₃ may each independently be a single bond, phenylene, biphenylyldiyl, naphthalenediyl, or dimethylfluorenediyl, and the phenylene, biphenyldiyl, naphthalenediyl and dimethylfluorenediyl may each independently be unsubstituted or substituted with one or more deuterium atoms.

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

More preferably, Ar' ₁ and Ar' ₂ are each independently selected from phenyl, triphenylsilyl phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, dimethylfluorenyl, spirobifluorenyl, It may be dibenzofuranyl, dibenzothiophenyl, or phenyl carbazolyl, and Ar' ₁ and Ar' ₂ may each independently be unsubstituted or substituted with one or more deuterium atoms.

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

.

.

For example, the compound represented by Formula 2 may be prepared by a manufacturing method as shown in Scheme 2-1 below when Formula 2A is linked to R' ₁₀ and L' ₁ is not a single bond, and Formula 2A is connected to R' ₁₀ When connected and L' ₁ is a single bond, it can be prepared by the same method as in Scheme 2-2 below, and other compounds can be similarly prepared.

[Scheme 2-1]

[Scheme 2-2]

In Schemes 2-1 and 2-2, R' ₁ to R' ₉ , X', Ar' ₁ , Ar' ₂ , L' ₁ to L' ₃ are as defined in Formula 2 and Formula 2A, Z' ₁ and Z' ₂ are halogen, preferably Z' ₁ and Z' ₂ are chloro or bromo.

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

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

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

hole blocking 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 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 passing to the electron transport layer without recombination in the light emitting layer, and is also called a hole blocking layer or a hole blocking layer. A material having high ionization energy is preferred 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 electron transport layer is a layer that receives electrons from the cathode or an electron injection layer formed on the cathode, transports electrons to the light emitting layer, and suppresses the transfer of holes in the light emitting layer. As an electron transport material, electrons are well injected from the cathode. As a material that can be received and transferred to the light emitting layer, a material having high electron mobility is suitable.

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

electron injection layer

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

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

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

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

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

organic light emitting device

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

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

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

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

Synthesis Example 1-1

The compound Trz1 (15 g, 41.9 mmol) and chrysen-2-ylboronic acid (12 g, 44 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (17.4 g, 125.8 mmol) was dissolved in 52 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 16.3 g of Compound 1-1. (Yield 71%, MS: 1 = 550)

Synthesis Example 1-2

The compound Trz2 (15 g, 34.6 mmol) and chrysen-2-ylboronic acid (9.9 g, 36.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.3 g, 103.7 mmol) was dissolved in 43 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.6 g of Compound 1-2. (Yield 72%, MS: [M+H] ⁺ = 626)

Synthesis Example 1-4

The compound Trz4 (15 g, 47.4 mmol) and (2-phenyldibenzo[b,d]furan-1-yl)boronic acid (14.4 g, 49.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (19.7 g, 142.3 mmol) was dissolved in 59 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.1 g of compound 1-4_P1. (Yield 65%, MS: [M+H] ⁺ = 524)

Compound 1-4_P1 (15 g, 28.6 mmol) and chrysen-2-ylboronic acid (8.2 g, 30.1 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (11.9 g, 85.9 mmol) was dissolved in 36 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.1 g of compound 1-4. (Yield 64%, MS: [M+H] ⁺ = 716)

Synthesis Example 1-6

Compound Trz5 (15 g, 33.5 mmol) and chrysen-3-ylboronic acid (9.6 g, 35.2 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (13.9 g, 100.5 mmol) was dissolved in 42 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15 g of compound 1-6. (Yield 70%, MS: [M+H] ⁺ = 640)

Synthesis Example 1-7

Compound Trz6 (15 g, 66.4 mmol) and (5-(dibenzo[b,d]furan-1-yl)naphthalen-1-yl)boronic acid (23.6 g, 69.7 mmol) were added to 300 ml of THF, stirred and refluxed. did Thereafter, potassium carbonate (27.5 g, 199.1 mmol) was dissolved in 83 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.7 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.8 g of compound 1-7_P1. (Yield 65%, MS: [M+H] ⁺ = 484)

Compound 1-7_P1 (15 g, 31 mmol) and (5-(dibenzo[b,d]furan-1-yl)naphthalen-1-yl)boronic acid (11 g, 32.5 mmol) were added to 300 ml of THF and stirred. and refluxed. Thereafter, potassium carbonate (12.9 g, 93 mmol) was dissolved in 39 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 138.2 g of compound 1-7. (Yield 66%, MS: [M+H] ⁺ = 6756)

Synthesis Example 1-8

Compound Trz7 (15 g, 36.8 mmol) and (2-chlorophenyl)boronic acid (6 g, 38.6 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (15.2 g, 110.3 mmol) was dissolved in 46 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.8 g of compound 1-8_P1. (Yield 72%, MS: [M+H] ⁺ = 484)

Compound 1-8_P1 (15 g, 31 mmol) and chrysen-3-ylboronic acid (8.9 g, 32.5 mmol) were added to 300 ml of 1,4-dioxane, stirred and refluxed. Thereafter, potassium phosphate (19.7 g, 93 mmol) was dissolved in 59 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.1 g of compound 1-8. (Yield 72%, MS: [M+H] ⁺ = 676)

Synthesis Example 1-10

Compound Trz6 (15 g, 66.4 mmol) and (4-(naphthalen-2-yl)dibenzo[b,d]furan-1-yl)boronic acid (23.6 g, 69.7 mmol) were added to 300 ml of THF, stirred and refluxed. did Thereafter, potassium carbonate (27.5 g, 199.1 mmol) was dissolved in 83 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.7 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.5 g of compound 1-10_P1. (Yield 67%, MS: [M+H] ⁺ = 484)

Compound 1-10_P1 (15 g, 31 mmol) and chrysen-3-ylboronic acid (8.9 g, 32.5 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (12.9 g, 93 mmol) was dissolved in 39 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.1 g of compound 1-10. (Yield 72%, MS: [M+H] ⁺ = 676)

Synthesis Example 1-11

The compound Trz1 (15 g, 41.9 mmol) and (4-chlorophenyl)boronic acid (6.9 g, 44 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (17.4 g, 125.8 mmol) was dissolved in 52 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.3 g of compound 1-11_P1. (Yield 68%, MS: [M+H] ⁺ = 434)

Compound 1-11_P1 (15 g, 341.7 mmol) and chrysen-4-ylboronic acid (97.6 g, 358.8 mmol) were added to 300 ml of 1,4-dioxane, stirred and refluxed. Thereafter, potassium phosphate (217.6 g, 1025.1 mmol) was dissolved in 653 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (1.7 g, 3.4 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 160.2 g of compound 1-11. (Yield 75%, MS: [M+H] ⁺ = 626)

Synthesis Example 1-13

The compound Trz4 (15 g, 47.4 mmol) and (8-phenyldibenzo[b,d]furan-1-yl)boronic acid (14.4 g, 49.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (19.7 g, 142.3 mmol) was dissolved in 59 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.6 g of compound 1-13_P1. (Yield 75%, MS: [M+H] ⁺ = 524)

Compound 1-13_P1 (15 g, 28.6 mmol) and chrysen-4-ylboronic acid (8.2 g, 30.1 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (11.9 g, 85.9 mmol) was dissolved in 36 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.1 g of compound 1-13. (Yield 64%, MS: [M+H] ⁺ = 716)

Synthesis Example 1-14

Compound Trz1 (15 g, 41.9 mmol) and chrysen-5-ylboronic acid (12 g, 44 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (17.4 g, 125.8 mmol) was dissolved in 52 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.2 g of compound 1-14. (Yield 66%, MS: [M+H] ⁺ = 550)

Synthesis Example 1-15

Compound Trz6 (15 g, 66.4 mmol) and (5-(dibenzo[b,d]furan-1-yl)naphthalen-2-yl)boronic acid (23.6 g, 69.7 mmol) were added to 300 ml of THF, stirred and refluxed. did Thereafter, potassium carbonate (27.5 g, 199.1 mmol) was dissolved in 83 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.7 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.6 g of compound 1-15_P1. (Yield 61%, MS: [M+H] ⁺ = 484)

Compound 1-15_P1 (15 g, 31 mmol) and chrysen-5-ylboronic acid (8.9 g, 32.5 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (12.9 g, 93 mmol) was dissolved in 39 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.4 g of compound 1-15. (Yield 64%, MS: [M+H] ⁺ = 676)

Synthesis Example 1-16

The compound Trz6 (15 g, 66.4 mmol) and (2-(dibenzo[b,d]furan-1-yl)phenyl)boronic acid (20.1 g, 69.7 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (27.5 g, 199.1 mmol) was dissolved in 83 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.7 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.3 g of compound 1-16_P1. (Yield 67%, MS: [M+H] ⁺ = 434)

Compound 1-16_P1 (15 g, 34.6 mmol) and chrysen-5-ylboronic acid (9.9 g, 36.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.3 g, 103.7 mmol) was dissolved in 43 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.2 g of compound 1-16. (Yield 75%, MS: [M+H] ⁺ = 626)

Synthesis Example 1-17

Compound Trz9 (15 g, 45.2 mmol) and (4-(dibenzo[b,d]furan-1-yl)phenyl)boronic acid (13.7 g, 47.4 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.7 g, 135.5 mmol) was dissolved in 56 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.3 g of compound 1-17_P1. (Yield 75%, MS: [M+H] ⁺ = 540)

Compound 1-17_P1 (15 g, 27.8 mmol) and chrysen-5-ylboronic acid (7.9 g, 29.2 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (11.5 g, 83.3 mmol) was dissolved in 35 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.4 g of compound 1-17. (Yield 66%, MS: [M+H] ⁺ = 732)

Synthesis Example 1-18

The compound Trz10 (15 g, 49.6 mmol) and (7-phenyldibenzo[b,d]furan-1-yl)boronic acid (15 g, 52.1 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (20.6 g, 148.9 mmol) was dissolved in 62 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.4 g of compound 1-18_P1. (Yield 65%, MS: [M+H] ⁺ = 510)

Compound 1-18_P1 (15 g, 29.4 mmol) and chrysen-5-ylboronic acid (8.4 g, 30.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (12.2 g, 88.2 mmol) was dissolved in 37 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13 g of compound 1-18. (Yield 63%, MS: [M+H] ⁺ = 702)

Synthesis Example 1-19

The compound Trz1 (15 g, 41.9 mmol) and chrysen-6-ylboronic acid (12 g, 44 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (17.4 g, 125.8 mmol) was dissolved in 52 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.4 g of Compound 1-19. (Yield 67%, MS: [M+H] ⁺ = 550)

Synthesis Example 1-20

Compound Trz7 (15 g, 36.8 mmol) and chrysen-6-ylboronic acid (10.5 g, 38.6 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (15.2 g, 110.3 mmol) was dissolved in 46 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.1 g of Compound 1-20. (Yield 73%, MS: [M+H] ⁺ = 600)

Synthesis Example 1-21

Compound Trz5 (15 g, 33.5 mmol) and chrysen-6-ylboronic acid (9.6 g, 35.2 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (13.9 g, 100.5 mmol) was dissolved in 42 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 16.1 g of compound 1-21. (Yield 75%, MS: [M+H] ⁺ = 640)

Synthesis Example 1-22

Compound Trz6 (15 g, 66.4 mmol) and (4-(dibenzo[b,d]furan-1-yl)naphthalen-1-yl)boronic acid (23.6 g, 69.7 mmol) were added to 300 ml of THF, stirred and refluxed. did Thereafter, potassium carbonate (27.5 g, 199.1 mmol) was dissolved in 83 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.7 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 23.1 g of compound 1-22_P1. (Yield 72%, MS: [M+H] ⁺ = 484)

Compound 1-22_P1 (15 g, 31 mmol) and chrysen-6-ylboronic acid (8.9 g, 32.5 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (12.9 g, 93 mmol) was dissolved in 39 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.4 g of compound 1-22. (Yield 69%, MS: [M+H] ⁺ = 676)

Synthesis Example 1-23

The compound Trz11 (15 g, 45.2 mmol) and (3-(dibenzo[b,d]furan-1-yl)phenyl)boronic acid (13.7 g, 47.4 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.7 g, 135.5 mmol) was dissolved in 56 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.5 g of compound 1-23_P1. (Yield 72%, MS: [M+H] ⁺ = 540)

Compound 1-23_P1 (15 g, 27.8 mmol) and chrysen-6-ylboronic acid (7.9 g, 29.2 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (11.5 g, 83.3 mmol) was dissolved in 35 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.2 g of compound 1-23. (Yield 65%, MS: [M+H] ⁺ = 732)

Synthesis Example 1-24

The compound Trz6 (15 g, 66.4 mmol) and (4-(dibenzo[b,d]furan-1-yl)phenyl)boronic acid (20.1 g, 69.7 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (27.5 g, 199.1 mmol) was dissolved in 83 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.7 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.7 g of compound 1-24_P1. (Yield 65%, MS: [M+H] ⁺ = 434)

Compound 1-24_P1 (15 g, 34.6 mmol) and chrysen-6-ylboronic acid (9.9 g, 36.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.3 g, 103.7 mmol) was dissolved in 43 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.6 g of Compound 1-24. (Yield 72%, MS: [M+H] ⁺ = 626)

Synthesis Example 1-25

The compound Trz12 (15 g, 34.6 mmol) and (3-chlorophenyl)boronic acid (5.7 g, 36.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.3 g, 103.7 mmol) was dissolved in 43 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.3 g of compound 1-25_P1. (Yield 70%, MS: [M+H] ⁺ = 510)

Compound 1-25_P1 (15 g, 29.4 mmol) and chrysen-6-ylboronic acid (8.4 g, 30.9 mmol) were added to 300 ml of 1,4-dioxane, stirred and refluxed. Thereafter, potassium phosphate (18.7 g, 88.2 mmol) was dissolved in 56 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.8 g of Compound 1-25. (Yield 67%, MS: [M+H] ⁺ = 702)

Synthesis Example 1-26

Compound Trz6 (15 g, 66.4 mmol) and (3-phenyldibenzo[b,d]furan-1-yl)boronic acid (20.1 g, 69.7 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (27.5 g, 199.1 mmol) was dissolved in 83 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.7 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.7 g of compound 1-26_P1. (Yield 65%, MS: [M+H] ⁺ = 434)

Compound 1-26_P1 (15 g, 34.6 mmol) and chrysen-6-ylboronic acid (9.9 g, 36.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.3 g, 103.7 mmol) was dissolved in 43 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.3 g of compound 1-26. (Yield 71%, MS: [M+H] ⁺ = 626)

Synthesis Example 1-27

The compound Trz6 (15 g, 66.4 mmol) and (4-phenyldibenzo[b,d]furan-1-yl)boronic acid (20.1 g, 69.7 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (27.5 g, 199.1 mmol) was dissolved in 83 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.7 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.5 g of compound 1-27_P1. (Yield 61%, MS: [M+H] ⁺ = 434)

Compound 1-27_P1 (15 g, 34.6 mmol) and chrysen-6-ylboronic acid (9.9 g, 36.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.3 g, 103.7 mmol) was dissolved in 43 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.7 g of Compound 1-27. (Yield 68%, MS: [M+H] ⁺ = 626)

Synthesis Example 1-29

Compound Trz1 (15 g, 41.9 mmol) and benzo[c]phenanthren-2-ylboronic acid (12 g, 44 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (17.4 g, 125.7 mmol) was dissolved in 52 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 16.3 g of compound 1-29. (Yield 71%, MS: [M+H] ⁺ = 550)

Synthesis Example 1-30

Compound Trz5 (15 g, 33.5 mmol) and benzo[c]phenanthren-2-ylboronic acid (9.6 g, 35.2 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (13.9 g, 100.5 mmol) was dissolved in 42 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.1 g of Compound 1-30. (Yield 75%, MS: [M+H] ⁺ = 640)

Synthesis Example 1-31

Compound 1-25_P1 (15 g, 29.4 mmol) and benzo[c]phenanthren-2-ylboronic acid (8.4 g, 30.9 mmol) were added to 300 ml of 1,4-dioxane, stirred and refluxed. Thereafter, potassium phosphate (18.7 g, 88.2 mmol) was dissolved in 56 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13 g of compound 1-31. (Yield 63%, MS: [M+H] ⁺ = 702)

Synthesis Example 1-33

Compound Trz6 (15 g, 66.4 mmol) and (6-([1,1'-biphenyl]-3-yl)dibenzo[b,d]furan-1-yl)boronic acid (24.1 g, 69.7 mmol) were mixed with THF It was added to 300 ml and stirred and refluxed. Thereafter, potassium carbonate (27.5 g, 199.1 mmol) was dissolved in 83 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.7 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.3 g of compound 1-33_P1. (Yield 66%, MS: [M+H] ⁺ = 510)

Compound 1-33_P1 (15 g, 29.4 mmol) and benzo[c]phenanthren-2-ylboronic acid (8.4 g, 30.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (12.2 g, 88.2 mmol) was dissolved in 37 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.2 g of compound 1-33. (Yield 69%, MS: [M+H] ⁺ = 702)

Synthesis Example 1-34

Compound Trz1 (15 g, 41.9 mmol) and benzo[c]phenanthren-3-ylboronic acid (12 g, 44 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (17.4 g, 125.7 mmol) was dissolved in 52 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.1 g of compound 1-34. (Yield 70%, MS: [M+H] ⁺ = 550)

Synthesis Example 1-35

The compound Trz6 (15 g, 66.4 mmol) and (3-(dibenzo[b,d]furan-1-yl)phenyl)boronic acid (20.1 g, 69.7 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (27.5 g, 199.1 mmol) was dissolved in 83 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.7 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.4 g of compound 1-35_P1. (Yield 71%, MS: [M+H] ⁺ = 434)

Compound 1-35_P1 (15 g, 34.6 mmol) and benzo[c]phenanthren-3-ylboronic acid (9.9 g, 36.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.3 g, 103.7 mmol) was dissolved in 43 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.8 g of compound 1-35. (Yield 73%, MS: [M+H] ⁺ = 626)

Synthesis Example 1-37

Compound 1-27_P1 (15 g, 34.6 mmol) and benzo[c]phenanthren-3-ylboronic acid (9.9 g, 36.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.3 g, 103.7 mmol) was dissolved in 43 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.7 g of Compound 1-37. (Yield 68%, MS: [M+H] ⁺ = 626)

Synthesis Example 1-38

Compound Trz1 (15 g, 41.9 mmol) and benzo[c]phenanthren-4-ylboronic acid (12 g, 44 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (17.4 g, 125.8 mmol) was dissolved in 52 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.2 g of Compound 1-38. (Yield 66%, MS: [M+H] ⁺ = 550)

Synthesis Example 1-39

The compound Trz12 (15 g, 34.6 mmol) and benzo[c]phenanthren-4-ylboronic acid (9.9 g, 36.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.3 g, 103.7 mmol) was dissolved in 43 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.9 g of compound 1-39. (Yield 69%, MS: [M+H] ⁺ = 626)

Synthesis Example 1-40

The compound Trz1 (15 g, 41.9 mmol) and (3-chlorophenyl)boronic acid (6.9 g, 44 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (17.4 g, 125.8 mmol) was dissolved in 52 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.4 g of compound 1-40_P1. (Yield 63%, MS: [M+H] ⁺ = 434)

Compound 1-40_P1 (15 g, 34.6 mmol) and benzo[c]phenanthren-4-ylboronic acid (9.9 g, 36.3 mmol) were added to 300 ml of 1,4-dioxane, stirred and refluxed. Thereafter, potassium phosphate (22 g, 103.7 mmol) was dissolved in 66 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.4 g of compound 1-40. (Yield 62%, MS: [M+H] ⁺ = 626)

Synthesis Example 1-41

The compound Trz4 (15 g, 47.4 mmol) and (4-phenyldibenzo[b,d]furan-1-yl)boronic acid (14.4 g, 49.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (19.7 g, 142.3 mmol) was dissolved in 59 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.1 g of compound 1-41_P1. (Yield 69%, MS: [M+H] ⁺ = 524)

Compound 1-41_P1 (15 g, 28.6 mmol) and benzo[c]phenanthren-4-ylboronic acid (8.2 g, 30.1 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (11.9 g, 85.9 mmol) was dissolved in 36 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.9 g of Compound 1-41. (Yield 63%, MS: [M+H] ⁺ = 716)

Synthesis Example 1-42

The compound Trz12 (15 g, 34.6 mmol) and benzo[c]phenanthren-5-ylboronic acid (9.9 g, 36.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.3 g, 103.7 mmol) was dissolved in 43 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.4 g of compound 1-42. (Yield 62%, MS: [M+H] ⁺ = 626)

Synthesis Example 1-43

Compound Trz1 (15 g, 41.9 mmol) and benzo[c]phenanthren-5-ylboronic acid (12 g, 44 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (17.4 g, 125.8 mmol) was dissolved in 52 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.4 g of compound 1-43. (Yield 67%, MS: [M+H] ⁺ = 550)

Synthesis Example 1-44

Compound 1-22_P1 (15 g, 31 mmol) and benzo[c]phenanthren-5-ylboronic acid (8.9 g, 32.5 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (12.9 g, 93 mmol) was dissolved in 39 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.1 g of Compound 1-44. (Yield 72%, MS: [M+H] ⁺ = 676)

Synthesis Example 1-46

Compound Trz6 (15 g, 66.4 mmol) and (3-(naphthalen-1-yl)dibenzo[b,d]furan-1-yl)boronic acid (23.6 g, 69.7 mmol) were added to 300 ml of THF, stirred and refluxed. did Thereafter, potassium carbonate (27.5 g, 199.1 mmol) was dissolved in 83 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.7 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.9 g of compound 1-46_P1. (Yield 62%, MS: [M+H] ⁺ = 484)

Compound 1-46_P1 (15 g, 31 mmol) and benzo[c]phenanthren-5-ylboronic acid (8.9 g, 32.5 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (12.9 g, 93 mmol) was dissolved in 39 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.8 g of compound 1-46. (Yield 66%, MS: [M+H] ⁺ = 676)

Synthesis Example 1-47

Compound Trz1 (15 g, 41.9 mmol) and benzo[c]phenanthren-6-ylboronic acid (12 g, 44 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (17.4 g, 125.8 mmol) was dissolved in 52 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.3 g of compound 1-47. (Yield 71%, MS: [M+H] ⁺ = 550)

Synthesis Example 1-48

Compound 1-15_P1 (15 g, 31 mmol) and benzo[c]phenanthren-6-ylboronic acid (8.9 g, 32.5 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (12.9 g, 93 mmol) was dissolved in 39 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.3 g of compound 1-48. (Yield 73%, MS: [M+H] ⁺ = 676)

Synthesis Example 1-49

The compound Trz13 (15 g, 47.4 mmol) and (2-(dibenzo[b,d]furan-1-yl)phenyl)boronic acid (14.4 g, 49.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (19.7 g, 142.3 mmol) was dissolved in 59 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.4 g of compound 1-49_P1. (Yield 74%, MS: [M+H] ⁺ = 524)

Compound 1-49_P1 (15 g, 28.6 mmol) and benzo[c]phenanthren-6-ylboronic acid (8.2 g, 30.1 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (11.9 g, 85.9 mmol) was dissolved in 36 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.3 g of compound 1-49. (Yield 65%, MS: [M+H] ⁺ = 716)

Synthesis Example 1-51

Compound Trz6 (15 g, 66.4 mmol) and (8-(naphthalen-2-yl)dibenzo[b,d]furan-1-yl)boronic acid (23.6 g, 69.7 mmol) were added to 300 ml of THF, stirred and refluxed. did Thereafter, potassium carbonate (27.5 g, 199.1 mmol) was dissolved in 83 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.7 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.2 g of compound 1-51_P1. (Yield 60%, MS: [M+H] ⁺ = 484)

Compound 1-51_P1 (15 g, 31 mmol) and benzo[c]phenanthren-6-ylboronic acid (8.9 g, 32.5 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (12.9 g, 93 mmol) was dissolved in 39 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.2 g of compound 1-51. (Yield 68%, MS: [M+H] ⁺ = 676)

Synthesis Example 1-52

The compound Trz1 (15 g, 41.9 mmol) and fluoranthen-2-ylboronic acid (10.8 g, 44 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (17.4 g, 125.8 mmol) was dissolved in 52 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.9 g of compound 1-52. (Yield 68%, MS: [M+H] ⁺ = 524)

Synthesis Example 1-53

The compound Trz2 (15 g, 34.6 mmol) and fluoranthen-2-ylboronic acid (8.9 g, 36.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.3 g, 103.7 mmol) was dissolved in 43 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.7 g of compound 1-53. (Yield 71%, MS: [M+H] ⁺ = 600)

Synthesis Example 1-54

Compound Trz7 (15 g, 36.8 mmol) and fluoranthen-2-ylboronic acid (9.5 g, 38.6 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (15.2 g, 110.3 mmol) was dissolved in 46 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.7 g of compound 1-54. (Yield 65%, MS: [M+H] ⁺ = 574)

Synthesis Example 1-55

Compound 1-22_P1 (15 g, 31 mmol) and fluoranthen-2-ylboronic acid (8 g, 32.5 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (12.9 g, 93 mmol) was dissolved in 39 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.3 g of compound 1-55. (Yield 71%, MS: [M+H] ⁺ = 650)

Synthesis Example 1-56

Compound 1-11_P1 (15 g, 33.5 mmol) and fluoranthen-2-ylboronic acid (8.7 g, 35.2 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (13.9 g, 100.5 mmol) was dissolved in 42 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.8 g of compound 1-56. (Yield 64%, MS: [M+H] ⁺ = 600)

Synthesis Example 1-57

Compound Trz5 (15 g, 33.5 mmol) and fluoranthen-2-ylboronic acid (8.7 g, 35.2 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (13.9 g, 100.5 mmol) was dissolved in 42 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15 g of compound 1-57. (Yield 73%, MS: [M+H] ⁺ = 614)

Synthesis Example 1-58

The compound Trz1 (15 g, 41.9 mmol) and (2-chlorophenyl)boronic acid (6.9 g, 44 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (17.4 g, 125.8 mmol) was dissolved in 52 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.1 g of compound 1-58_P1. (Yield 72%, MS: [M+H] ⁺ = 434)

Compound 1-58_P1 (15 g, 34.6 mmol) and fluoranthen-2-ylboronic acid (8.9 g, 36.3 mmol) were added to 300 ml of 1,4-dioxane, stirred and refluxed. Thereafter, potassium phosphate (22 g, 103.7 mmol) was dissolved in 66 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.8 g of compound 1-58. (Yield 62%, MS: [M+H] ⁺ = 600)

Synthesis Example 1-59

The compound Trz5 (15 g, 33.5 mmol) and (2-chlorophenyl)boronic acid (5.5 g, 35.2 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (13.9 g, 100.5 mmol) was dissolved in 42 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.9 g of compound 1-59_P1. (Yield 62%, MS: [M+H] ⁺ = 524)

Compound 1-59_P1 (15 g, 28.6 mmol) and fluoranthen-2-ylboronic acid (7.4 g, 30.1 mmol) were added to 300 ml of 1,4-dioxane, stirred and refluxed. Thereafter, potassium phosphate (18.2 g, 85.9 mmol) was dissolved in 55 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.2 g of compound 1-59. (Yield 62%, MS: [M+H] ⁺ = 690)

Synthesis Example 1-62

Compound Trz6 (15 g, 66.4 mmol) and (7-(naphthalen-2-yl)dibenzo[b,d]furan-1-yl)boronic acid (23.6 g, 69.7 mmol) were added to 300 ml of THF, stirred and refluxed. did Thereafter, potassium carbonate (27.5 g, 199.1 mmol) was dissolved in 83 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.7 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.8 g of compound 1-62_P1. (Yield 68%, MS: [M+H] ⁺ = 484)

Compound 1-62_P1 (15 g, 31 mmol) and fluoranthen-2-ylboronic acid (8 g, 32.5 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (12.9 g, 93 mmol) was dissolved in 39 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.5 g of compound 1-62. (Yield 72%, MS: [M+H] ⁺ = 650)

Synthesis Example 1-63

The compound Trz6 (15 g, 66.4 mmol) and (8-phenyldibenzo[b,d]furan-1-yl)boronic acid (20.1 g, 69.7 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (27.5 g, 199.1 mmol) was dissolved in 83 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.7 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.8 g of compound 1-63_P1. (Yield 62%, MS: [M+H] ⁺ = 434)

Compound 1-63_P1 (15 g, 34.6 mmol) and fluoranthen-2-ylboronic acid (8.9 g, 36.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.3 g, 103.7 mmol) was dissolved in 43 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.3 g of compound 1-63. (Yield 74%, MS: [M+H] ⁺ = 600)

Synthesis Example 1-64

The compound Trz6 (15 g, 66.4 mmol) and (6-phenyldibenzo[b,d]furan-1-yl)boronic (20.1 g, 69.7 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (27.5 g, 199.1 mmol) was dissolved in 83 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.7 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.8 g of compound 1-64_P1. (Yield 69%, MS: [M+H] ⁺ = 434)

Compound 1-64_P1 (15 g, 34.6 mmol) and (2-chlorophenyl)boronic acid (5.7 g, 36.3 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (14.3 g, 103.7 mmol) was dissolved in 43 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13 g of compound 1-64_P2. (Yield 74%, MS: [M+H] ⁺ = 510)

Compound 1-64_P2 (15 g, 29.4 mmol) and fluoranthen-2-ylboronic acid (7.6 g, 30.9 mmol) were added to 300 ml of 1,4-dioxane, stirred and refluxed. Thereafter, potassium phosphate (18.7 g, 88.2 mmol) was dissolved in 56 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.9 g of Compound 1-64. (Yield 70%, MS: [M+H] ⁺ = 676)

Synthesis Example 1-65

The compound Trz1 (15 g, 41.9 mmol) and fluoranthen-3-ylboronic acid (10.8 g, 44 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (17.4 g, 125.8 mmol) was dissolved in 52 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.2 g of compound 1-65. (Yield 60%, MS: [M+H] ⁺ = 524)

Synthesis Example 1-66

Compound Trz6 (15 g, 66.4 mmol) and (4-(dibenzo[b,d]furan-1-yl)naphthalen-2-yl)boronic acid (23.6 g, 69.7 mmol) were added to 300 ml of THF, stirred and refluxed. did Thereafter, potassium carbonate (27.5 g, 199.1 mmol) was dissolved in 83 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.7 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.8 g of compound 1-66_P1. (Yield 65%, MS: [M+H] ⁺ = 484)

Compound 1-66_P1 (15 g, 31 mmol) and fluoranthen-3-ylboronic acid (8 g, 32.5 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (12.9 g, 93 mmol) was dissolved in 39 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.9 g of compound 1-66. (Yield 64%, MS: [M+H] ⁺ = 650)

Synthesis Example 1-67

Compound 1-24_P1 (15 g, 34.6 mmol) and fluoranthen-3-ylboronic acid (8.9 g, 36.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.3 g, 103.7 mmol) was dissolved in 43 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.3 g of Compound 1-67. (Yield 69%, MS: [M+H] ⁺ = 600)

Synthesis Example 1-68

Compound 1-26_P1 (15 g, 34.6 mmol) and fluoranthen-3-ylboronic acid (8.9 g, 36.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.3 g, 103.7 mmol) was dissolved in 43 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.3 g of compound 1-68. (Yield 74%, MS: [M+H] ⁺ = 600)

Synthesis Example 1-69

The compound Trz12 (15 g, 34.6 mmol) and fluoranthen-7-ylboronic acid (8.9 g, 36.3 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (14.3 g, 103.7 mmol) was dissolved in 43 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.1 g of compound 1-69. (Yield 68%, MS: [M+H] ⁺ = 600)

Synthesis Example 1-70

Compound 1-40_P1 (15 g, 34.6 mmol) and fluoranthen-7-ylboronic acid (8.9 g, 36.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.3 g, 103.7 mmol) was dissolved in 43 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.9 g of compound 1-70. (Yield 67%, MS: [M+H] ⁺ = 600)

Synthesis Example 1-71

The compound Trz7 (15 g, 36.8 mmol) and (3-chlorophenyl)boronic acid (6 g, 38.6 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (15.2 g, 110.3 mmol) was dissolved in 46 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.1 g of compound 1-71_P1. (Yield 74%, MS: [M+H] ⁺ = 484)

Compound 1-71_P1 (15 g, 31 mmol) and fluoranthen-7-ylboronic acid (8 g, 32.5 mmol) were added to 300 ml of 1,4-dioxane, stirred and refluxed. Thereafter, potassium phosphate (19.7 g, 93 mmol) was dissolved in 59 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.3 g of Compound 1-71. (Yield 61%, MS: [M+H] ⁺ = 650)

Synthesis Example 1-72

The compound Trz4 (15 g, 47.4 mmol) and (2-(dibenzo[b,d]furan-1-yl)phenyl)boronic acid (14.4 g, 49.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (19.7 g, 142.3 mmol) was dissolved in 59 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.9 g of compound 1-72_P1. (Yield 64%, MS: [M+H] ⁺ = 524)

Compound 1-72_P1 (15 g, 28.6 mmol) and fluoranthen-7-ylboronic acid (7.4 g, 30.1 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (11.9 g, 85.9 mmol) was dissolved in 36 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.2 g of Compound 1-72. (Yield 62%, MS: [M+H] ⁺ = 690)

Synthesis Example 1-73

The compound Trz6 (15 g, 66.4 mmol) and (7-phenyldibenzo[b,d]furan-1-yl)boronic acid (20.1 g, 69.7 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (27.5 g, 199.1 mmol) was dissolved in 83 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.7 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.2 g of compound 1-73_P1. (Yield 60%, MS: [M+H] ⁺ = 434)

Compound 1-73_P1 (15 g, 34.6 mmol) and (2-chlorophenyl)boronic acid (5.7 g, 36.3 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (14.3 g, 103.7 mmol) was dissolved in 43 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.3 g of compound 1-73_P2. (Yield 64%, MS: [M+H] ⁺ = 510)

Compound 1-73_P2 (15 g, 29.4 mmol) and fluoranthen-7-ylboronic acid (7.6 g, 30.9 mmol) were added to 300 ml of 1,4-dioxane, stirred and refluxed. Thereafter, potassium phosphate (18.7 g, 88.2 mmol) was dissolved in 56 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.7 g of compound 1-73. (Yield 69%, MS: [M+H] ⁺ = 676)

Synthesis Example 1-74

Compound Trz1 (15 g, 41.9 mmol) and fluoranthen-8-ylboronic acid (10.8 g, 44 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (17.4 g, 125.8 mmol) was dissolved in 52 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.8 g of compound 1-74. (Yield 72%, MS: [M+H] ⁺ = 524)

Synthesis Example 1-75

The compound Trz2 (15 g, 34.6 mmol) and (3-chlorophenyl)boronic acid (5.7 g, 36.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.3 g, 103.7 mmol) was dissolved in 43 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.3 g of compound 1-75_P1. (Yield 64%, MS: [M+H] ⁺ = 510)

Compound 1-75_P1 (15 g, 34.6 mmol) and fluoranthen-8-ylboronic acid (8.9 g, 36.3 mmol) were added to 300 ml of 1,4-dioxane, stirred and refluxed. Thereafter, potassium phosphate (22 g, 103.7 mmol) was dissolved in 66 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 16.6 g of compound 1-75. (Yield 71%, MS: [M+H] ⁺ = 676)

Synthesis Example 1-76

Compound 1-35_P1 (15 g, 34.6 mmol) and fluoranthen-8-ylboronic acid (8.9 g, 36.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.3 g, 103.7 mmol) was dissolved in 43 ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.3 g of compound 1-76. (Yield 64%, MS: [M+H] ⁺ = 600)

Synthesis Example 1-79

Compound 1-10_P1 (15 g, 31 mmol) and fluoranthen-8-ylboronic acid (8 g, 32.5 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (12.9 g, 93 mmol) was dissolved in 39 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.1 g of compound 1-79. (Yield 75%, MS: [M+H] ⁺ = 650)

Synthesis Example 2-1

1-bromo-7-chloronaphthalen-2-ol (15 g, 58.3 mmol) and (2-fluorophenyl)boronic acid (8.6 g, 61.2 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (24.2 g, 174.8 mmol) was dissolved in 72 ml of water, and after stirring sufficiently, Tetrakis (triphenylphosphine) palladium (0) (0.7 g, 0.6 mmol) was added. After reacting for 6 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.4 g of compound A_P1. (Yield 78%, MS: [M+H] ⁺ = 273)

Compound A_P1 (15 g, 55 mmol) and potassium carbonate (22.8 g, 165 mmol) were added to 150 ml of DMAc and stirred and refluxed. After reacting for 5 hours, the mixture was cooled to room temperature, poured into 300 ml of water, solidified, and filtered to obtain a solid. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.5 g of Compound A. (Yield 61%, MS: [M+H] ⁺ = 253)

Compound A (15 g, 59.4 mmol) and compound amine1 (30.6 g, 62.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (24.6 g, 178.1 mmol) was dissolved in 74 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 27.6 g of compound 2-1. (Yield 70%, MS: [M+H] ⁺ = 664)

Synthesis Example 2-2

Compound A (15 g, 59.4 mmol) and compound amine2 (27.5 g, 62.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (24.6 g, 178.1 mmol) was dissolved in 74 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 26.2 g of compound 2-2. (Yield 72%, MS: [M+H] ⁺ = 614)

Synthesis Example 2-3

Compound A (15 g, 59.4 mmol) and compound amine3 (25.9 g, 62.3 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (24.6 g, 178.1 mmol) was dissolved in 74 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 23.4 g of compound 2-3. (Yield 67%, MS: [M+H] ⁺ = 588)

Synthesis Example 2-4

Compound A (15 g, 59.4 mmol) and compound amine4 (23.6 g, 62.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (24.6 g, 178.1 mmol) was dissolved in 74 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 24.2 g of Compound 2-4. (Yield 74%, MS: [M+H] ⁺ = 552)

Synthesis Example 2-5

Compound A (15 g, 59.4 mmol) and compound amine5 (32.3 g, 62.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (24.6 g, 178.1 mmol) was dissolved in 74 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 26.6 g of Compound 2-5. (Yield 65%, MS: [M+H] ⁺ = 690)

Synthesis Example 2-6

Compound A (15 g, 59.4 mmol) and compound amine6 (30.6 g, 62.3 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (24.6 g, 178.1 mmol) was dissolved in 74 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 29.1 g of compound 2-6. (Yield 74%, MS: [M+H] ⁺ = 664)

Synthesis Example 2-7

Compound A (15 g, 59.4 mmol) and compound amine7 (33.7 g, 62.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (24.6 g, 178.1 mmol) was dissolved in 74 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 27.9 g of Compound 2-7. (Yield 66%, MS: [M+H] ⁺ = 714)

Synthesis Example 2-8

Compound A (15 g, 59.4 mmol) and compound amine8 (34 g, 62.3 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (24.6 g, 178.1 mmol) was dissolved in 74 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 30.7 g of Compound 2-8. (Yield 72%, MS: [M+H] ⁺ = 718)

Synthesis Example 2-9

Trifluoromethanesulfonic anhydride (33.5 g, 118.7 mmol) and Deuterium oxide (11.9 g, 593.6 mmol) were added to the mixture at 0 °C and stirred for 5 hours to form a solution. Compound A (15 g, 59.4 mmol) was added to 120 ml of 1,2,4-trichlorobenzene and stirred. Thereafter, the prepared mixed solution of Trifluoromethanesulfonic anhydride and Deuterium oxide was slowly added dropwise to the mixed solution of Compound A and 1,2,4-trichlorobenzene, and the temperature was raised to 140 °C and stirred while maintaining. After reacting for 3 hours, it was cooled to room temperature, and the organic layer and the water layer were separated. Then, the organic layer was neutralized with an aqueous solution of potassium carbonate. After washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 5.4 g of compound subA-1. (Yield 36%, MS: [M+H] ⁺ = 255)

Compound subA-1 (15 g, 59.6 mmol) and compound amine9 (30.7 g, 62.6 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (24.7 g, 178.8 mmol) was dissolved in 74 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 28.9 g of compound 2-9. (Yield 73%, MS: [M+H] ⁺ = 666)

Synthesis Example 2-10

Trifluoromethanesulfonic anhydride (67 g, 237.4 mmol) and Deuterium oxide (23.8 g, 1187.2 mmol) were added and stirred for 6 hours to form a solution at 0 °C. Compound A (15 g, 59.4 mmol) was added to 120 ml of 1,2,4-trichlorobenzene and stirred. Thereafter, the prepared mixed solution of Trifluoromethanesulfonic anhydride and Deuterium oxide was slowly added dropwise to the mixed solution of Compound A and 1,2,4-trichlorobenzene, and the temperature was raised to 140 °C and stirred while maintaining. After reacting for 10 hours, it was cooled to room temperature and the organic layer and the water layer were separated. Then, the organic layer was neutralized with an aqueous solution of potassium carbonate. After washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.2 g of compound subA-2. (Yield 41%, MS: [M+H] ⁺ = 258)

Compound subA-2 (15 g, 58.9 mmol) and compound amine10 (29 g, 61.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (24.4 g, 176.7 mmol) was dissolved in 73 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 25.4 g of compound 2-10. (Yield 67%, MS: [M+H] ⁺ = 645)

Synthesis Example 2-11

Compound subA-2 (15 g, 58.9 mmol) and compound amine11 (30.9 g, 61.8 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (24.4 g, 176.7 mmol) was dissolved in 73 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 26.3 g of Compound 2-11. (Yield 66%, MS: [M+H] ⁺ = 677)

Synthesis Example 2-12

A solution was prepared by adding trifluoromethanesulfonic anhydride (83.7 g, 296.8 mmol) and Deuterium oxide (29.7 g, 1484 mmol) and stirring for 6 hours at 0 °C. Compound A (15 g, 59.4 mmol) was added to 120 ml of 1,2,4-trichlorobenzene and stirred. Thereafter, the prepared mixed solution of Trifluoromethanesulfonic anhydride and Deuterium oxide was slowly added dropwise to the mixed solution of Compound A and 1,2,4-trichlorobenzene, and the temperature was raised to 140 °C and stirred while maintaining. After reacting for 14 hours, it was cooled to room temperature, and the organic layer and water layer were separated. Then, the organic layer was neutralized with an aqueous solution of potassium carbonate. After washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.9 g of compound subA-3. (Yield 45%, MS: [M+H] ⁺ = 259)

Compound subA-3 (15 g, 58 mmol) and compound amine12 (31.8 g, 60.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (24 g, 173.9 mmol) was dissolved in 72 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 26.4 g of Compound 2-12. (Yield 65%, MS: [M+H] ⁺ = 701)

Synthesis Example 2-13

Compound subA-3 (15 g, 58 mmol) and compound amine13 (23.4 g, 60.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (24 g, 173.9 mmol) was dissolved in 72 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 21.5 g of compound 2-13. (Yield 66%, MS: [M+H] ⁺ = 563)

Synthesis Example 2-14

Compound subA-3 (15 g, 58 mmol) and compound amine14 (26 g, 60.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (24 g, 173.9 mmol) was dissolved in 72 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 25.3 g of compound 2-14. (Yield 72%, MS: [M+H] ⁺ = 606)

Synthesis Example 2-15

Trifluoromethanesulfonic anhydride (117.2 g, 415.5 mmol) and Deuterium oxide (41.6 g, 2077.6 mmol) were added and stirred for 6 hours to form a solution at 0 °C. Compound A (15 g, 59.4 mmol) was added to 120 ml of 1,2,4-trichlorobenzene and stirred. Thereafter, the prepared mixed solution of Trifluoromethanesulfonic anhydride and Deuterium oxide was slowly added dropwise to the mixed solution of Compound A and 1,2,4-trichlorobenzene, and the temperature was raised to 140 °C and stirred while maintaining. After reacting for 20 hours, it was cooled to room temperature and the organic layer and the water layer were separated. Then, the organic layer was neutralized with an aqueous solution of potassium carbonate. After washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 5.8 g of compound subA-4. (Yield 38%, MS: [M+H] ⁺ = 260)

Compound subA-4 (15 g, 57.8 mmol) and compound amine15 (27 g, 60.6 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (23.9 g, 173.3 mmol) was dissolved in 72 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 23.8 g of compound 2-15. (Yield 66%, MS: [M+H] ⁺ = 625)

Synthesis Example 2-16

Compound subA-4 (15 g, 57.8 mmol) and compound amine16 (32.4 g, 60.6 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (23.9 g, 173.3 mmol) was dissolved in 72 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 26.8 g of Compound 2-16. (Yield 65%, MS: [M+H] ⁺ = 714)

Synthesis Example 2-17

Compound subA-4 (15 g, 57.8 mmol) and compound amine17 (28.7 g, 60.6 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (23.9 g, 173.3 mmol) was dissolved in 72 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 24.9 g of compound 2-17. (Yield 66%, MS: [M+H] ⁺ = 653)

Synthesis Example 2-18

Trifluoromethanesulfonic anhydride (150.7 g, 534.2 mmol) and Deuterium oxide (53.5 g, 2671.2 mmol) were added and stirred for 6 hours to form a solution at 0 °C. Compound A (15 g, 59.4 mmol) was added to 120 ml of 1,2,4-trichlorobenzene and stirred. Thereafter, the prepared mixed solution of Trifluoromethanesulfonic anhydride and Deuterium oxide was slowly added dropwise to the mixed solution of Compound A and 1,2,4-trichlorobenzene, and the temperature was raised to 140 °C and stirred while maintaining. After reacting for 28 hours, it was cooled to room temperature and the organic layer and the water layer were separated. Then, the organic layer was neutralized with an aqueous solution of potassium carbonate. After washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.5 g of compound subA-5. (Yield 42%, MS: [M+H] ⁺ = 262)

Compound subA-5 (15 g, 57.3 mmol) and compound amine18 (32.9 g, 60.2 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (23.8 g, 171.9 mmol) was dissolved in 71 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 31.3 g of compound 2-18. (Yield 75%, MS: [M+H] ⁺ = 729)

Synthesis Example 2-19

Compound subA-5 (15 g, 57.3 mmol) and compound amine19 (36.6 g, 60.2 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (23.8 g, 171.9 mmol) was dissolved in 71 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 30.3 g of Compound 2-19. (Yield 67%, MS: [M+H] ⁺ = 789)

Synthesis Example 2-20

Compound 2-1 (10 g, 15.1 mmol), PtO ₂ (1 g, 4.5 mmol), and 75 ml of D ₂ O were added to a shaker tube, and the tube was sealed and heated at 250 °C and 600 psi for 12 hours. When the reaction was completed, chloroform was added and the reaction solution was transferred to a separatory funnel and extracted. The extract was dried with MgSO ₄ , concentrated, and the sample was subjected to silica gel column chromatography to prepare 3.2 g of compound 2-20. (Yield 31%, MS: [M+H] ⁺ = 694)

Synthesis Example 2-21

Compound 2-2 (10 g, 16.3 mmol), PtO ₂ (1.1 g, 4.9 mmol), and 81 ml of D2O were added to a shaker tube, and then the tube was sealed and heated at 250 °C and 600 psi for 12 hours. When the reaction was completed, chloroform was added and the reaction solution was transferred to a separatory funnel and extracted. The extract was dried with MgSO ₄ , concentrated, and the sample was purified by silica gel column chromatography to prepare 4.7 g of compound 2-21. (Yield 45%, MS: [M+H] ⁺ = 641)

Synthesis Example 2-22

Compound 2-3 (10 g, 17 mmol), PtO ₂ (1.2 g, 5.1 mmol), and 85 ml of D ₂ O were added to a shaker tube, and the tube was sealed and heated at 250 °C and 600 psi for 12 hours. When the reaction was completed, chloroform was added and the reaction solution was transferred to a separatory funnel and extracted. The extract was dried with MgSO ₄ , concentrated, and the sample was purified by silica gel column chromatography to prepare 4.4 g of compound 2-22. (Yield 42%, MS: [M+H] ⁺ = 615)

Synthesis Example 2-23

Compound A (15 g, 59.4 mmol) and compound amine20 (28.4 g, 62.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (24.6 g, 178.1 mmol) was dissolved in 74 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.6 g of compound 2-23_P1. (Yield 66%, MS: [M+H] ⁺ = 628)

Compound 2-23_P1 (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, and the tube was sealed and heated at 250 °C and 600 psi for 12 hours. When the reaction was completed, chloroform was added and the reaction solution was transferred to a separatory funnel and extracted. The extract was dried with MgSO ₄ , concentrated, and the sample was purified by silica gel column chromatography to prepare 4.4 g of compound 2-23. (Yield 42%, MS: [M+H] ⁺ = 655)

Synthesis Example 2-24

Compound A (15 g, 59.4 mmol) and compound amine21 (35.4 g, 62.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (24.6 g, 178.1 mmol) was dissolved in 74 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 28.5 g of compound 2-24_P1. (Yield 65%, MS: [M+H] ⁺ = 740)

Compound 2-24_P1 (10 g, 13.5 mmol), PtO ₂ (0.9 g, 4.1 mmol), and D ₂ O 68 ml were added to a shaker tube, and the tube was sealed and heated at 250 °C and 600 psi for 12 hours. When the reaction was completed, chloroform was added and the reaction solution was transferred to a separatory funnel and extracted. The extract was dried with MgSO ₄ , concentrated, and the sample was purified by silica gel column chromatography to prepare 4.4 g of compound 2-24. (Yield 42%, MS: [M+H] ⁺ = 774)

Synthesis Example 2-25

1-bromo-6-chloronaphthalen-2-ol (15 g, 58.3 mmol) and (2-fluorophenyl)boronic acid (8.6 g, 61.2 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (24.2 g, 174.8 mmol) was dissolved in 72 ml of water, and after stirring sufficiently, Tetrakis (triphenylphosphine) palladium (0) (0.7 g, 0.6 mmol) was added. After reacting for 6 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.5 g of compound B_P1. (Yield 66%, MS: [M+H] ⁺ = 273)

Compound B_P1 (15 g, 55 mmol) and potassium carbonate (22.8 g, 165 mmol) were added to 150 ml of DMAc and stirred and refluxed. After reacting for 5 hours, the mixture was cooled to room temperature, poured into 300 ml of water, solidified, and filtered to obtain a solid. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.5 g of Compound B. (Yield 65%, MS: [M+H] ⁺ = 253)

Compound B (15 g, 59.4 mmol) and compound amine22 (25.9 g, 62.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (24.6 g, 178.1 mmol) was dissolved in 74 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 23.7 g of compound 2-25. (Yield 68%, MS: [M+H] ⁺ = 588)

Synthesis Example 2-26

Compound B (15 g, 59.4 mmol) and compound amine23 (33.1 g, 62.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (24.6 g, 178.1 mmol) was dissolved in 74 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 27.9 g of compound 2-26. (Yield 67%, MS: [M+H] ⁺ = 703)

Synthesis Example 2-27

Compound B (15 g, 59.4 mmol) and compound amine24 (25.9 g, 62.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (24.6 g, 178.1 mmol) was dissolved in 74 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 25.4 g of compound 2-27. (Yield 73%, MS: [M+H] ⁺ = 588)

Synthesis Example 2-28

Compound B (15 g, 59.4 mmol) and compound amine25 (24.6 g, 62.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (24.6 g, 178.1 mmol) was dissolved in 74 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 22.9 g of compound 2-28. (Yield 68%, MS: [M+H] ⁺ = 568)

Synthesis Example 2-29

Compound B (15 g, 59.4 mmol) and compound amine26 (30.6 g, 62.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (24.6 g, 178.1 mmol) was dissolved in 74 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 26.4 g of compound 2-29. (Yield 67%, MS: [M+H] ⁺ = 664)

Synthesis Example 2-30

Compound B (15 g, 59.4 mmol) and compound amine27 (33.7 g, 62.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (24.6 g, 178.1 mmol) was dissolved in 74 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 29.6 g of Compound 2-30. (Yield 70%, MS: [M+H] ⁺ = 714)

Synthesis Example 2-31

Compound B (15 g, 59.4 mmol) and compound amine28 (33.1 g, 62.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (24.6 g, 178.1 mmol) was dissolved in 74 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 27.5 g of compound 2-31. (Yield 66%, MS: [M+H] ⁺ = 703)

Synthesis Example 2-32

Compound B (15 g, 59.4 mmol) and compound amine29 (31.3 g, 62.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (24.6 g, 178.1 mmol) was dissolved in 74 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 26 g of compound 2-32. (Yield 65%, MS: [M+H] ⁺ = 675)

Synthesis Example 2-33

Trifluoromethanesulfonic anhydride (33.5 g, 118.7 mmol) and Deuterium oxide (11.9 g, 593.6 mmol) were added to the mixture at 0 °C and stirred for 5 hours to form a solution. Compound B (15 g, 59.4 mmol) was added to 120 ml of 1,2,4-trichlorobenzene and stirred. Thereafter, the prepared mixed solution of Trifluoromethanesulfonic anhydride and Deuterium oxide was slowly added dropwise to the mixed solution of Compound A and 1,2,4-trichlorobenzene, and the temperature was raised to 140 °C and stirred while maintaining. After reacting for 4 hours, it was cooled to room temperature and the organic layer and the water layer were separated. Then, the organic layer was neutralized with an aqueous solution of potassium carbonate. After washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.5 g of compound subB-1. (Yield 43%, MS: [M+H] ⁺ = 255)

Compound subB-1 (15 g, 58.9 mmol) and compound amine30 (30.4 g, 61.8 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (24.4 g, 176.7 mmol) was dissolved in 73 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 27.8 g of compound 2-33. (Yield 71%, MS: [M+H] ⁺ = 666)

Synthesis Example 2-34

Compound subB-1 (15 g, 58.9 mmol) and compound amine31 (35.6 g, 61.8 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (24.4 g, 176.7 mmol) was dissolved in 73 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 33.1 g of compound 2-34. (Yield 75%, MS: [M+H] ⁺ = 750)

Synthesis Example 2-35

A solution was prepared by adding trifluoromethanesulfonic anhydride (50.2 g, 178.1 mmol) and Deuterium oxide (17.8 g, 890.4 mmol) and stirring for 6 hours at 0 °C. Compound B (15 g, 59.4 mmol) was added to 120 ml of 1,2,4-trichlorobenzene and stirred. Thereafter, the prepared mixed solution of Trifluoromethanesulfonic anhydride and Deuterium oxide was slowly added dropwise to the mixed solution of Compound A and 1,2,4-trichlorobenzene, and the temperature was raised to 140 °C and stirred while maintaining. After reacting for 7 hours, it was cooled to room temperature and the organic layer and the water layer were separated. Then, the organic layer was neutralized with an aqueous solution of potassium carbonate. After washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.7 g of compound subB-2. (Yield 44%, MS: [M+H] ⁺ = 256)

Compound subB-2 (15 g, 58.7 mmol) and compound amine32 (25.9 g, 61.6 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (24.3 g, 176 mmol) was dissolved in 73 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 26.2 g of Compound 2-35. (Yield 75%, MS: [M+H] ⁺ = 596)

Synthesis Example 2-36

Compound subB-2 (15 g, 58.7 mmol) and compound amine33 (30.6 g, 61.6 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (24.3 g, 176 mmol) was dissolved in 73 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 27.6 g of compound 2-36. (Yield 70%, MS: [M+H] ⁺ = 672)

Synthesis Example 2-37

Trifluoromethanesulfonic anhydride (67 g, 237.4 mmol) and Deuterium oxide (23.8 g, 1187.2 mmol) were added and stirred for 6 hours to form a solution at 0 °C. Compound B (15 g, 59.4 mmol) was added to 120 ml of 1,2,4-trichlorobenzene and stirred. Thereafter, the prepared mixed solution of Trifluoromethanesulfonic anhydride and Deuterium oxide was slowly added dropwise to the mixed solution of Compound B and 1,2,4-trichlorobenzene, and the temperature was raised to 140 °C and stirred while maintaining. After reacting for 10 hours, it was cooled to room temperature and the organic layer and the water layer were separated. Then, the organic layer was neutralized with an aqueous solution of potassium carbonate. After washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 5.9 g of compound subB-3. (Yield 39%, MS: [M+H] ⁺ = 258)

Compound subB-3 (15 g, 58.4 mmol) and compound amine34 (33.9 g, 61.4 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (24.2 g, 175.3 mmol) was dissolved in 73 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 30.6 g of compound 2-37. (Yield 72%, MS: [M+H] ⁺ = 729)

Synthesis Example 2-38

Trifluoromethanesulfonic anhydride (100.5 g, 356.2 mmol) and Deuterium oxide (35.7 g, 1780.8 mmol) were added and stirred for 6 hours to form a solution at 0 °C. Compound B (15 g, 59.4 mmol) was added to 120 ml of 1,2,4-trichlorobenzene and stirred. Thereafter, the prepared mixed solution of Trifluoromethanesulfonic anhydride and Deuterium oxide was slowly added dropwise to the mixed solution of Compound B and 1,2,4-trichlorobenzene, and the temperature was raised to 140 °C and stirred while maintaining. After reacting for 17 hours, it was cooled to room temperature and the organic layer and the water layer were separated. Then, the organic layer was neutralized with an aqueous solution of potassium carbonate. After washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 5.4 g of compound subB-4. (Yield 35%, MS: [M+H] ⁺ = 259)

Compound subB-4 (15 g, 58 mmol) and compound amine35 (25.8 g, 60.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (24 g, 173.9 mmol) was dissolved in 72 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 22.7 g of compound 2-38. (Yield 65%, MS: [M+H] ⁺ = 603)

Synthesis Example 2-39

Trifluoromethanesulfonic anhydride (117.2 g, 415.5 mmol) and Deuterium oxide (41.6 g, 2077.6 mmol) were added and stirred for 6 hours to form a solution at 0 °C. Compound B (15 g, 59.4 mmol) was added to 120 ml of 1,2,4-trichlorobenzene and stirred. Thereafter, the prepared mixed solution of Trifluoromethanesulfonic anhydride and Deuterium oxide was slowly added dropwise to the mixed solution of Compound B and 1,2,4-trichlorobenzene, and the temperature was raised to 140 °C and stirred while maintaining. After reacting for 21 hours, it was cooled to room temperature and the organic layer and the water layer were separated. Then, the organic layer was neutralized with an aqueous solution of potassium carbonate. After washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 5.7 g of compound subB-5. (Yield 37%, MS: [M+H] ⁺ = 260)

Compound subB-5 (15 g, 57.8 mmol) and compound amine36 (22.5 g, 60.6 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (23.9 g, 173.3 mmol) was dissolved in 72 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 22.2 g of compound 2-39. (Yield 70%, MS: [M+H] ⁺ = 550)

Synthesis Example 2-40

Compound subB-5 (15 g, 57.8 mmol) and compound amine37 (34.4 g, 60.6 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (23.9 g, 173.3 mmol) was dissolved in 72 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 30.2 g of compound 2-40. (Yield 70%, MS: [M+H] ⁺ = 747)

Synthesis Example 2-41

Trifluoromethanesulfonic anhydride (134 g, 474.9 mmol) and Deuterium oxide (47.6 g, 2374.4 mmol) were added and stirred for 6 hours to form a solution at 0 °C. Compound B (15 g, 59.4 mmol) was added to 120 ml of 1,2,4-trichlorobenzene and stirred. Thereafter, the prepared mixed solution of Trifluoromethanesulfonic anhydride and Deuterium oxide was slowly added dropwise to the mixed solution of Compound B and 1,2,4-trichlorobenzene, and the temperature was raised to 140 °C and stirred while maintaining. After reacting for 25 hours, it was cooled to room temperature and the organic layer and the water layer were separated. Then, the organic layer was neutralized with an aqueous solution of potassium carbonate. After washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.6 g of compound subB-6. (Yield 43%, MS: [M+H] ⁺ = 261)

Compound subB-6 (15 g, 57.5 mmol) and compound amine38 (24.1 g, 60.4 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (23.9 g, 172.6 mmol) was dissolved in 72 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 22.3 g of Compound 2-41. (Yield 67%, MS: [M+H] ⁺ = 579)

Synthesis Example 2-42

Compound subB-6 (15 g, 57.5 mmol) and compound amine39 (33.3 g, 60.4 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (23.9 g, 172.6 mmol) was dissolved in 72 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 30.3 g of compound 2-42. (Yield 72%, MS: [M+H] ⁺ = 732)

Synthesis Example 2-43

Compound subB-6 (15 g, 57.5 mmol) and compound amine40 (30.3 g, 60.4 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (23.9 g, 172.6 mmol) was dissolved in 72 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 26.7 g of compound 2-43. (Yield 68%, MS: [M+H] ⁺ = 684)

Synthesis Example 2-44

Compound B (15 g, 59.4 mmol) and compound amine41 (35.4 g, 62.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (24.6 g, 178.1 mmol) was dissolved in 74 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 32.5 g of compound 2-44_P1. (Yield 74%, MS: [M+H] ⁺ = 740)

Compound 2-44_P1 (10 g, 13.5 mmol), PtO ₂ (0.9 g, 4.1 mmol), and 68 ml of D2O were added to a shaker tube, and the tube was sealed and heated at 250 °C and 600 psi for 12 hours. When the reaction was completed, chloroform was added and the reaction solution was transferred to a separatory funnel and extracted. The extract was dried with MgSO ₄ , concentrated, and the sample was purified by silica gel column chromatography to prepare 4.6 g of compound 2-44. (Yield 44%, MS: [M+H] ⁺ = 772)

Synthesis Example 2-45

Compound 2-26 (10 g, 14.2 mmol), PtO ₂ (1 g, 4.3 mmol), and 71 ml of D ₂ O were added to a shaker tube, and the tube was sealed and heated at 250 °C and 600 psi for 12 hours. When the reaction was completed, chloroform was added and the reaction solution was transferred to a separatory funnel and extracted. The extract was dried with MgSO ₄ , concentrated, and the sample was purified by silica gel column chromatography to prepare 3.4 g of compound 2-45. (Yield 33%, MS: [M+H] ⁺ = 734)

Synthesis Example 2-46

Compound B (15 g, 59.4 mmol) and compound amine42 (29.3 g, 62.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (24.6 g, 178.1 mmol) was dissolved in 74 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 27.8 g of compound 2-46_P1. (Yield 73%, MS: [M+H] ⁺ = 642)

Compound 2-46_P1 (10 g, 15.6 mmol), PtO ₂ (1.1 g, 4.7 mmol), and 78 ml of D ₂ O were added to a shaker tube, and the tube was sealed and heated at 250 °C and 600 psi for 12 hours. When the reaction was completed, chloroform was added and the reaction solution was transferred to a separatory funnel and extracted. The extract was dried with MgSO ₄ , concentrated, and the sample was purified by silica gel column chromatography to prepare 3.2 g of compound 2-46. (Yield 31%, MS: [M+H] ⁺ = 666)

Synthesis Example 2-47

Compound B (15 g, 59.4 mmol) and compound amine43 (30 g, 62.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (24.6 g, 178.1 mmol) was dissolved in 74 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26.4 g of compound 2-47_P1. (Yield 68%, MS: [M+H] ⁺ = 654)

Compound 2-47_P1 (10 g, 15.3 mmol), PtO ₂ (1 g, 4.6 mmol), and 76 ml of D ₂ O were added to a shaker tube, and the tube was sealed and heated at 250 °C and 600 psi for 12 hours. When the reaction was completed, chloroform was added and the reaction solution was transferred to a separatory funnel and extracted. The extract was dried with MgSO ₄ , concentrated, and the sample was purified by silica gel column chromatography to prepare 4.6 g of compound 2-47. (Yield 44%, MS: [M+H] ⁺ = 684)

Synthesis Example 2-48

In a nitrogen atmosphere, compound C (15 g, 59.4 mmol), compound amine44 (20.5 g, 59.4 mmol), and sodium tert-butoxide (8.6 g, 89 mmol) were added to 300 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 4 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 21.3 g of compound 2-48. (Yield 64%, MS: [M+H] ⁺ = 562)

Synthesis Example 2-49

In a nitrogen atmosphere, compound C (15 g, 59.4 mmol), compound amine45 (28.7 g, 59.4 mmol), and sodium tert-butoxide (8.6 g, 89 mmol) were added to 300 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 26.1 g of compound 2-49. (Yield 63%, MS: [M+H] ⁺ = 700)

Synthesis Example 2-50

In a nitrogen atmosphere, compound C (15 g, 59.4 mmol), compound amine46 (25.4 g, 59.4 mmol), and sodium tert-butoxide (8.6 g, 89 mmol) were added to 300 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 28.3 g of compound 2-50. (Yield 74%, MS: [M+H] ⁺ = 644)

Synthesis Example 2-51

Compound C (15 g, 59.4 mmol) and compound amine47 (27.9 g, 62.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (24.6 g, 178.1 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 19.5 g of compound 2-51. (Yield 61%, MS: [M+H] ⁺ = 538)

Synthesis Example 2-52

In a nitrogen atmosphere, compound D (15 g, 59.4 mmol), compound amine48 (19.1 g, 59.4 mmol), and sodium tert-butoxide (8.6 g, 89 mmol) were added to 300 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 21.7 g of compound 2-52. (Yield 68%, MS: [M+H] ⁺ = 538)

Synthesis Example 2-53

In a nitrogen atmosphere, compound D (15 g, 59.4 mmol), compound amine49 (21.7 g, 59.4 mmol), and sodium tert-butoxide (8.6 g, 89 mmol) were added to 300 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 25.2 g of compound 2-53. (Yield 73%, MS: [M+H] ⁺ = 582)

Synthesis Example 2-54

Compound D (15 g, 59.4 mmol) and compound amine50 (35.7 g, 62.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (24.6 g, 178.1 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 28.3 g of compound 2-54. (Yield 72%, MS: [M+H] ⁺ = 664)

Synthesis Example 2-55

Compound D (15 g, 59.4 mmol) and compound amine51 (37.4 g, 62.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (24.6 g, 178.1 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 28.2 g of compound 2-55. (Yield 69%, MS: [M+H] ⁺ = 690)

Synthesis Example 2-56

In a nitrogen atmosphere, compound E (15 g, 59.4 mmol), compound amine52 (26 g, 59.4 mmol), and sodium tert-butoxide (8.6 g, 89 mmol) were added to 300 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 4 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 25.6 g of compound 2-56. (Yield 66%, MS: [M+H] ⁺ = 654)

Synthesis Example 2-57

In a nitrogen atmosphere, compound E (15 g, 59.4 mmol), compound amine53 (19.9 g, 59.4 mmol), and sodium tert-butoxide (8.6 g, 89 mmol) were added to 300 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 23.6 g of compound 2-57. (Yield 72%, MS: [M+H] ⁺ = 552)

Synthesis Example 2-58

Compound E (15 g, 59.4 mmol) and compound amine54 (34.1 g, 62.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (24.6 g, 178.1 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 23.5 g of compound 2-58. (Yield 62%, MS: [M+H] ⁺ = 638)

Synthesis Example 2-59

Compound E (15 g, 59.4 mmol) and compound amine55 (32.6 g, 62.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (24.6 g, 178.1 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 25.8 g of Compound 2-59. (Yield 71%, MS: [M+H] ⁺ = 614)

Synthesis Example 2-60

In a nitrogen atmosphere, compound F (15 g, 59.4 mmol), compound amine56 (23.6 g, 59.4 mmol), and sodium tert-butoxide (8.6 g, 89 mmol) were added to 300 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 24.8 g of compound 2-60. (Yield 68%, MS: [M+H] ⁺ = 614)

Synthesis Example 2-61

In a nitrogen atmosphere, compound F (15 g, 59.4 mmol), compound amine57 (21.5 g, 59.4 mmol), and sodium tert-butoxide (8.6 g, 89 mmol) were added to 300 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 21.9 g of compound 2-61. (Yield 64%, MS: [M+H] ⁺ = 578)

Synthesis Example 2-62

In a nitrogen atmosphere, compound F (15 g, 59.4 mmol), compound amine58 (20.7 g, 59.4 mmol), and sodium tert-butoxide (8.6 g, 89 mmol) were added to 300 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 23.8 g of compound 2-62. (Yield 71%, MS: [M+H] ⁺ = 566)

Synthesis Example 2-63

Compound F (15 g, 59.4 mmol) and compound amine59 (34.5 g, 62.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (24.6 g, 178.1 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and an organic layer and an aqueous layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 23.7 g of compound 2-63. (Yield 62%, MS: [M+H] ⁺ = 644)

Synthesis Example 2-64

In a nitrogen atmosphere, compound G (15 g, 59.4 mmol), compound amine60 (22.1 g, 59.4 mmol), and sodium tert-butoxide (8.6 g, 89 mmol) were added to 300 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 24.4 g of compound 2-64. (Yield 70%, MS: [M+H] ⁺ = 588)

Synthesis Example 2-65

In a nitrogen atmosphere, compound G (15 g, 59.4 mmol), compound amine61 (24.4 g, 59.4 mmol), and sodium tert-butoxide (8.6 g, 89 mmol) were added to 300 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 24.9 g of compound 2-65. (Yield 67%, MS: [M+H] ⁺ = 627)

Synthesis Example 2-66

In a nitrogen atmosphere, compound G (15 g, 59.4 mmol), compound amine62 (21.5 g, 59.4 mmol), and sodium tert-butoxide (8.6 g, 89 mmol) were added to 300 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 5 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 24.3 g of compound 2-66. (Yield 71%, MS: [M+H] ⁺ = 578)

Synthesis Example 2-67

Compound G (15 g, 59.4 mmol) and compound amine63 (34.5 g, 62.3 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (24.6 g, 178.1 mmol) was dissolved in 100 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 29.4 g of compound 2-67. (Yield 77%, MS: [M+H] ⁺ = 644)

Example 1: Manufacturing of organic light emitting device

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

The following compound HI-1 was formed to a thickness of 1150 Å as a hole injection layer on the prepared ITO transparent electrode, but the following compound A-1 was p-doped at a concentration of 1.5% by weight. The following compound HT-1 was vacuum deposited on the hole injection layer to form a hole transport layer having a thickness of 800 Å. Subsequently, an electron blocking layer was formed by vacuum depositing the following compound EB-1 to a film thickness of 150 Å on the hole transport layer.

Then, on the EB-1 deposited film, a host and a dopant compound Dp-7 in which Compound 1-1 as a first host and Compound 2-1 as a second host were mixed at a weight ratio of 50:50 and a dopant compound Dp-7 were vacuum deposited at a weight ratio of 98:2 Thus, a red light emitting layer having a thickness of 400 Å was formed.

A hole blocking layer was formed on the light emitting layer by vacuum depositing the compound HB-1 to a film thickness of 30 Å. Subsequently, the following compound ET-1 and the following compound LiQ were vacuum deposited at a weight ratio of 2:1 on the hole blocking layer to form an electron injection and transport layer with a thickness of 300 Å. A negative electrode was formed by sequentially depositing lithium fluoride (LiF) to a thickness of 12 Å and aluminum to a thickness of 1000 Å on the electron injection and transport layer.

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

Examples 2 to 84 Comparative Examples 1 to 12

The organic light emitting diodes of Examples 2 to 84 and Comparative Examples 1 to 12 were manufactured in the same manner as in Example 1, except that the host material was changed as shown in Tables 1 to 7 below.

Experimental Example 1: Evaluation of device characteristics

When current was applied to the organic light emitting devices manufactured in Examples 1 to 107 and Comparative Examples 1 to 12, voltage, efficiency (10 mA/cm ² standard) and lifetime (20 mA/cm ² standard) were measured. And the results are shown in Tables 1 to 7 below. Here, the lifetime T95 means the time required for the luminance to decrease from the initial luminance (5,000 nit) to 95%.

1st host 2nd host @10 mA/cm ² @20 mA/cm ² Voltage
(V) efficiency
(cd/A) life span
(T95, hr) Example 1 compound 1-1 compound 2-1 3.44 24.1 190 Example 2 compound 2-3 3.40 24.3 189 Example 3 Compounds 2-14 3.33 24.0 181 Example 4 compound 1-2 compound 2-3 3.42 23.9 193 Example 5 Compounds 2-7 3.35 23.8 196 Example 6 Compounds 2-14 3.42 24.1 195 Example 7 Compounds 1-6 compound 2-3 3.29 23.8 181 Example 8 Compounds 2-14 3.41 24.1 195 Example 9 compound 2-25 3.33 24.3 187 Example 10 Compounds 1-13 Compounds 2-8 3.49 23.2 181 Example 11 compounds 2-19 3.54 23.6 180 Example 12 Compounds 2-30 3.51 24.2 181 Example 13 compounds 1-16 Compounds 2-33 3.55 24.4 180 Example 14 Compounds 2-35 3.46 24.7 183 Example 15 Compounds 2-17 3.33 24.3 192

1st host 2nd host @10 mA/cm ² @20 mA/cm ² Voltage
(V) efficiency
(cd/A) life span
(T95, hr) Example 16 compounds 1-19 compound 2-3 3.32 24.9 194 Example 17 Compounds 2-14 3.46 24.3 194 Example 18 Compounds 1-20 compound 2-3 3.42 24.5 192 Example 19 Compounds 2-14 3.40 24.3 193 Example 20 compound 2-29 3.33 24.6 188 Example 21 Compound 1-22 compound 2-3 3.39 24.3 179 Example 22 Compounds 2-14 3.41 23.9 192 Example 23 Compounds 2-33 3.40 24.3 193 Example 24 Compounds 1-26 Compounds 2-35 3.51 23.5 194 Example 25 compound 2-38 3.55 23.1 189 Example 26 compound 2-42 3.52 23.3 184 Example 27 compound 1-29 compound 2-3 3.33 24.2 183 Example 28 Compounds 2-14 3.39 23.8 185 Example 29 compound 2-50 3.42 23.9 184 Example 30 compound 1-30 compound 2-52 3.52 24.2 178 Example 31 compound 2-55 3.41 23.1 191 Example 32 compound 2-67 3.33 23.3 186

1st host 2nd host @10 mA/cm ² @20 mA/cm ² Voltage
(V) efficiency
(cd/A) life span
(T95, hr) Example 33 compound 1-34 compound 2-3 3.39 25.0 204 Example 34 Compounds 2-14 3.33 25.2 191 Example 35 compound 2-65 3.40 25.6 196 Example 36 compound 1-35 compound 2-2 3.34 23.9 201 Example 37 compound 2-6 3.30 24.1 203 Example 38 Compounds 2-12 3.3 24.2 200 Example 39 compound 1-38 Compounds 2-15 3.53 23.3 184 Example 40 Compounds 2-16 3.4 24.1 185 Example 41 Compounds 2-17 3.3 23.9 188 Example 42 compound 1-40 Compounds 2-18 3.36 24.5 193 Example 43 compound 2-22 3.43 25.3 192 Example 44 Compounds 2-31 3.32 26.2 201 Example 45 compound 1-43 compound 2-3 3.33 25.1 200 Example 46 Compounds 2-14 3.30 25.2 205 Example 47 Compounds 2-37 3.41 25.3 201

1st host 2nd host @10 mA/cm ² @20 mA/cm ² Voltage
(V) efficiency
(cd/A) life span
(T95, hr) Example 48 compound 1-46 compound 2-40 3.33 25.4 201 Example 49 compound 2-46 3.20 25.6 203 Example 50 compound 2-49 3.29 25.9 201 Example 51 compound 1-48 compound 2-57 3.3 24.1 208 Example 52 compound 2-62 3.50 24.3 197 Example 53 compound 2-66 3.42 24.3 193 Example 54 compound 1-52 compound 2-11 3.50 24.2 185 Example 55 compound 2-21 3.49 24.1 184 Example 56 compound 2-23 3.41 24.4 198 Example 57 compound 1-54 compound 2-3 3.41 24.8 191 Example 58 Compounds 2-14 3.38 24.3 183 Example 59 compound 2-26 3.35 23.8 192

1st host 2nd host @10 mA/cm ² @20 mA/cm ² Voltage
(V) efficiency
(cd/A) life span
(T95, hr) Example 60 compound 1-55 compound 2-24 3.46 24.2 193 Example 61 compound 2-27 3.33 24.3 182 Example 62 compound 1-57 compound 2-32 3.43 24.9 182 Example 63 Compounds 2-34 3.53 24.1 192 Example 64 compounds 2-39 3.46 23.4 195 Example 65 compound 1-58 Compounds 2-36 3.57 23.6 196 Example 66 compound 2-41 3.58 23.3 191 Example 67 compound 2-44 3.39 24.6 193 Example 68 compound 1-62 compound 2-3 3.41 24.5 192 Example 69 Compounds 2-14 3.35 24.6 199 Example 70 compound 2-58 3.39 24.2 201 Example 71 compound 1-65 compound 2-3 3.32 25.1 192 Example 72 Compounds 2-14 3.35 25.3 201 Example 73 compound 2-64 3.31 25.9 203

1st host 2nd host @10 mA/cm ² @20 mA/cm ² Voltage
(V) efficiency
(cd/A) life span
(T95, hr) Example 74 compound 1-68 compound 2-47 3.56 24.2 195 Example 75 compound 2-51 3.41 24.1 183 Example 76 compound 1-70 compound 2-54 3.55 24.2 196 Example 77 compound 2-56 3.42 24.3 199 Example 78 compound 2-59 3.4 25.6 181 Example 79 compound 1-75 compound 2-1 3.49 24.1 185 Example 80 compound 2-61 3.35 24.2 186 Example 81 compound 2-63 3.31 25.3 187 Example 82 compound 1-79 compound 2-48 3.32 25.0 190 Example 83 compound 2-27 3.43 25.2 198 Example 84 compound 2-59 3.35 25.1 189

1st host 2nd host @10 mA/cm ² @20 mA/cm ² Voltage
(V) efficiency
(cd/A) life span
(T95, hr) Comparative Example 1 compound 1-1 - 3.94 17.4 96 Comparative Example 2 compound 1-2 - 3.92 18.6 94 Comparative Example 3 Compounds 1-6 - 3.93 18.2 95 Comparative Example 4 Compounds 1-20 - 3.87 19.6 105 Comparative Example 5 compound 1-45 - 3.86 19.7 100 Comparative Example 6 compound 1-54 - 3.85 19.1 103 Comparative Example 7 - Compounds 2-4 3.87 19.5 98 Comparative Example 8 - Compounds 2-14 3.88 19.6 99 Comparative Example 9 - compound 2-25 3.89 19.1 105 Comparative Example 10 - Compounds 2-35 3.86 19.5 102 Comparative Example 11 - compound 2-42 3.85 19.6 100 Comparative Example 12 compound 2-57 3.92 19.9 96

As shown in Tables 1 to 7, organic light emitting devices of Examples using the materials represented by Chemical Formulas 1 and 2 together as host materials of the light emitting layer are comparative examples using only one of the compounds represented by Chemical Formulas 1 and 2. Compared to the organic light emitting device, it exhibited excellent driving voltage, luminous efficiency, and lifespan characteristics.

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

Claims (11)

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

In Formula 1,
Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C _6-60 aryl; Or a C _2-60 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O and S, but Ar ₁ and Ar ₂ one of which is substituted or unsubstituted C _6-60 aryl, and at least one of Ar ₁ and Ar ₂ is benzo[c]phenanthrenyl, chrysenyl, fluoranthenyl, or benzonaphthofuranyl, wherein the benzo[c]phenanthrenyl, chrysenyl, fluoranthenyl, or benzonaphthofuranil is unsubstituted or substituted with one or more deuterium;
L ₁ to L ₃ are each independently a single bond; or a substituted or unsubstituted C _6-60 arylene;
R ₁ is hydrogen; heavy hydrogen; Substituted or unsubstituted C _6-60 aryl; Or a C _2-60 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O and S,
a is an integer from 0 to 7;
[Formula 2]

In Formula 2,
X' is O or S;
Any one of R' ₁ to R' ₁₀ is connected to the following Formula 2A, the others are hydrogen or deuterium,
[Formula 2A]

In Formula 2A
L' ₁ to L' ₃ are each independently a single bond; or a substituted or unsubstituted C _6-60 arylene;
Ar' ₁ and Ar' ₂ are each independently phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, dimethylfluorenyl, spirobifluorenyl, dibenzofuranyl, dibenzothiophenyl, or phenyl carbazolyl, wherein Ar' ₁ and Ar' ₂ are each independently unsubstituted or substituted.
According to claim 1,
The compound represented by Formula 1 is represented by any one of the following Formulas 1-1 to 1-3,
Organic Light-Emitting Elements:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In Formulas 1-1 to 1-3,
Ar ₁ and Ar ₂ and L ₁ to L ₃ are as defined in claim 1,
R ₁ is deuterium; Substituted or unsubstituted C _6-60 aryl; Or a C _2-60 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O and S.
According to claim 1,
Ar ₁ and Ar ₂ are each independently selected from phenyl, triphenylsilyl phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, chrysenyl, benzo[c]phenanthrenyl, fluoranthenyl, dibenzofuran Ranyl, dibenzothiophenyl, or benzonaphthofuranyl, wherein Ar ₁ and Ar ₂ are each independently unsubstituted or substituted with one or more deuterium atoms,
One of Ar ₁ and Ar ₂ is phenyl, triphenylsilyl phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, chrysenyl, or fluoranthenyl, and the phenyl, triphenylsilyl phenyl, biphenyl lyl, terphenylyl, naphthyl, phenanthrenyl, chrysenyl, or fluoranthenyl is unsubstituted or substituted with at least one deuterium;
At least one of Ar ₁ and Ar ₂ is benzo[c]phenanthrenyl, chrysenyl, fluoranthenyl, or benzonaphthofuranil, and the benzo[c]phenanthrenyl, chrysenyl, fluoranthenyl, or benzo Naphthofuranil is unsubstituted or substituted with at least one deuterium,
organic light emitting device.
According to claim 1,
L ₁ to L ₃ are each independently a single bond, phenylene, biphenyldiyl, or naphthalenediyl;
The phenylene, biphenyldiyl and naphthalenediyl are each independently unsubstituted or substituted with one or more deuterium,
organic light emitting device.
According to claim 1,
R ₁ is each independently selected from hydrogen, deuterium, phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, triphenylenyl, naphthyl phenyl, phenyl naphthyl, fluoranthenyl, dibenzofuranyl, di benzothiophenyl, benzonaphthofuranil, or benzonaphthothiophenyl;
The above phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, triphenylenyl, naphthyl phenyl, phenyl naphthyl, fluoranthenyl, dibenzofuranyl, dibenzothiophenyl, benzonaphthofuranil and benzo Each naphthothiophenyl is independently unsubstituted or substituted with at least one deuterium,
organic light emitting device.
According to claim 1,
a is 0 or 1;
organic light emitting device.
According to claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of
Organic Light-Emitting Elements:

.
According to claim 1,
Formula 2A is connected to any one of R' ₁ , R' ₂ , R' ₄ , R' ₅ and R' ₈ to R' ₁₀ of Formula 2,
organic light emitting device.
According to claim 1,
L' ₁ to L' ₃ are each independently a single bond, phenylene, biphenylyldiyl, naphthalenediyl, or dimethylfluorenediyl;
The phenylene, biphenyldiyl, naphthalenediyl and dimethylfluorenediyl are each independently unsubstituted or substituted with one or more deuterium,
organic light emitting device.
According to claim 1,
Ar' ₁ and Ar' ₂ are each independently selected from phenyl, triphenylsilyl phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, dimethylfluorenyl, spirobifluorenyl, dibenzofuranyl, dibenzothiophenyl, or phenyl carbazolyl;
Wherein Ar' ₁ and Ar' ₂ are each independently unsubstituted or substituted with one or more deuterium,
organic light emitting device.
According to claim 1,
The compound represented by Formula 2 is any one selected from the group consisting of
Organic Light-Emitting Elements:

.

Images