KR20210033928A - Novel hetero-cyclic compound and organic light emitting device comprising the same - Google Patents

Abstract

The present invention provides a novel heterocyclic compound and an organic light emitting device using the same. The compound represented by chemical formula 1 can be used as a material for an organic material layer of the organic light emitting device, and thus can improve efficiency, lower driving voltage, and/or improve lifespan characteristics in the organic light emitting device.

Description

Novel hetero-cyclic compound and organic light emitting device comprising the same

The present invention relates to a novel heterocyclic compound and an organic light emitting device including the same.

In general, the organic light emission phenomenon refers to a phenomenon in which electrical energy is converted into light energy by using an organic material. Organic light-emitting devices using the organic light-emitting phenomenon have a wide viewing angle, excellent contrast, and fast response time, and are excellent in luminance, driving voltage, and response speed characteristics, so many studies are being conducted.

An organic light-emitting device generally has a structure including an anode and a cathode, and an organic material layer between the anode and the cathode. The organic material layer is often made of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light-emitting device.For example, it may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. In the structure of such an 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 excitons are formed when the injected holes and electrons meet. When it falls back to the ground, it glows.

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

Korean Patent Publication No. 10-2000-0051826

The present invention relates to a novel heterocyclic compound and an organic light emitting device including the same.

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

[Formula 1]

In Formula 1,

X ₁ to X ₃ are each independently N or CR ₈ , but at least any one is N,

Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted aryl having 6 to 60 carbon atoms; Or substituted or unsubstituted O, N, Si and S is a heteroaryl having 2 to 60 carbon atoms including one or more of,

R ₁ to R ₈ are each independently hydrogen; heavy hydrogen; halogen; Hydroxy; Nitrile; Nitro; Amino; Substituted or unsubstituted C2 to C60 alkyl; Substituted or unsubstituted 2 to 60 alkoxy; Substituted or unsubstituted 2 to 60 alkenyl; Substituted or unsubstituted 6 to 60 aryl; Or substituted or unsubstituted O, N, Si and S is a heteroaryl having 2 to 60 carbon atoms including one or more of,

One of A and B is a substituent represented by the following formula 1-1, and the other is hydrogen or deuterium,

[Formula 1-1]

In Formula 1-1,

R ₉ to R ₁₃ are each independently hydrogen; heavy hydrogen; halogen; Hydroxy; Nitrile; Nitro; Amino; Substituted or unsubstituted C2 to C60 alkyl; Substituted or unsubstituted 2 to 60 alkoxy; Substituted or unsubstituted 2 to 60 alkenyl; Substituted or unsubstituted 6 to 60 aryl; A substituted or unsubstituted heteroaryl having 2 to 60 carbon atoms including one or more of O, N, Si and S, or R ₉ to R ₁₂ are bonded to adjacent groups to form a fused ring

n is an integer from 1 to 6.

In addition, the present invention is a first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes a compound represented by Formula 1 do.

The compound represented by Chemical Formula 1 may be used as a material for an organic material layer of an organic light-emitting device, and may improve efficiency, low driving voltage, and/or lifetime characteristics in the organic light-emitting device. In particular, the compound represented by Formula 1 may be used as a hole injection, hole transport, hole injection and transport, light emission, electron transport, or electron injection material.

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

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

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

및

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

And

Means a bond connected to another substituent.

In the present specification, the term "substituted or unsubstituted" refers to 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; Alkyl sulfoxy group; Arylsulfoxy group; Silyl group; Boron group; Alkyl group; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; Aralkenyl group; Alkylaryl group; Alkylamine group; Aralkylamine group; Heteroarylamine group; Arylamine group; Arylphosphine group; Or it means substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing one or more of N, O, and S atoms, or substituted or unsubstituted with two or more substituents connected among the above-exemplified substituents. . For example, "a substituent to which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent to 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 compound having the following structure, but is not limited thereto.

In the present specification, the ester group may be substituted with a C1-C25 linear, branched or cyclic alkyl group or an aryl group having 6 to 25 carbon atoms in the oxygen of the ester group. Specifically, it may be a compound 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 it is preferably 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

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

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, and the like, but is not limited thereto.

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

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. 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, cycloheptylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but are not limited thereto.

In the present specification, the alkenyl group may be a linear or branched chain, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to an exemplary 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, and the like, but are 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 cycloalkyl group has 3 to 20 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. 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 is preferably 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to an exemplary embodiment, the aryl group has 6 to 30 carbon atoms. According to an exemplary embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a phenyl group, a biphenyl group, or a terphenyl group, but the monocyclic aryl group is not limited thereto. The polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, 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,

Can be, 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 a heterogeneous element, and the number of carbon atoms is not particularly limited, but it is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, acridyl group , Pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group , Carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, isoxazolyl group, thiiadia There are a zolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but are not limited thereto.

In the present specification, the aryl group among the aralkyl group, aralkenyl group, alkylaryl group, and arylamine group is the same as the example of the aryl group described above. In the present specification, the alkyl group among the aralkyl group, the alkylaryl group and the alkylamine group is the same as the example of the aforementioned alkyl group. In the present specification, for heteroaryl among heteroarylamines, the description of the aforementioned heterocyclic group may be applied. In the present specification, the alkenyl group of the aralkenyl group is the same as the example 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 aforementioned heterocyclic group 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 bonding of two substituents. In the present specification, the heterocycle is not a monovalent group, and the description of the aforementioned heterocyclic group may be applied, except that two substituents are bonded to each other and formed.

Preferably, Formula 1 may be any one selected from compounds represented by the following Formulas 1-A and 1-B.

In Formulas 1-A and 1-B,

Description of X ₁ , X ₂ , X ₃ , Ar ₁ , Ar ₂ , and R ₉ to R ₁₂ are as defined above.

Preferably, all of X ₁ to X ₃ are N.

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

Preferably, Formula 1-1 may be any one selected from the group consisting of the following compounds.

Preferably, the compound represented by Formula 1 may be any one selected from the group consisting of the following compounds.

The compound represented by Chemical Formula 1 can be prepared by a manufacturing method such as the following Scheme 1 or 2.

[Scheme 1]

[Scheme 2]

In Reaction Schemes 1 and 2, the definitions other than X are as defined above, and X is halogen and more preferably bromo or chloro. The reaction is a Suzuki coupling reaction, 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 the manufacturing examples to be described later.

In addition, the present invention provides an organic light-emitting device including the compound represented by Formula 1 above. For example, the present invention provides a first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes a compound represented by Formula 1 do.

The organic material layer of the organic light emitting device of the present invention may have a single-layer structure, but may have a multilayer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like as an organic material layer. However, the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic layers.

In addition, the organic material layer may include a hole injection layer, a hole transport layer, an electron blocking layer, or a layer for simultaneously injecting and transporting holes, and the hole injection layer, a hole transport layer, an electron blocking layer, or a hole injecting and transporting at the same time. The layer includes the compound represented by Chemical Formula 1.

In addition, the organic material layer may include an emission layer, and the emission layer includes a compound represented by Formula 1 above.

Specifically, the emission layer may include a host material.

In this case, the host material may include the compound represented by Formula 1.

In addition, the organic material layer may include an electron transport layer, an electron injection layer, or a layer that simultaneously injects and transports electrons, and the electron transport layer, an electron injection layer, or a layer that simultaneously injects and transports electrons is represented by Formula 1 above. Contains compounds.

In addition, the electron transport layer, the electron injection layer, or the layer that simultaneously transports and injects electrons includes the compound represented by Formula 1 above.

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

In addition, the organic light-emitting device according to the present invention may be a normal type organic light-emitting device in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate. In addition, the organic light-emitting device according to the present invention may be an inverted type organic light-emitting device in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate. For example, the structure of an organic light emitting device according to an embodiment of the present invention is illustrated in FIGS. 1 and 2.

1 shows an example of an organic light-emitting device comprising a substrate 1, an anode 2, a light-emitting layer 3, and a cathode 4. In such a structure, the compound represented by Formula 1 may be included in the emission layer.

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 a cathode 4 are shown as an example of an organic light-emitting device. In such a structure, the compound represented by Formula 1 may be included in at least one of the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the hole blocking layer, and the electron injection and transport layer.

The organic light-emitting device according to the present invention may be manufactured by materials and methods known in the art, except that at least one of the organic material layers includes the compound represented by Chemical Formula 1. In addition, when the organic light-emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.

For example, the organic light emitting device according to the present invention may be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate. At this time, using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, the anode is formed by depositing a metal or a conductive metal oxide or an alloy thereof on the substrate. And, after forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer thereon, it can be prepared 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, an organic material layer, and an anode material on a substrate.

In addition, the compound represented by Formula 1 may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light emitting device. Here, the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, roll coating, and the like, but is not limited thereto.

In addition to such a method, an organic light emitting device may be manufactured by sequentially depositing an organic material layer and an anode material from a cathode material on a substrate (WO 2003/012890). However, the manufacturing method is not limited thereto.

For example, the first electrode is an anode, the second electrode is a cathode, or the first electrode is a cathode, and the second electrode is an anode.

As the anode material, a material having a large work function is preferable so that holes can be smoothly injected into the organic material 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;} Poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), conductive polymers such as polypyrrole and polyaniline, and the like, but are not limited thereto.

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

The hole injection material is a layer that injects holes from the electrode, and the hole injection material has the ability to transport holes, so that it has a hole injection effect at the anode, an excellent hole injection effect for the light emitting layer or the light emitting material, and is generated in the light emitting layer. A compound that prevents the excitons from moving to the electron injection layer or the electron injection material and has excellent thin film formation ability is preferable. It is preferable that the HOMO (highest occupied molecular orbital) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of hole injection materials include metal porphyrin, oligothiophene, arylamine-based organic substances, hexanitrile hexaazatriphenylene-based organic substances, quinacridone-based organic substances, and perylene-based organic substances. Organic substances, anthraquinone, polyaniline, and polythiophene-based conductive polymers, but are not limited thereto.

The hole transport layer is a layer that receives holes from the hole injection layer and transports holes to the light emitting layer.As a hole transport material, a material capable of transporting holes from the anode or the hole injection layer to the light emitting layer and having high mobility for holes This is suitable. Specific examples include an arylamine-based organic material, a conductive polymer, and a block copolymer including a conjugated portion and a non-conjugated portion, but are not limited thereto.

As the light-emitting material, a material capable of emitting light in a visible light region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable. Specific examples of 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compound; Benzoxazole, benzthiazole, and benzimidazole-based compounds; Poly(p-phenylenevinylene) (PPV)-based polymer; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited thereto.

The emission layer may include a host material and a dopant material. Host materials include condensed aromatic ring derivatives or heterocyclic-containing compounds. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Dopant materials include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, periflanthene and the like having an arylamino group, and the styrylamine compound is substituted or unsubstituted As a compound in which at least one arylvinyl group is substituted on the arylamine, one or two or more substituents selected from the group consisting of aryl group, silyl group, alkyl group, cycloalkyl group, and arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, and styryltetraamine, but are not limited thereto. In addition, examples of the metal complex include, but are not limited to, an iridium complex and a platinum complex.

The electron transport material is a layer that receives electrons from the electron injection layer and transports electrons to the emission layer. The electron transport material is a material that can transfer electrons from the cathode to the emission layer, and has high mobility for electrons. This is suitable. Specific examples include Al complex 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 that have a low work function and are followed by an aluminum layer or a silver layer. Specifically, they are cesium, barium, calcium, ytterbium, and samarium, and in each case an aluminum layer or a silver layer follows.

The electron injection layer is a layer that injects electrons from the electrode, has the ability to transport electrons, has an electron injection effect from the cathode, an excellent electron injection effect for the light emitting layer or the light emitting material, and hole injection of excitons generated in the light emitting layer A compound that prevents migration to the layer and is excellent in thin film forming ability is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, and their derivatives, metals Complex compounds and nitrogen-containing 5-membered ring derivatives, but are not limited thereto.

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

The organic light-emitting device according to the present invention may be a top emission type, a bottom emission type, or a double-sided emission type depending on the material used.

In addition, the compound represented by Formula 1 may be included in an organic solar cell or an organic transistor in addition to the organic light emitting device.

Hereinafter, preferred embodiments are presented to aid in understanding the invention. However, the following examples are only for illustrating the present invention, and the present invention is not limited thereto.

Preparation Example 1: Preparation of compound a

(1) Preparation of compound a-1

Naphthalen-2-amine (naphthalen-2-amine, 200.0 g, 1.0 eq), 1-bromo-2-iodobenzene (1-bromo-2-iodobenzene, 395.1 g, 1.0 eq), sodium tert-butoxide (NaOt-Bu, 268.4 g, 2 eq), palladium acetate (Pd(OAc) ₂ , 3.13 g, 0.01 eq), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (4,5 -Bis (diphenylphosphino)-9,9-dimethylxanthene, Xantphos, 16.1 g, 0.02 eq) and toluene (Toluene, 2 L) dissolved in reflux and stirred at 60 ℃. When the reaction was completed after 2 hours, sodium tert-butoxide was removed by silica filter, and the solvent was removed by distillation under reduced pressure. After dissolving in chloroform, washing with water, magnesium sulfate and acid clay were added, stirred, filtered, and concentrated under reduced pressure. Thereafter, compound a-1 was obtained through column chromatography under the condition of ethyl acetate:hexane = 1:50. (316.5 g, yield 76%, MS: [M+H] ⁺ =299)

(2) Preparation of compound a(5H-benzo[b]carbazole)

Compound a-1 (316.5 g, 1.0 eq) bis(tri-tert-butylphosphine) palladium(0) (Pd(t-Bu ₃ P) ₂ , 5.42 g, 0.01 eq), potassium carbonate (K ₂ CO ₃ , 293.4 g, 2.00 eq) was added to diethylacetamide (DMAc, 3 L), and the mixture was refluxed and stirred. After 3 hours, the reactant was poured into water to crystallize and then filtered to obtain a solid. The filtered solid is completely dissolved in 1,2-dichlorobenzene (1 L) at 100 ℃, washed with water, and then added magnesium sulfate and acid clay to the solution containing the product, stirred, and filtered. And concentrated under reduced pressure. After purification by column chromatography to obtain a compound a (5H-benzo[b]carbazole). (131.4 g, yield 57%, MS: [M+H] ⁺ =218)

Preparation Example 2: Preparation of compound b

Using 2-bromo-1-iodonaphthalene instead of 1-bromo-2-idobenzene, the following compound b(13H-dibenzo[ a,h]carbazole) was obtained.

Preparation Example 3: Preparation of compound c

Using 2,3-dibromonaphthalene instead of 1-bromo-2-idobenzene, the following compound c(6H-dibenzo[b,h] was used in the same manner as the preparation method of compound a) carbazole) was obtained.

Preparation Example 4: Preparation of compound d

Using 1-bromo-2-iodonaphthalene instead of 1-bromo-2-iodonaphthalene, the following compound d(7H-dibenzo[ b,g]carbazole) was obtained.

Preparation Example 5: Preparation of Compound E

(1) Preparation of compound E-3

1-bromo-6-chloronaphthalen-2-ol (1-bromo-6-chloronaphthalen-2-ol, 100.0 g, 1.0 eq), (2-fluorophenyl) boronic acid ((2-fluorophenyl) boronic acid , 65.2 g, 1.2 eq), calcium carbonate (K ₂ CO ₃ , 131 g, 3.0 eq) _{, tetrakis(triphenylphosphine)palladium(0) (Pd(PPh 3} ) ₄ , Tetrakis(triphenylphosphine)palladium(0) ), 13.5 g, 0.03 eq) were dissolved in tetrahydrofuran (THF, 1 L) and water (300 ml), followed by heating and stirring at 80°C. After 2 hours, when the reaction was completed, the organic solvent layer was separated, magnesium sulfate and acid clay were added, stirred, filtered, and concentrated under reduced pressure. This was subjected to column chromatography to obtain compound E-3. (86.8 g, yield 82%, MS: [M+H] ⁺ =224)

(2) Preparation of compound E-2

Compound E-3 (100.2 g) and calcium carbonate (K ₂ CO ₃ , 132.2 g, 3 eq) were added to diethylacetamide (DMAc, 1 L) and heated and stirred at 80°C. When the reaction was completed after 1 hour, the reaction product was poured into water (2 L) to drop crystals and filtered to obtain a solid. The obtained solid was dissolved in toluene (1 L) and washed with water. The organic solvent layer was separated, magnesium sulfate and acid clay were added, stirred, and filtered. Ethyl acetate was poured, leaving only 20% of the filtered solvent to drop crystals and filtered. Through this, compound E-2 was obtained. (62.0 g, yield 77%, MS: [M+H] ⁺ =253)

(3) Preparation of compound E-1

After dissolving compound E-2 (68.8 g) in chloroform (CHCl ₃ , 1 L), dibromine (Br ₂ , 15.7 ml, 1.1 eq) was slowly added while stirring. When the reaction was completed after 1 hour, the _{mixture was washed with sodium sulfite (Na 2} SO ₃ ) aqueous solution, and the organic solvent layer was separated, magnesium sulfate and acid clay were added, stirred, and filtered. Ethyl acetate was poured, leaving only 20% of the filtered solvent to drop crystals and filtered. Through this, compound E-1 was obtained. (51.6 g, yield 56%, MS: [M+H] ⁺ =332)

(4) Preparation of compound E

Compound E-1 (51.6 g, 1.0 eq), bis (pinacolato) diboron, 70.5 g, 1.2 eq), (1,1'-bis (diphenylphosphino) ferrocene) palladium Dichloride (Pd(dppf)Cl ₂ , (1,1'-Bis(diphenylphosphino)ferrocene)palladium dichloride, 3.38 g, 0.02 eq) and potassium acetate (KOAc, potassium acetate, 45.4 g, 2.00 eq) were added to 1,4-dioxane (1,4-Dioxnae, 600 ml), followed by heating and stirring at 100°C. When the reaction was completed after 3 hours, the solvent was removed under reduced pressure. The filtered solid was completely dissolved in chloroform (CHCl ₃ ), washed with water, and the solution in which the product was dissolved was concentrated under reduced pressure to remove about 80% of the solvent. Ethanol was added to this in a reflux state, and the crystals were dropped, cooled, and filtered to obtain compound E. (70.1 g, yield 80%, MS: [M+H] ⁺ =379)

Preparation Example 6: Preparation of Compound F

Using 1-bromo-7-chloronaphthalen-2-ol instead of 1-bromo-6-chloronaphthalen-2-ol, the following compound F was obtained in the same manner as in the preparation method of compound E. (MS: [M+H] ⁺ =379)

An intermediate for preparing compounds 1 to 55 of Examples 1 to 55 below by reacting the compounds prepared in Preparation Examples 5 and 6 with an intermediate containing triazine through a Suzuki coupling reaction Each was used as a compound.

Example 1: Preparation of compound 1

In a nitrogen atmosphere, sub1 (20 g, 41.3 mmol), compound a (9.8 g, 45.5 mmol) and sodium tert-butoxide (11.9 g, 124 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (105 mg, 0.2 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 1. (13.7 g, yield 50%, MS: [M+H] ⁺ =665)

Example 2: Preparation of compound 2

In a nitrogen atmosphere, sub2 (20 g, 41.3 mmol), compound a (9.8 g, 45.5 mmol) and sodium tert-butoxide (11.9 g, 124 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (105 mg, 0.2 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 2. (17.0 g, yield 62%, MS: [M+H] ⁺ =665)

Example 3: Preparation of compound 3

In a nitrogen atmosphere, sub3 (20 g, 41.3 mmol), compound a (11 g, 41.2 mmol) and sodium tert-butoxide (10.8 g, 112 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (96 mg, 0.19 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 3. (16.0 g, yield 60%, MS: [M+H] ⁺ =715)

Example 4: Preparation of compound 4

In a nitrogen atmosphere, sub4 (20 g, 31.5 mmol), compound a (7.5 g, 34.7 mmol) and sodium tert-butoxide (9.1 g, 94.6 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (105 mg, 0.2 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 4. (15.4 g, yield 60%, MS: [M+H] ⁺ =815)

Example 5: Preparation of compound 5

In a nitrogen atmosphere, sub5 (20 g, 32.8 mmol), compound a (7.8 g, 36.1 mmol) and sodium tert-butoxide (9.5 g, 98.3 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (84 mg, 0.16 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 5. (13.5 g, yield 52%, MS: [M+H] ⁺ =791)

Example 6: Preparation of compound 6

In a nitrogen atmosphere, sub6 (20 g, 33.2 mmol), compound a (7.9 g, 36.6 mmol) and sodium tert-butoxide (9.6 g, 99.7 mmol) were added to xylene (200 ml) and stirred. Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (85 mg, 0.16 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 6. (15.2 g, yield 58%, MS: [M+H] ⁺ =715)

Example 7: Preparation of compound 7

In a nitrogen atmosphere, sub7 (20 g, 34.8 mol), compound a (8.3 g, 38.3 mmol) and sodium tert-butoxide (10.0 g, 104 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (89 mg, 0.17 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 7. (16.8 g, yield 61%, MS: [M+H] ⁺ =755)

Example 8: Preparation of compound 8

In a nitrogen atmosphere, sub8 (20 g, 32.0 mmol), compound a (7.7 g, 35.3 mmol) and sodium tert-butoxide (9.2 g, 96.1 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (81.8 mg, 0.16 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 8. (16.5 g, yield 65%, MS: [M+H] ⁺ =805)

Example 9: Preparation of compound 9

In a nitrogen atmosphere, sub9 (20 g, 30.8 mmol), compound a (7.4 g, 33.8 mmol) and sodium tert-butoxide (8.9 g, 92.3 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (78.6 mg, 0.15 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 9. (14.6 g, yield 60%, MS: [M+H] ⁺ =831)

Example 10: Preparation of compound 10

In a nitrogen atmosphere, sub10 (20 g, 29.0 mmol), compound a (6.9 g, 31.9 mmol) and sodium tert-butoxide, 8.4 g, 86.9 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (74 mg, 0.15 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 10. (12.6 g, yield 55%, MS: [M+H] ⁺ =871)

Example 11: Preparation of compound 11

In a nitrogen atmosphere, sub11 (20 g, 30.0 mmol), compound a (7.2 g, 33.0 mmol) and sodium tert-butoxide (8.7 g, 90.1 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (76.7 mg, 0.15 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 11. (13.3 g, yield 56%, MS: [M+H] ⁺ =847)

Example 12: Preparation of compound 12

In a nitrogen atmosphere, sub12 (20 g, 30.8 mmol), compound a (7.4 g, 33.9 mmol) and sodium tert-butoxide (8.9 g, 92.4 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (78.7 mg, 0.15 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 12. (11.5 g, yield 47%, MS: [M+H] ⁺ =830)

Example 13: Preparation of compound 13

In a nitrogen atmosphere, sub13 (20 g, 29.0 mmol), compound a (6.9 g, 31.8 mmol) and sodium tert-butoxide (8.3 g, 86.9 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (73.9 mg, 0.145 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 13. (15.4 g, yield 59%, MS: [M+H] ⁺ =907)

Example 14: Preparation of compound 14

In a nitrogen atmosphere, sub14 (20 g, 31.3 mmol), compound a (7.5 g, 34.4 mmol) and sodium tert-butoxide (9.0 g, 93.9 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (80 mg, 0.16 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 14. (12.0 g, yield 45%, MS: [M+H] ⁺ =854)

Example 15: Preparation of compound 15

In a nitrogen atmosphere, sub1 (20 g, 41.3 mmol), compound b (12.2 g, 45.5 mmol) and sodium tert-butoxide (11.9 g, 124 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (105 mg, 0.2 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 15. (14.7 g, yield 50%, MS: [M+H] ⁺ =715)

Example 16: Preparation of compound 16

In a nitrogen atmosphere, sub2 (20 g, 41.3 mmol), compound b (12.1 g, 45.5 mmol) and sodium tert-butoxide (11.9 g, 124 mmol) were added to xylene (200 ml) and stirred. Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (105 mg, 0.2 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 16. (15.3 g, yield 52%, MS: [M+H] ⁺ =715)

Example 17: Preparation of compound 17

In a nitrogen atmosphere, sub17 (20 g, 37.5 mmol), compound b (11.0 g, 41.2 mmol) and sodium tert-butoxide (10.8 g, 112 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (95.7 mg, 0.18 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 17. (17.5 g, yield 61%, MS: [M+H] ⁺ =765)

Example 18: Preparation of compound 18

In a nitrogen atmosphere, sub18 (20 g, 32.8 mmol), compound b (9.6 g, 36.1 mmol) and sodium tert-butoxide (9.5 g, 98.3 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (83.7 mg, 0.164 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 18. (15.4 g, yield 56%, MS: [M+H] ⁺ =841)

Example 19: Preparation of compound 19

In a nitrogen atmosphere, sub19 (20 g, 31.4 mmol), compound b (9.2 g, 34.6 mmol) and sodium tert-butoxide (9.1 g, 94.3 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (80.3 mg, 0.157 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 19. (13.6 g, yield 50%, MS: [M+H] ⁺ =868)

Example 20: Preparation of compound 20

In a nitrogen atmosphere, sub20 (20 g, 32.0 mmol), compound b (9.4 g, 35.3 mmol) and sodium tert-butoxide (9.2 g, 96.1 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (8a mg, 0.160 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 20. (15.1 g, yield 55%, MS: [M+H] ⁺ =855)

Example 21: Preparation of compound 21

In a nitrogen atmosphere, sub21 (20 g, 30.8 mmol), compound b (9.0 g, 33.8 mmol) and sodium tert-butoxide (8.9 g, 92.3 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (78 mg, 0.154 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 21. (14.3 g, yield 53%, MS: [M+H] ⁺ =882)

Example 22: Preparation of compound 22

In a nitrogen atmosphere, sub22 (20 g, 29.0 mmol), compound b (8.5 g, 31.9 mmol) and sodium tert-butoxide (8,4 g, 86.9 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (74 mg, 0.145 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 22. (16.0 g, yield 60%, MS: [M+H] ⁺ =922)

Example 23: Preparation of compound 23

In a nitrogen atmosphere, sub23 (20 g, 27.6 mmol), compound b (8.1 g, 30.3 mmol) and sodium tert-butoxide (8.0 g, 82.7 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (70.4 mg, 0.138 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 23. (13.7 g, yield 52%, MS: [M+H] ⁺ =957)

Example 24: Preparation of compound 24

In a nitrogen atmosphere, sub1 (20 g, 41.3 mmol), compound c (12.2 g, 45.5 mmol) and sodium tert-butoxide (11.9 g, 124 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (105 mg, 0.207 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 24. (15.3 g, yield 52%, MS: [M+H] ⁺ =715)

Example 25: Preparation of compound 25

In a nitrogen atmosphere, sub2 (20 g, 41.3 mmol), compound c (12.2 g, 45.5 mmol) and sodium tert-butoxide (11.9 g, 124 mmol) were added to xylene (200 ml) and stirred. Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (105 mg, 0.207 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 25. (19.8 g, yield 67%, MS: [M+H] ⁺ =715)

Example 26: Preparation of compound 26

In a nitrogen atmosphere, sub3 (20 g, 37.5 mmol), compound c (11.0 g, 41.2 mmol) and sodium tert-butoxide (10.8 g, 112 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (95 mg, 0.187 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 26. (16.6 g, yield 58%, MS: [M+H] ⁺ =765)

Example 27: Preparation of compound 27

In a nitrogen atmosphere, sub27 (20 g, 35.7 mmol), compound c (10.5 g, 39.3 mmol) and sodium tert-butoxide (10.3 g, 107 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (91.2 mg, 0.179 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 27. (16.6 g, yield 59%, MS: [M+H] ⁺ =791)

Example 28: Preparation of compound 28

In a nitrogen atmosphere, sub28 (20 g, 31.5 mmol), compound c (9.3 g, 34.7 mmol) and sodium tert-butoxide (9.1 g, 94.6 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (80.5 mg, 0.158 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 28. (12.8 g, yield 46%, MS: [M+H] ⁺ =886)

Example 29: Preparation of compound 29

In a nitrogen atmosphere, sub29 (20 g, 32.0 mmol), compound c (9.4 g, 35.3 mmol) and sodium tert-butoxide (9.2 g, 96.1 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (81.8 mg, 0.160 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 29. (13.9 g, yield 51%, MS: [M+H] ⁺ =855)

Example 30: Preparation of compound 30

In a nitrogen atmosphere, sub30 (20 g, 30.8 mmol), compound c (9.0 g, 33.8 mmol) and sodium tert-butoxide (8.9 g, 92.3 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (78.6 mg, 0.154 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 30. (13.5 g, yield 50%, MS: [M+H] ⁺ =882)

Example 31: Preparation of compound 31

In a nitrogen atmosphere, sub31 (20 g, 33.9 mmol), compound c (10.0 g, 37.3 mmol) and sodium tert-butoxide (9.8 g, 101 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (86 mg, 0.169 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 31. (13.9 g, yield 50%, MS: [M+H] ⁺ =821)

Example 32: Preparation of compound 32

In a nitrogen atmosphere, sub32 (20 g, 31.2 mmol), compound c (9.2 g, 34.4 mmol) and sodium tert-butoxide (9.0 g, 93.7 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (79 mg, 0.156 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 32. (14.7 g, yield 54%, MS: [M+H] ⁺ =872)

Example 33: Preparation of compound 33

In a nitrogen atmosphere, sub12 (20 g, 30.8 mmol), compound c (9.1 g, 33.9 mmol) and sodium tert-butoxide (8.9 g, 92.4 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (78 mg, 0.154 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 33. (13.5 g, yield 50%, MS: [M+H] ⁺ =881)

Example 34: Preparation of compound 34

In a nitrogen atmosphere, sub34 (20 g, 28.6 mmol), compound c (8.4 g, 31.5 mmol) and sodium tert-butoxide (8.2 g, 85.8 mmol) were added to xylene (200 ml) and stirred. Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (73 mg, 0.143 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 34. (13.3 g, yield 50%, MS: [M+H] ⁺ =931)

Example 35: Preparation of compound 35

In a nitrogen atmosphere, sub35 (20 g, 27.6 mmol), compound c (8.1 g, 30.3 mmol) and sodium tert-butoxide (8.0 g, 82.7 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (70.4 mg, 0.138 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 35. (13.2 g, yield 50%, MS: [M+H] ⁺ =857)

Example 36: Preparation of compound 36

In a nitrogen atmosphere, sub36 (20 g, 30.8 mmol), compound c (9.1 g, 33.9 mmol) and sodium tert-butoxide (8.9 g, 92.4 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (79 mg, 0.154 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 36. (11.9 g, yield 44%, MS: [M+H] ⁺ =881)

Example 37: Preparation of compound 37

In a nitrogen atmosphere, sub1 (20 g, 41.3 mmol), compound d (12.2 g, 45.5 mmol) and sodium tert-butoxide (11.9 g, 124 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (105 mg, 0.207 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 37. (13.6 g, yield 46%, MS: [M+H] ⁺ =715)

Example 38: Preparation of compound 38

In a nitrogen atmosphere, sub2 (20 g, 41.3 mmol), compound d (6.4 g, 45.5 mmol) and sodium tert-butoxide (11.9 g, 124 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (105 mg, 0.207 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 38. (15.3 g, yield 52%, MS: [M+H] ⁺ =715)

Example 39: Preparation of compound 39

In a nitrogen atmosphere, sub39 (20 g, 34.2 mmol), compound d (10.1 g, 37.7 mmol) and sodium tert-butoxide (9.9 g, 102 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (87 mg, 0.171 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 39. (14.2 g, yield 51%, MS: [M+H] ⁺ =815)

Example 40: Preparation of compound 40

In a nitrogen atmosphere, sub40 (20 g, 31.5 mmol), compound d (9.3 g, 34.7 mmol) and sodium tert-butoxide (9.1 g, 94.6 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (80 mg, 0.158 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 40. (12.8 g, yield 47%, MS: [M+H] ⁺ =865)

Example 41: Preparation of compound 41

In a nitrogen atmosphere, sub41 (20 g, 31.4 mmol), compound d (9.2 g, 34.6 mmol) and sodium tert-butoxide (9.1 g, 94.3 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (80 mg, 0.157 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 41. (14.9 g, yield 55%, MS: [M+H] ⁺ =868)

Example 42: Preparation of compound 42

In a nitrogen atmosphere, sub42 (20 g, 34.8 mmol), compound d (10.2 g, 38.3 mmol) and sodium tert-butoxide (10.0 g, 104 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (89 mg, 0.174 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 42. (14.6 g, yield 52%, MS: [M+H] ⁺ =805)

Example 43: Preparation of compound 43

In a nitrogen atmosphere, sub43 (20 g, 32.06 mmol), compound d (9.4 g, 35.3 mmol) and sodium tert-butoxide (9.2 g, 96.1 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (81 mg, 0.16 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 43. (13.4 g, yield 49%, MS: [M+H] ⁺ =855)

Example 44: Preparation of compound 44

In a nitrogen atmosphere, sub44 (20 g, 33.9 mmol), compound d (10.0 g, 37.3 mmol) and sodium tert-butoxide (9.8 g, 101 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (86 mg, 0.169 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 44. (15.3 g, yield 55%, MS: [M+H] ⁺ =821)

Example 45: Preparation of compound 45

In a nitrogen atmosphere, sub45 (20 g, 30.0 mmol), compound d (8.8 g, 33.0 mmol) and sodium tert-butoxide (8.7 g, 90.1 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (76 mg, 0.15 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 45. (14.8 g, yield 55%, MS: [M+H] ⁺ =898)

Example 46: Preparation of compound 46

In a nitrogen atmosphere, sub46 (20 g, 26.7 mmol), compound d (7.8 g, 29.4 mmol) and sodium tert-butoxide (7.7 g, 80.1 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (68 mg, 0.133 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 46. (13.1 g, yield 50%, MS: [M+H] ⁺ =981)

Example 47: Preparation of compound 47

In a nitrogen atmosphere, sub47 (20 g, 27.6 mmol), compound d (8.1 g, 30.3 mmol) and sodium tert-butoxide (8.0 g, 82.7 mmol) were added to xylene (200 ml) and stirred and Ryu said. After this, bis(tri-tert-butylphosphine)palladium(0) (70 mg, 0.138 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 47. (14.7 g, yield 56%, MS: [M+H] ⁺ =957)

Example 48: Preparation of compound 48

In a nitrogen atmosphere, sub48 (20 g, 27.6 mmol), compound d (8.1 g, 30.3 mmol) and sodium tert-butoxide (8.0 g, 82.7 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (70 mg, 0.138 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 48. (16.1 g, yield 61%, MS: [M+H] ⁺ =957)

Example 49: Preparation of compound 49

In a nitrogen atmosphere, sub49 (20 g, 30.1 mmol), compound a (7.2 g, 33.1 mmol) and sodium tert-butoxide (8.7 g, 90.3 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (77 mg, 0.151 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 49. (16.8 g, yield 66%, MS: [M+H] ⁺ =845)

Example 50: Preparation of compound 50

In a nitrogen atmosphere, sub50 (20 g, 29.4 mmol), compound a (7.0 g, 32.3 mmol) and sodium tert-butoxide (8.5 g, 88.2 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (75 mg, 0.147 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 50. (13.1 g, yield 52%, MS: [M+H] ⁺ =861)

Example 51: Preparation of compound 51

In a nitrogen atmosphere, sub51 (20 g, 27.1 mmol), compound a (6.5 g, 29.8 mmol) and sodium tert-butoxide (7.8 g, 81.2 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (69 mg, 0.135 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 51. (12.9 g, yield 52%, MS: [M+H] ⁺ =921)

Example 52: Preparation of compound 52

In a nitrogen atmosphere, sub52 (20 g, 24.6 mmol), compound b (5.9 g, 27.0 mmol) and sodium tert-butoxide (7.1 g, 73.7 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (62 mg, 0.123 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 52. (11.3 g, yield 44%, MS: [M+H] ⁺ =1046)

Example 53: Preparation of compound 53

In a nitrogen atmosphere, sub53 (20 g, 29.4 mmol), compound c (8.6 g, 32.3 mmol) and sodium tert-butoxide (8.5 g, 88.2 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (75 mg, 0.147 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 53. (11.8 g, yield 44%, MS: [M+H] ⁺ =912)

Example 54: Preparation of compound 54

In a nitrogen atmosphere, sub54 (20 g, 28.7 mmol), compound c (8.4 g, 31.6 mmol) and sodium tert-butoxide (8.3 g, 86.2 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (73 mg, 0.144 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 54. (12.2 g, yield 44%, MS: [M+H] ⁺ =928)

Example 55: Preparation of compound 55

In a nitrogen atmosphere, sub55 (20 g, 26.5 mmol), compound d (7.8 g, 29.1 mmol) and sodium tert-butoxide (7.6 g, 79.4 mmol) were added to xylene (200 ml) and stirred and Refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (67 mg, 0.132 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was dissolved in chloroform (500 ml) again, washed twice with water, and the organic layer was separated, treated with magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain compound 55. (12.5 g, yield 48%, MS: [M+H] ⁺ =987)

Experimental Example 1

A glass substrate coated with a thin film of ITO (indium tin oxide) having a thickness of 1,000 Å was put in distilled water dissolved in a detergent and washed with ultrasonic waves. At this time, Fischer Co. product was used as a detergent, and distilled water secondarily filtered with a filter made by Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, it was repeated twice with distilled water to perform ultrasonic cleaning for 10 minutes. After washing with distilled water, ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator.

The HI-1 compound was formed as a hole injection layer on the prepared ITO transparent electrode to a thickness of 1150 Å, but the compound A-1 was p-doped at a concentration of 1.5%. The following HT-1 compound 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 evaporation of the following EB-1 compound having a film thickness of 150 Å on the hole transport layer. Subsequently, on the electron blocking layer, the compound 1 prepared in Example 1 and the following Dp-7 compound were vacuum-deposited at a weight ratio of 98:2 to form a red light emitting layer having a thickness of 400 Å. A hole blocking layer was formed by vacuum vapor deposition of the following HB-1 compound having a thickness of 30 Å on the light emitting layer. Subsequently, the following ET-1 compound and the following LiQ compound 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. Lithium fluoride (LiF) at a thickness of 12 Å and aluminum at a thickness of 1,000 Å were sequentially deposited on the electron injection and transport layer to form a negative electrode.

In the above process, the deposition rate of the organic material was maintained at 0.4 ~ 0.7 Å/sec, the deposition rate of lithium fluoride at the negative electrode was 0.3 Å/sec, and the deposition rate of aluminum was 2 Å/sec, and the vacuum degree during deposition was 2×10 ^-7 ~ An organic light-emitting device was manufactured by maintaining ^{5x10 -6 torr.}

Experimental Examples 2 to 55 and Comparative Experimental Examples 1 to 11

In the organic light-emitting device of Experimental Example 1, an organic light-emitting device was manufactured in the same manner as in Experimental Example 1, except that the compounds shown in Tables 1 and 2 were used instead of compound 1.

^{When a current of 10 mA/cm 2} was applied to the organic light emitting devices prepared in Experimental Examples 1 to 55 and Comparative Experimental Examples 1 to 11, voltage, efficiency and life were measured (based on 6000 nit) and the results are shown in the following table It is shown in 1-3. The lifetime T ₉₅ refers to the time it takes for the luminance to decrease from the initial luminance (6000 nit) to 95%.

division Host material Driving voltage (V) Efficiency (cd/A) Life T ₉₅ (hr) Luminous color Experimental Example 1 Compound 1 3.68 44.5 280 Red Experimental Example 2 Compound 2 3.65 42.9 284 Red Experimental Example 3 Compound 3 3.71 43.4 275 Red Experimental Example 4 Compound 4 3.72 42.9 268 Red Experimental Example 5 Compound 5 3.84 43.1 278 Red Experimental Example 6 Compound 6 3.59 45.5 284 Red Experimental Example 7 Compound 7 3.63 44.0 291 Red Experimental Example 8 Compound 8 3.59 45.7 290 Red Experimental Example 9 Compound 9 3.63 45.8 281 Red Experimental Example 10 Compound 10 3.68 47.0 297 Red Experimental Example 11 Compound 11 3.62 46.7 261 Red Experimental Example 12 Compound 12 3.71 46.7 271 Red Experimental Example 13 Compound 13 3.70 46.9 261 Red Experimental Example 14 Compound 14 3.65 46.4 264 Red Experimental Example 15 Compound 15 3.72 46.6 292 Red Experimental Example 16 Compound 16 3.60 45.3 284 Red Experimental Example 17 Compound 17 3.54 45.7 310 Red Experimental Example 18 Compound 18 3.50 45.1 321 Red Experimental Example 19 Compound 19 3.58 47.0 315 Red Experimental Example 20 Compound 20 3.67 50.2 327 Red Experimental Example 21 Compound 21 3.67 48.7 332 Red Experimental Example 22 Compound 22 3.66 49.7 341 Red Experimental Example 23 Compound 23 3.63 48.8 352 Red Experimental Example 24 Compound 24 3.59 46.5 324 Red Experimental Example 25 Compound 25 3.49 46.6 310 Red Experimental Example 26 Compound 26 3.51 43.8 309 Red Experimental Example 27 Compound 27 3.55 45.3 298 Red Experimental Example 28 Compound 28 3.61 48.2 321 Red Experimental Example 29 Compound 29 3.68 47.3 316 Red Experimental Example 30 Compound 30 3.63 46.5 303 Red Experimental Example 31 Compound 31 3.54 48.0 307 Red Experimental Example 32 Compound 32 3.62 49.2 318 Red Experimental Example 33 Compound 33 3.63 48.5 354 Red Experimental Example 34 Compound 34 3.48 48.3 336 Red Experimental Example 35 Compound 35 3.55 47.9 351 Red

division Host material Driving voltage (V) Efficiency (cd/A) Life T ₉₅ (hr) Luminous color Experimental Example 36 Compound 36 3.62 48.1 346 Red Experimental Example 37 Compound 37 3.63 49.2 329 Red Experimental Example 38 Compound 38 3.62 47.5 362 Red Experimental Example 39 Compound 39 3.54 48.7 350 Red Experimental Example 40 Compound 40 3.60 49.4 345 Red Experimental Example 41 Compound 41 3.54 50.6 341 Red Experimental Example 42 Compound 42 3.48 48.9 324 Red Experimental Example 43 Compound 43 3.33 50.2 346 Red Experimental Example 44 Compound 44 3.45 49.7 315 Red Experimental Example 45 Compound 45 3.32 48.9 316 Red Experimental Example 46 Compound 46 3.54 49.5 308 Red Experimental Example 47 Compound 47 3.42 47.0 298 Red Experimental Example 48 Compound 48 3.64 47.2 311 Red Experimental Example 49 Compound 49 3.71 46.4 287 Red Experimental Example 50 Compound 50 3.58 47.5 296 Red Experimental Example 51 Compound 51 3.39 48.9 320 Red Experimental Example 52 Compound 52 3.45 49.4 313 Red Experimental Example 53 Compound 53 3.47 50.1 315 Red Experimental Example 54 Compound 54 3.53 49.5 294 Red Experimental Example 55 Compound 55 3.41 48.9 315 Red Comparative Experimental Example 1 C-1 4.55 32.5 102 Red Comparative Experiment 2 C-2 4.54 36.8 111 Red Comparative Experiment 3 C-3 4.15 34.4 120 Red Comparative Experimental Example 4 C-4 4.34 36.5 92 Red Comparative Experimental Example 5 C-5 3.99 39.4 105 Red Comparative Experiment 6 C-6 4.15 37.5 134 Red Comparative Experimental Example 7 C-7 5.12 34.2 87 Red Comparative Experimental Example 8 C-8 4.94 34.6 98 Red Comparative Experimental Example 9 C-9 4.75 32.4 107 Red Comparative Experimental Example 10 C-10 4.35 39.8 163 Red Comparative Experimental Example 11 RH-1 4.32 37.6 196 Red

According to Tables 1 and 2, it was confirmed that the organic light-emitting device of the Experimental Example had a significantly lower driving voltage and remarkably high efficiency and life than the organic light-emitting device of Comparative Experimental Example.

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

Claims (9)

Compound represented by the following formula (1):
[Formula 1]

In Formula 1,
X ₁ to X ₃ are each independently N or CR ₈ , but at least any one is N,
Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted aryl having 6 to 60 carbon atoms; Or substituted or unsubstituted O, N, Si and S is a heteroaryl having 2 to 60 carbon atoms including one or more of,
R ₁ to R ₈ are each independently hydrogen; heavy hydrogen; halogen; Hydroxy; Nitrile; Nitro; Amino; Substituted or unsubstituted C2 to C60 alkyl; Substituted or unsubstituted 2 to 60 alkoxy; Substituted or unsubstituted 2 to 60 alkenyl; Substituted or unsubstituted 6 to 60 aryl; Or substituted or unsubstituted O, N, Si and S is a heteroaryl having 2 to 60 carbon atoms including one or more of,
One of A and B is a substituent represented by the following formula 1-1, and the other is hydrogen or deuterium,
[Formula 1-1]

In Formula 1-1,
R ₉ to R ₁₃ are each independently hydrogen; heavy hydrogen; halogen; Hydroxy; Nitrile; Nitro; Amino; Substituted or unsubstituted C2 to C60 alkyl; Substituted or unsubstituted 2 to 60 alkoxy; Substituted or unsubstituted 2 to 60 alkenyl; Substituted or unsubstituted 6 to 60 aryl; A substituted or unsubstituted heteroaryl having 2 to 60 carbon atoms including one or more of O, N, Si and S, or R ₉ to R ₁₂ are bonded to adjacent groups to form a fused ring
n is an integer from 1 to 6.
The method of claim 1,
Formula 1 is any one selected from the compounds represented by the following formulas 1-A and 1-B, a compound:

In Formulas 1-A and 1-B,
Description of X ₁ , X ₂ , X ₃ , Ar ₁ , Ar ₂ , and R ₉ to R ₁₂ are as defined in claim 1.
The method of claim 1,
X ₁ to X ₃ are all N, the compound.
The method of claim 1,
Ar ₁ and Ar ₂ are each independently any one selected from the group consisting of:

The method of claim 1,
Formula 1-1 is any one selected from the group consisting of the following compounds, a compound:

The method of claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of the following compounds:

A first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the compound according to any one of claims 1 to 6 That is, an organic light-emitting device.
The method of claim 7,
The organic material layer may include an emission layer, and the emission layer includes a host material.
The method of claim 8,
The host material includes a compound represented by Formula 1 above.

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