KR20210036857A - Novel compound and organic light emitting device comprising the same - Google Patents

Abstract

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

Description

Novel compound and organic light emitting device comprising the same

The present invention relates to a novel compound and an organic light emitting device comprising 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. An organic light-emitting device using the organic light-emitting phenomenon has a wide viewing angle, excellent contrast, and 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 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 compound and an organic light emitting device comprising the same.

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

[Formula 1]

In Formula 1,

Each X is independently N or CH, provided that at least one of X is N,

Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C _6-60 aryl; _{Substituted or unsubstituted C 2-60} heteroaryl including any one or more heteroatoms selected from the group consisting of N, O and S,

Each R is independently hydrogen; heavy hydrogen; halogen; Cyano; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted C _2-60 alkynyl; Substituted or unsubstituted C _3-30 cycloalkyl; Substituted or unsubstituted C _6-60 aryl; _{Substituted or unsubstituted C 2-60} heteroaryl including any one or more heteroatoms selected from the group consisting of N, O and S,

L is a divalent linker of the following formula (2),

[Formula 2]

In Chemical Formula 2,

Each R'is independently hydrogen; heavy hydrogen; halogen; Cyano; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted C _2-60 alkynyl; Substituted or unsubstituted C _3-30 cycloalkyl; Substituted or unsubstituted C _6-60 aryl; _{It is a C 2-60} heteroaryl containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S.

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 comprises 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.
FIG. 2 shows an example of an organic light emitting device comprising a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 7, an electron transport layer 8, and a cathode 4 I did it.
3 shows a substrate (1), an anode (2), a hole injection layer (5), a hole transport layer (6), an electron suppression layer (9), a light emitting layer (7), a hole blocking layer (10), an electron transport and injection transport layer. An example of an organic light-emitting device comprising (12) and a cathode (4) is shown.

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.

또는

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

or

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, triazole 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, thiazolyl group, Isoxazolyl group, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group, dibenzofuranyl group, and the like, 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.

In Formula 1, preferably, all of X are N.

Preferably, Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C _6-18 aryl, or a substituent represented by the following formula (3):

[Formula 3]

In Chemical Formula 3,

Y is O, S, or N-(phenyl).

Preferably, Ar ₁ and Ar ₂ are phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, dibenzofuranyl, dibenzothiophenyl, 9-phenyl-carbazolyl, or carbazole-9- It's work. Preferably, Ar ₁ and Ar ₂ are identical to each other.

Preferably, each R is independently hydrogen or deuterium.

Preferably, each R'is independently hydrogen or deuterium.

Preferably, L is any one selected from the group consisting of:

.

.

More preferably, L is any one selected from the group consisting of:

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

On the other hand, the compound represented by Formula 1 can be prepared by the same manufacturing method as in Scheme 1 below.

[Scheme 1]

In Reaction Scheme 1, the definitions other than X'are as previously defined, and X'is halogen, more preferably bromo or chloro.

Reaction Scheme 1 is an amine substitution reaction, preferably carried out in the presence of a palladium catalyst and a base, and the reactor for the amine substitution reaction may 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 comprises 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, or a layer that simultaneously injects and transports holes, and the hole injection layer, a hole transport layer, or a layer that simultaneously injects and transports holes is represented by Formula 1 above. Including the indicated compound.

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

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

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 an example of an organic light-emitting device comprising a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light-emitting layer 7, an electron transport layer 8, and a cathode 4 I did it. In such a structure, the compound represented by Formula 1 may be included in one or more of the hole injection layer, the hole transport layer, the light emitting layer, and the electron transport layer.

3 shows a substrate (1), an anode (2), a hole injection layer (5), a hole transport layer (6), an electron suppression layer (9), a light emitting layer (7), a hole blocking layer (10), an electron transport and injection transport layer. An example of an organic light-emitting device consisting of 12 and a cathode 4 is shown. In such a structure, the compound represented by Formula 1 may be included in one or more of the hole injection layer, the hole transport layer, the electron suppression layer, the emission layer, the hole blocking layer, and the electron transport and injection 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 layer is a layer that injects holes from the electrode, and has the ability to transport holes as a hole injection material, 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 from the light emitting layer. A compound that prevents the movement of excitons to the electron injection layer or the electron injection material and has excellent ability to form a thin film 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 layer is a layer that receives electrons from the electron injection layer and transports electrons to the emission layer. As an electron transport material, a material capable of injecting electrons from the cathode and transferring them to the emission layer, and a material having high mobility for electrons is suitable. Do. 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, perylene tetracarboxylic acid, preorenylidene methane, anthrone, etc. 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.

The preparation of the compound represented by Formula 1 and the organic light-emitting device including the same will be described in detail in the following Examples. However, the following examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

[Example]

Example 1: Preparation of compound 1

In a nitrogen atmosphere, compound sub_a-1 (15 g, 56 mmol) and compound sub_b-1 (15.2 g, 61.6 mmol) were added to THF (300 ml), followed by stirring and refluxing. Thereafter, potassium carbonate (31 g, 224.1 mmol) was dissolved in water (93 ml), stirred sufficiently, and then bis (tri-tert-butylphosphine) palladium (0) (0.6 g, 1.1 mmol) was added. After the reaction for 12 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound sub1 (12.4 g, yield 51%).

MS: [M+H] ⁺ = 434

In a nitrogen atmosphere, compound sub1 (10 g, 23 mmol), compound A (7.4 g, 25.4 mmol), and sodium tert-butoxide (4.4 g, 46.1 mmol) were added to xylene (200 ml), followed by stirring and refluxing. After this, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.5 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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 compound 1 (8.7 g, yield 55%).

MS: [M+H] ⁺ = 689

Example 2: Preparation of compound 2

In a nitrogen atmosphere, compound sub_a-1 (15 g, 56 mmol) and compound sub_b-2 (15.2 g, 61.6 mmol) were added to THF (300 ml), followed by stirring and refluxing. Thereafter, potassium carbonate (31 g, 224.1 mmol) was dissolved in water (93 ml), stirred sufficiently, and then bis (tri-tert-butylphosphine) palladium (0) (0.6 g, 1.1 mmol) was added. After the reaction for 12 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound sub2 (16.3 g, yield 67%).

MS: [M+H] ⁺ = 434

In a nitrogen atmosphere, compound sub2 (10 g, 23 mmol), compound A (7.4 g, 25.4 mmol), and sodium tert-butoxide (4.4 g, 46.1 mmol) were added to xylene (200 ml), followed by stirring and refluxing. After this, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.5 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 completely dissolved in chloroform again, 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 compound 2 (10.6 g, yield 67%).

MS: [M+H] ⁺ = 689

Example 3: Preparation of compound 3

In a nitrogen atmosphere, compound sub_a-2 (15 g, 43.6 mmol) and compound sub_b-2 (11.8 g, 48 mmol) were added to THF (300 ml), followed by stirring and refluxing. Thereafter, potassium carbonate (24.1 g, 174.5 mmol) was dissolved in water (72 ml), stirred sufficiently, and bis (tri-tert-butylphosphine) palladium (0) (0.4 g, 0.9 mmol) was added. After the reaction for 11 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound sub3 (13.1 g, yield 59%).

MS: [M+H] ⁺ = 510

In a nitrogen atmosphere, compound sub3 (10 g, 19.6 mmol), compound A (6.3 g, 21.6 mmol), and sodium tert-butoxide (3.8 g, 39.2 mmol) were added to xylene (200 ml), followed by stirring and refluxing. After this, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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 compound 3 (8.1 g, yield 54%).

MS: [M+H] ⁺ = 765

Example 4: Preparation of compound 4

In a nitrogen atmosphere, compound sub_a-1 (15 g, 56 mmol) and compound sub_b-3 (15.2 g, 61.6 mmol) were added to THF (300 ml), followed by stirring and refluxing. Thereafter, potassium carbonate (31 g, 224.1 mmol) was dissolved in water (93 ml), stirred sufficiently, and then bis (tri-tert-butylphosphine) palladium (0) (0.6 g, 1.1 mmol) was added. After the reaction for 12 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound sub4 (18.3 g, yield 64%).

MS: [M+H] ⁺ = 510

In a nitrogen atmosphere, compound sub4 (10 g, 23 mmol), compound A (7.4 g, 25.4 mmol), and sodium tert-butoxide (4.4 g, 46.1 mmol) were added to xylene (200 ml), followed by stirring and refluxing. After this, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.5 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 completely dissolved in chloroform again, 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 compound 4 (10 g, yield 63%).

MS: [M+H] ⁺ = 689

Example 5: Preparation of compound 5

In a nitrogen atmosphere, compound sub_a-3 (15 g, 47.2 mmol) and compound sub_b-3 (12.8 g, 51.9 mmol) were added to THF (300 ml), followed by stirring and refluxing. Thereafter, potassium carbonate (26.1 g, 188.8 mmol) was dissolved in water (78 ml), stirred sufficiently, and then bis (tri-tert-butylphosphine) palladium (0) (0.5 g, 0.9 mmol) was added. After the reaction for 10 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound sub5 (13 g, yield 57%).

MS: [M+H] ⁺ = 484

In a nitrogen atmosphere, compound sub5 (10 g, 20.7 mmol), compound A (6.6 g, 22.8 mmol), and sodium tert-butoxide (4 g, 41.4 mmol) were added to xylene (200 ml), followed by stirring and refluxing. After this, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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 compound 5 (9.2 g, yield 60%).

MS: [M+H] ⁺ = 739

Example 6: Preparation of compound 6

In a nitrogen atmosphere, compound sub_a-4 (15 g, 41.9 mmol) and compound sub_b-3 (11.4 g, 46.1 mmol) were added to THF (300 ml), followed by stirring and refluxing. Thereafter, potassium carbonate (23.2 g, 167.7 mmol) was dissolved in water (70 ml), stirred sufficiently, and then bis (tri-tert-butylphosphine) palladium (0) (0.4 g, 0.8 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound sub6 (11.8 g, yield 54%).

MS: [M+H] ⁺ = 524

In a nitrogen atmosphere, compound sub6 (10 g, 19.1 mmol), compound A (6.1 g, 21 mmol), and sodium tert-butoxide (3.7 g, 38.2 mmol) were added to xylene (200 ml), followed by stirring and refluxing. After this, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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 compound 6 (9.1 g, yield 61%).

MS: [M+H] ⁺ = 779

Example 7: Preparation of compound 7

In a nitrogen atmosphere, compound sub_a-1 (15 g, 56 mmol) and compound sub_b-4 (15.2 g, 61.6 mmol) were added to THF (300 ml), followed by stirring and refluxing. Thereafter, potassium carbonate (31 g, 224.1 mmol) was dissolved in water (93 ml), stirred sufficiently, and then bis (tri-tert-butylphosphine) palladium (0) (0.6 g, 1.1 mmol) was added. After the reaction for 11 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound sub7 (15.5 g, yield 64%).

MS: [M+H] ⁺ = 434

In a nitrogen atmosphere, compound sub7 (10 g, 23 mmol), compound A (7.4 g, 25.4 mmol), and sodium tert-butoxide (4.4 g, 46.1 mmol) were added to xylene (200 ml), followed by stirring and refluxing. After this, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.5 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 completely dissolved in chloroform again, 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 compound 7 (9.5 g, yield 60%).

MS: [M+H] ⁺ = 689

Example 8: Preparation of compound 8

In a nitrogen atmosphere, compound sub_a-1 (15 g, 56 mmol) and compound sub_b-5 (15.2 g, 61.6 mmol) were added to THF (300 ml), followed by stirring and refluxing. Thereafter, potassium carbonate (31 g, 224.1 mmol) was dissolved in water (93 ml), stirred sufficiently, and then bis (tri-tert-butylphosphine) palladium (0) (0.6 g, 1.1 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound sub8 (14.1 g, yield 58%).

MS: [M+H] ⁺ = 434

In a nitrogen atmosphere, compound sub8 (10 g, 23 mmol), compound A (7.4 g, 25.4 mmol), and sodium tert-butoxide (4.4 g, 46.1 mmol) were added to xylene (200 ml), followed by stirring and refluxing. After this, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.5 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 completely dissolved in chloroform again, 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 compound 8 (10 g, yield 63%).

MS: [M+H] ⁺ = 689

Example 9: Preparation of compound 9

In a nitrogen atmosphere, compound sub_a-5 (15 g, 34.6 mmol) and compound sub_b-5 (9.4 g, 38 mmol) were added to THF (300 ml), followed by stirring and refluxing. Thereafter, potassium carbonate (19.1 g, 138.3 mmol) was dissolved in water (57 ml), stirred sufficiently, and then bis (tri-tert-butylphosphine) palladium (0) (0.4 g, 0.7 mmol) was added. After the reaction for 12 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound sub9 (14.1 g, yield 68%).

MS: [M+H] ⁺ = 600

In a nitrogen atmosphere, compound sub9 (10 g, 16.7 mmol), compound A (5.3 g, 18.4 mmol), and sodium tert-butoxide (3.2 g, 33.4 mmol) were added to xylene (200 ml), followed by stirring and refluxing. After this, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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 compound 9 (9.8 g, yield 69%).

MS: [M+H] ⁺ = 855

Example 10: Preparation of compound 10

In a nitrogen atmosphere, compound sub_a-1 (15 g, 56 mmol) and compound sub_b-6 (15.2 g, 61.6 mmol) were added to THF (300 ml), followed by stirring and refluxing. Thereafter, potassium carbonate (31 g, 224.1 mmol) was dissolved in water (93 ml), stirred sufficiently, and then bis (tri-tert-butylphosphine) palladium (0) (0.6 g, 1.1 mmol) was added. After the reaction for 11 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound sub10 (16.5 g, yield 68%).

MS: [M+H] ⁺ = 434

In a nitrogen atmosphere, compound sub10 (10 g, 23.1 mmol), compound A (7.4 g, 25.4 mmol), and sodium tert-butoxide (4.4 g, 46.2 mmol) were added to xylene (200 ml), followed by stirring and refluxing. After this, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.5 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 completely dissolved in chloroform again, 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 compound 10 (10.2 g, yield 64%).

MS: [M+H] ⁺ = 689

Example 11: Preparation of compound 11

In a nitrogen atmosphere, compound sub_a-6 (15 g, 43.6 mmol) and compound sub_b-7 (11.8 g, 48 mmol) were added to THF (300 ml), followed by stirring and refluxing. Thereafter, potassium carbonate (24.1 g, 174.5 mmol) was dissolved in water (72 ml), stirred sufficiently, and bis (tri-tert-butylphosphine) palladium (0) (0.4 g, 0.9 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound sub11 (15.3 g, yield 69%).

MS: [M+H] ⁺ = 510

In a nitrogen atmosphere, compound sub11 (10 g, 19.6 mmol), compound A (6.3 g, 21.6 mmol), and sodium tert-butoxide (3.8 g, 39.2 mmol) were added to xylene (200 ml), followed by stirring and refluxing. After this, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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 compound 11 (8.1 g, yield 54%).

MS: [M+H] ⁺ = 765

Example 12: Preparation of compound 12

In a nitrogen atmosphere, compound sub_a-7 (15 g, 47.2 mmol) and compound sub_b-8 (12.8 g, 51.9 mmol) were added to THF (300 ml), followed by stirring and refluxing. Thereafter, potassium carbonate (26.1 g, 188.8 mmol) was dissolved in water (78 ml), stirred sufficiently, and then bis (tri-tert-butylphosphine) palladium (0) (0.5 g, 0.9 mmol) was added. After the reaction for 11 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound sub12 (15.7 g, yield 69%).

MS: [M+H] ⁺ = 484

In a nitrogen atmosphere, compound sub12 (10 g, 20.7 mmol), compound A (6.6 g, 22.7 mmol), and sodium tert-butoxide (4 g, 41.3 mmol) were added to xylene (200 ml), followed by stirring and refluxing. After this, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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 compound 12 (8.2 g, yield 54%).

MS: [M+H] ⁺ = 739

Example 13: Preparation of compound 13

In a nitrogen atmosphere, compound sub_a-8 (15 g, 40.8 mmol) and compound sub_b-9 (11.1 g, 44.9 mmol) were added to THF (300 ml), followed by stirring and refluxing. Thereafter, potassium carbonate (22.5 g, 163.1 mmol) was dissolved in 68 ml of water, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.4 g, 0.8 mmol) was added. After the reaction for 12 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound sub13 (11.7 g, yield 54%).

MS: [M+H] ⁺ = 534

In a nitrogen atmosphere, compound sub13 (10 g, 18.8 mmol), compound A (6 g, 20.6 mmol), and sodium tert-butoxide (3.6 g, 37.5 mmol) were added to xylene (200 ml), followed by stirring and refluxing. After this, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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 compound 13 (9.8 g, yield 66%).

MS: [M+H] ⁺ = 789

Example 14: Preparation of compound 14

In a nitrogen atmosphere, compound sub_a-9 (15 g, 28.1 mmol) and compound sub_b-10 (7.6 g, 31 mmol) were added to THF (300 ml), followed by stirring and refluxing. Thereafter, potassium carbonate (15.6 g, 112.6 mmol) was dissolved in water (47 ml), stirred sufficiently, and then bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound sub14 (10.4 g, yield 53%).

MS: [M+H] ⁺ = 699

In a nitrogen atmosphere, compound sub14 (10 g, 14.3 mmol), compound A (4.6 g, 15.7 mmol), and sodium tert-butoxide (2.7 g, 28.6 mmol) were added to xylene (200 ml), followed by stirring and refluxing. After this, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.3 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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 compound 14 (9.1 g, yield 67%).

MS: [M+H] ⁺ = 954

Example 15: Preparation of compound 15

In a nitrogen atmosphere, compound sub_a-1 (15 g, 56 mmol) and compound sub_b-11 (15.2 g, 61.6 mmol) were added to THF (300 ml), followed by stirring and refluxing. Thereafter, potassium carbonate (31 g, 224.1 mmol) was dissolved in water (93 ml), stirred sufficiently, and then bis (tri-tert-butylphosphine) palladium (0) (0.6 g, 1.1 mmol) was added. After the reaction for 11 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound sub15 (15 g, yield 62%).

MS: [M+H] ⁺ = 434

In a nitrogen atmosphere, compound sub15 (10 g, 23 mmol), compound A (7.4 g, 25.4 mmol), and sodium tert-butoxide (4.4 g, 46.1 mmol) were added to xylene (200 ml), followed by stirring and refluxing. After this, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.5 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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 compound 15 (8.6 g, yield 54%).

MS: [M+H] ⁺ = 689

Example 16: Preparation of compound 16

In a nitrogen atmosphere, compound sub_a-10 (15 g, 34.6 mmol) and compound sub_b-12 (9.4 g, 38 mmol) were added to THF (300 ml), followed by stirring and refluxing. Thereafter, potassium carbonate (19.1 g, 138.3 mmol) was dissolved in 57 ml of water, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.4 g, 0.7 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound sub16 (14.1 g, yield 68%).

MS: [M+H] ⁺ = 600

In a nitrogen atmosphere, compound sub16 (10 g, 16.7 mmol), compound A (5.3 g, 18.3 mmol), and sodium tert-butoxide (3.2 g, 33.3 mmol) were added to xylene (200 ml), followed by stirring and refluxing. After this, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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 compound 16 (7.7 g, yield 54%).

MS: [M+H] ⁺ = 855

Example 17: Preparation of compound 17

In a nitrogen atmosphere, compound sub_a-1 (15 g, 56 mmol) and compound sub_b-13 (15.2 g, 61.6 mmol) were added to THF (300 ml), followed by stirring and refluxing. Thereafter, potassium carbonate (31 g, 224.1 mmol) was dissolved in water (93 ml), stirred sufficiently, and then bis (tri-tert-butylphosphine) palladium (0) (0.6 g, 1.1 mmol) was added. After the reaction for 10 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound sub17 (15.8 g, yield 65%).

MS: [M+H] ⁺ = 434

In a nitrogen atmosphere, compound sub17 (10 g, 23 mmol), compound A (7.4 g, 25.4 mmol), and sodium tert-butoxide (4.4 g, 46.1 mmol) were added to xylene (200 ml), followed by stirring and refluxing. After this, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.5 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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 compound 17 (9.5 g, yield 60%).

MS: [M+H] ⁺ = 689

Example 18: Preparation of compound 18

In a nitrogen atmosphere, compound sub_a-1 (15 g, 56 mmol) and compound sub_b-14 (15.2 g, 61.6 mmol) were added to THF (300 ml), followed by stirring and refluxing. Thereafter, potassium carbonate (31 g, 224.1 mmol) was dissolved in water (93 ml), stirred sufficiently, and then bis (tri-tert-butylphosphine) palladium (0) (0.6 g, 1.1 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound sub18 (16.5 g, yield 68%).

MS: [M+H] ⁺ = 434

In a nitrogen atmosphere, compound sub18 (10 g, 23 mmol), compound A (7.4 g, 25.4 mmol), and sodium tert-butoxide (4.4 g, 46.1 mmol) were added to xylene (200 ml), followed by stirring and refluxing. After this, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.5 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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 compound 18 (10.2 g, yield 64%).

MS: [M+H] ⁺ = 689

Example 19: Preparation of compound 19

In a nitrogen atmosphere, compound sub_a-11 (15 g, 43.6 mmol) and compound sub_b-15 (11.8 g, 48 mmol) were added to THF (300 ml), followed by stirring and refluxing. Thereafter, potassium carbonate (24.1 g, 174.5 mmol) was dissolved in water (72 ml), stirred sufficiently, and then bis (tri-tert-butylphosphine) palladium (0) (0.4 g, 0.9 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound sub19 (15.1 g, yield 68%).

MS: [M+H] ⁺ = 510

In a nitrogen atmosphere, compound sub19 (10 g, 19.6 mmol), compound A (6.3 g, 21.6 mmol), and sodium tert-butoxide (3.8 g, 39.2 mmol) were added to xylene (200 ml), followed by stirring and refluxing. After this, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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 compound 19 (8.2 g, yield 55%).

MS: [M+H] ⁺ = 765

Example 20: Preparation of compound 20

In a nitrogen atmosphere, compound sub_a-12 (15 g, 40.8 mmol) and compound sub_b-16 (11.1 g, 44.9 mmol) were added to THF (300 ml), followed by stirring and refluxing. Thereafter, potassium carbonate (22.5 g, 163.1 mmol) was dissolved in 68 ml of water, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.4 g, 0.8 mmol) was added. After the reaction for 10 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound sub20 (13 g, yield 60%).

MS: [M+H] ⁺ = 534

In a nitrogen atmosphere, compound sub20 (10 g, 18.7 mmol), compound A (6 g, 20.6 mmol), and sodium tert-butoxide (3.6 g, 37.5 mmol) were added to xylene (200 ml), followed by stirring and refluxing. After this, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 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 completely dissolved in chloroform again, 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 compound 20 (7.8 g, yield 53%).

MS: [M+H] ⁺ = 789

Example 21: Preparation of compound 21

In a nitrogen atmosphere, compound sub_a-13 (15 g, 31.1 mmol) and compound sub_b-17 (8.4 g, 34.2 mmol) were added to THF (300 ml) and stirred and refluxed. Thereafter, potassium carbonate (17.2 g, 124.2 mmol) was dissolved in 52 ml of water, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound sub21 (12.1 g, yield 60%).

MS: [M+H] ⁺ = 649

In a nitrogen atmosphere, compound sub21 (10 g, 15.4 mmol), compound A (4.9 g, 16.9 mmol), and sodium tert-butoxide (3 g, 30.8 mmol) were added to xylene (200 ml), followed by stirring and refluxing. After this, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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 compound 21 (8.2 g, yield 59%).

MS: [M+H] ⁺ = 904

Example 22: Preparation of compound 22

In a nitrogen atmosphere, compound sub_a-14 (15 g, 36.8 mmol) and compound sub_b-18 (10 g, 40.5 mmol) were added to THF (300 ml), followed by stirring and refluxing. Thereafter, potassium carbonate (20.3 g, 147.1 mmol) was dissolved in water (61 ml), stirred sufficiently, and then bis (tri-tert-butylphosphine) palladium (0) (0.4 g, 0.7 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound sub22 (12.9 g, yield 61%).

MS: [M+H] ⁺ = 574

In a nitrogen atmosphere, compound sub22 (10 g, 17.4 mmol), compound A (5.6 g, 19.2 mmol), and sodium tert-butoxide (3.3 g, 34.8 mmol) were added to xylene (200 ml), followed by stirring and refluxing. After this, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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 compound 22 (8.4 g, yield 58%).

MS: [M+H] ⁺ = 829

Example 23: Preparation of compound 23

In a nitrogen atmosphere, compound sub_a-15 (15 g, 40.1 mmol) and compound sub_b-19 (10.9 g, 44.1 mmol) were added to THF (300 ml), followed by stirring and refluxing. Thereafter, potassium carbonate (22.2 g, 160.5 mmol) was dissolved in water (67 ml), stirred sufficiently, and bis (tri-tert-butylphosphine) palladium (0) (0.4 g, 0.8 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound sub23 (11.7 g, yield 54%).

MS: [M+H] ⁺ = 540

In a nitrogen atmosphere, compound sub23 (10 g, 18.5 mmol), compound A (5.9 g, 20.4 mmol), and sodium tert-butoxide (3.6 g, 37 mmol) were added to xylene (200 ml), followed by stirring and refluxing. After this, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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 compound 23 (7.9 g, yield 54%).

MS: [M+H] ⁺ = 795

Example 24: Preparation of compound 24

In a nitrogen atmosphere, compound sub_a-16 (15 g, 34.6 mmol) and compound sub_b-20 (9.4 g, 38 mmol) were added to THF (300 ml), followed by stirring and refluxing. Thereafter, potassium carbonate (19.1 g, 138.3 mmol) was dissolved in water (57 ml), stirred sufficiently, and then bis (tri-tert-butylphosphine) palladium (0) (0.4 g, 0.7 mmol) was added. After the reaction for 10 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound sub24 (10.4 g, yield 50%).

MS: [M+H] ⁺ = 600

In a nitrogen atmosphere, compound sub24 (10 g, 16.7 mmol), compound A (5.3 g, 18.3 mmol), and sodium tert-butoxide (3.2 g, 33.3 mmol) were added to xylene (200 ml), followed by stirring and refluxing. After this, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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 compound 24 (8.5 g, yield 60%).

MS: [M+H] ⁺ = 855

Example 25: Preparation of compound 25

In a nitrogen atmosphere, compound sub_a-1 (15 g, 56 mmol) and compound sub_b-21 (15.2 g, 61.6 mmol) were added to THF (300 ml), followed by stirring and refluxing. Thereafter, potassium carbonate (31 g, 224.1 mmol) was dissolved in water (93 ml), stirred sufficiently, and then bis (tri-tert-butylphosphine) palladium (0) (0.6 g, 1.1 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound sub25 (14.8 g, yield 61%).

MS: [M+H] ⁺ = 434

In a nitrogen atmosphere, compound sub25 (10 g, 23 mmol), compound A (7.4 g, 25.4 mmol), and sodium tert-butoxide (4.4 g, 46.1 mmol) were added to xylene (200 ml), followed by stirring and refluxing. After this, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.5 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 completely dissolved in chloroform again, 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 compound 25 (7.9 g, yield 50%).

MS: [M+H] ⁺ = 689

Example 26: Preparation of compound 26

In a nitrogen atmosphere, compound sub_a-17 (15 g, 33.3 mmol) and compound sub_b-22 (9 g, 36.7 mmol) were added to THF (300 ml) and stirred and refluxed. Thereafter, potassium carbonate (18.4 g, 133.3 mmol) was dissolved in water (55 ml), stirred sufficiently, and then bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.7 mmol) was added. After the reaction for 10 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound sub26 (11.9 g, yield 58%).

MS: [M+H] ⁺ = 616

In a nitrogen atmosphere, compound sub26 (10 g, 16.2 mmol), compound A (5.2 g, 17.9 mmol), and sodium tert-butoxide (3.1 g, 32.5 mmol) were added to xylene (200 ml), followed by stirring and refluxing. After this, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.3 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 completely dissolved in chloroform again, 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 compound 26 (8.3 g, yield 59%).

MS: [M+H] ⁺ = 871

Example 27: Preparation of compound 27

In a nitrogen atmosphere, compound sub_a-18 (15 g, 35.4 mmol) and compound sub_b-23 (9.6 g, 38.9 mmol) were added to THF (300 ml), followed by stirring and refluxing. Thereafter, potassium carbonate (19.6 g, 141.5 mmol) was dissolved in 59 ml of water, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.4 g, 0.7 mmol) was added. After the reaction for 11 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, 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 sub27. (Yield 69%, MS: [M+H] ⁺ = 590)

In a nitrogen atmosphere, compound sub27 (10 g, 16.9 mmol), compound A (5.4 g, 18.6 mmol), and sodium tert-butoxide (3.3 g, 33.9 mmol) were added to xylene (200 ml), followed by stirring and refluxing. After this, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.3 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 completely dissolved in chloroform again, 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 compound 27 (9.9 g, yield 69%).

MS: [M+H] ⁺ = 845

Example 28: Preparation of compound 28

In a nitrogen atmosphere, compound sub_a-12 (15 g, 40.8 mmol) and compound sub_b-24 (11.1 g, 44.9 mmol) were added to THF (300 ml), followed by stirring and refluxing. Thereafter, potassium carbonate (22.5 g, 163.1 mmol) was dissolved in water (68 ml), stirred sufficiently, and then bis (tri-tert-butylphosphine) palladium (0) (0.4 g, 0.8 mmol) was added. After the reaction for 12 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound sub28 (14.3 g, yield 66%).

MS: [M+H] ⁺ = 534

In a nitrogen atmosphere, compound sub28 (10 g, 18.7 mmol), compound A (6 g, 20.6 mmol), and sodium tert-butoxide (3.6 g, 37.5 mmol) were added to xylene (200 ml), followed by stirring and refluxing. After this, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 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 completely dissolved in chloroform again, 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 compound 28 (10.2 g, yield 69%).

MS: [M+H] ⁺ = 789

Example 29: Preparation of compound 29

In a nitrogen atmosphere, compound sub_a-19 (15 g, 43.6 mmol) and compound sub_b-25 (11.8 g, 48 mmol) were added to THF (300 ml), followed by stirring and refluxing. Thereafter, potassium carbonate (24.1 g, 174.5 mmol) was dissolved in water (72 ml), stirred sufficiently, and bis (tri-tert-butylphosphine) palladium (0) (0.4 g, 0.9 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound sub29 (14.7 g, yield 66%).

MS: [M+H] ⁺ = 510

In a nitrogen atmosphere, compound sub29 (10 g, 19.6 mmol), compound A (6.3 g, 21.6 mmol), and sodium tert-butoxide (3.8 g, 39.2 mmol) were added to xylene (200 ml), followed by stirring and refluxing. After this, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 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 completely dissolved in chloroform again, 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 compound 29 (9.1 g, yield 61%).

MS: [M+H] ⁺ = 765

Example 30: Preparation of compound 30

In a nitrogen atmosphere, compound sub_a-20 (15 g, 35.7 mmol) and compound sub_b-26 (9.7 g, 39.3 mmol) were added to THF (300 ml), followed by stirring and refluxing. Thereafter, potassium carbonate (19.7 g, 142.9 mmol) was dissolved in 59 ml of water, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.4 g, 0.7 mmol) was added. After the reaction for 11 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound sub30 (12.5 g, yield 60%).

MS: [M+H] ⁺ = 586

In a nitrogen atmosphere, compound sub30 (10 g, 17.1 mmol), compound A (5.5 g, 18.8 mmol), and sodium tert-butoxide (3.3 g, 34.1 mmol) were added to xylene (200 ml), followed by stirring and refluxing. After this, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.3 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 completely dissolved in chloroform again, 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 compound 30 (9.9 g, yield 69%).

MS: [M+H] ⁺ = 841

Example 31: Preparation of compound 31

In a nitrogen atmosphere, compound sub_a-21 (15 g, 41.9 mmol) and compound sub_b-27 (11.4 g, 46.1 mmol) were added to THF (300 ml), followed by stirring and refluxing. Thereafter, potassium carbonate (23.2 g, 167.7 mmol) was dissolved in 70 ml of water, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.4 g, 0.8 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound sub31 (14.3 g, yield 65%).

MS: [M+H] ⁺ = 524

In a nitrogen atmosphere, compound sub31 (10 g, 19.1 mmol), compound A (6.1 g, 21 mmol), and sodium tert-butoxide (3.7 g, 38.2 mmol) were added to xylene (200 ml), followed by stirring and refluxing. After this, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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 compound 31 (9.7 g, yield 65%).

MS: [M+H] ⁺ = 779

[Experimental Example]

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, a product made by Fischer Co. was used as a detergent, and distilled water secondarily filtered with a filter manufactured 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.

On the prepared ITO transparent electrode, the following HI-1 compound was formed to a thickness of 1150Å, but a hole injection layer was formed by p-doping the following compound A-1 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, the following EB-1 compound was vacuum-deposited on the hole transport layer to form an electron suppressing layer having a thickness of 150 Å. The following RH-1 compound and the following Dp-7 compound were vacuum-deposited at a weight ratio of 98:2 on the electron suppressing layer to form a red light emitting layer having a thickness of 400 Å. The following HB-1 compound was vacuum-deposited on the emission layer to form a hole blocking layer having a thickness of 30 Å. On the hole blocking layer, the following ET-1 compound and the following LiQ compound were vacuum-deposited at a weight ratio of 2:1 to form an electron injection and transport layer having a thickness of 300 Å. Lithium fluoride (LiF) in a thickness of 12 Å and aluminum in 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 organic materials 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. ^{Maintaining -7} ~ 5 × 10 ^-6 torr, an organic light emitting device was manufactured.

Experimental Examples 2 to 31

An organic light-emitting device was manufactured in the same manner as in Experimental Example 1, except that the compound shown in Table 1 was used instead of Compound 1.

Comparative Experimental Examples 1 to 9

An organic light-emitting device was manufactured in the same manner as in Experimental Example 1, except that the compound shown in Table 2 was used instead of Compound 1. The compounds shown in Table 2 are as follows.

When a current was applied to the organic light emitting device prepared in the Experimental Examples and Comparative Experimental Examples, voltage and efficiency were measured (10 mA/cm ² ), and the results are shown in Tables 1 and 2 below. Life T95 refers to the time it takes for the luminance to decrease from the initial luminance (6000 nit) to 95%.

compound
(Host of the light-emitting layer) Driving voltage
(V@10mA/cm ² ) efficiency
(cd/A@10mA/cm ² ) Life T95
(hr@10mA/cm ² ) Luminous color Experimental Example 1 Compound 1 3.70 24.5 190 Red Experimental Example 2 Compound 2 3.71 24.2 181 Red Experimental Example 3 Compound 3 3.74 25.4 173 Red Experimental Example 4 Compound 4 3.72 26.1 170 Red Experimental Example 5 Compound 5 3.73 25.5 187 Red Experimental Example 6 Compound 6 3.80 25.4 161 Red Experimental Example 7 Compound 7 3.83 24.5 183 Red Experimental Example 8 Compound 8 3.84 24.7 188 Red Experimental Example 9 Compound 9 3.72 24.3 201 Red Experimental Example 10 Compound 10 3.72 25.5 164 Red Experimental Example 11 Compound 11 3.75 24.4 167 Red Experimental Example 12 Compound 12 3.78 25.2 188 Red Experimental Example 13 Compound 13 3.74 24.7 203 Red Experimental Example 14 Compound 14 3.71 26.2 198 Red Experimental Example 15 Compound 15 3.70 25.3 181 Red Experimental Example 16 Compound 16 3.79 26.5 204 Red Experimental Example 17 Compound 17 3.72 25.7 173 Red Experimental Example 18 Compound 18 3.73 24.6 184 Red Experimental Example 19 Compound 19 3.70 26.3 173 Red Experimental Example 20 Compound 20 3.75 25.4 184 Red Experimental Example 21 Compound 21 3.69 26.5 190 Red Experimental Example 22 Compound 22 3.72 26.7 203 Red Experimental Example 23 Compound 23 3.75 25.8 176 Red Experimental Example 24 Compound 24 3.68 24.4 172 Red Experimental Example 25 Compound 25 3.74 26.5 188 Red Experimental Example 26 Compound 26 3.68 25.3 179 Red Experimental Example 27 Compound 27 3.75 26.1 187 Red Experimental Example 28 Compound 28 3.73 24.0 191 Red Experimental Example 29 Compound 29 3.72 26.7 188 Red Experimental Example 30 Compound 30 3.75 24.5 203 Red Experimental Example 31 Compound 31 3.64 25.4 192 Red

compound
(Host of the light-emitting layer) Driving voltage
(V@10mA/cm ² ) efficiency
(cd/A@10mA/cm ² ) Life T95
(hr@10mA/cm ² ) Luminous color Comparative Experimental Example 1 RH-1 4.14 21.3 139 Red Comparative Experiment 2 C-1 3.97 21.0 120 Red Comparative Experiment 3 C-2 3.98 20.7 141 Red Comparative Experimental Example 4 C-3 4.01 20.1 78 Red Comparative Experimental Example 5 C-4 3.95 19.3 94 Red Comparative Experiment 6 C-5 4.03 19.4 57 Red Comparative Experimental Example 7 C-6 4.04 20.3 25 Red Comparative Experimental Example 8 C-7 3.93 19.5 148 Red Comparative Experimental Example 9 C-8 4.01 20.4 153 Red

As shown in Table 1, when the compound of the present invention was used as the host of the red light emitting layer, the driving voltage was significantly lowered compared to the material of the comparative example, and the efficiency was also greatly increased, from which energy transfer from the host to the red dopant. I could see that this was going well. In addition, it was found that while maintaining high efficiency, the life characteristics could be greatly improved. This is due to the fact that the compound of the present invention has higher stability against electrons and holes than the compound of Comparative Experimental Example. Accordingly, it can be seen that when the compound of the present invention is used as a host of a red emission layer, the driving voltage, luminous efficiency, and lifetime characteristics of the organic light-emitting device can be improved.

1: substrate 2: anode
3: light-emitting layer 4: cathode
5: hole injection layer 6: hole transport layer
7: light emitting layer 8: electron transport layer
9: electron suppression layer 10: hole blocking layer
11: electron transport and injection layer

Claims (10)

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

In Formula 1,
Each X is independently N or CH, provided that at least one of X is N,
Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C _6-60 aryl; _{Substituted or unsubstituted C 2-60} heteroaryl including any one or more heteroatoms selected from the group consisting of N, O and S,
Each R is independently hydrogen; heavy hydrogen; halogen; Cyano; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted C _2-60 alkynyl; Substituted or unsubstituted C _3-30 cycloalkyl; Substituted or unsubstituted C _6-60 aryl; _{Substituted or unsubstituted C 2-60} heteroaryl including any one or more heteroatoms selected from the group consisting of N, O and S,
L is a divalent linker of the following formula (2),
[Formula 2]

In Chemical Formula 2,
Each R'is independently hydrogen; heavy hydrogen; halogen; Cyano; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted C _2-60 alkynyl; Substituted or unsubstituted C _3-30 cycloalkyl; Substituted or unsubstituted C _6-60 aryl; _{It is a C 2-60} heteroaryl containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S.
The method of claim 1,
X is all N,
compound.
The method of claim 1,
Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C _6-18 aryl, or a substituent represented by the following formula (3),
compound:
[Formula 3]

In Chemical Formula 3,
Y is O, S, or N-(phenyl).
The method of claim 1,
Ar ₁ and Ar ₂ are phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, dibenzofuranyl, dibenzothiophenyl, 9-phenyl-carbazolyl, or carbazol-9-yl,
compound.
The method of claim 1,
Each R is independently hydrogen or deuterium,
compound.
The method of claim 1,
Each R'is independently hydrogen or deuterium,
compound.
The method of claim 1,
L is any one selected from the group consisting of,
compound:

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

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 8. That is, an organic light emitting device.
The method of claim 9,
The organic material layer containing the compound is a light emitting layer,
Organic light emitting device.

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