KR102463816B1 - 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.

Description

Novel compound and organic light emitting device using the same

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

In general, the organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy using an organic material. The organic light emitting device using the organic light emitting phenomenon has a wide viewing angle, excellent contrast, fast response time, and 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 layer is often formed 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, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. When a voltage is applied between the two electrodes in the structure of the organic light emitting device, holes are injected into the organic material layer from the anode and electrons from the cathode are injected into the organic material layer. When the injected holes and electrons meet, excitons are formed, and the excitons It lights up when it falls back to the ground state.

The 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,

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

Ar ₁ is C _2-60 heteroaryl including any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,

Ar ₂ is substituted or unsubstituted C _6-60 aryl; Or substituted or unsubstituted C _2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S,

each R is independently hydrogen; heavy hydrogen; halogen; substituted or unsubstituted C _1-60 alkyl; substituted or unsubstituted C _1-60 alkoxy; substituted or unsubstituted C _6-60 aryl; or C _2-60 heteroaryl including any one or more heteroatoms selected from the group consisting of N, O and S.

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

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

1 shows an example of an organic light emitting device including a substrate 1 , an anode 2 , an organic material layer 3 , and a cathode 4 .
2 is a substrate (1), anode (2), hole injection layer (5), hole transport layer (6), electron blocking layer (7), light emitting layer (8), hole blocking layer (9), electron transport layer (10) , an example of an organic light emitting device including an electron injection layer 11 and a cathode 4 is shown.
3 is 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 (8), a hole blocking layer (9), an electron injection and transport layer ( 12) and an example of an organic light emitting device including a cathode 4 are shown.

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

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

및

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

and

means a bond connected to another substituent.

As used herein, the term "substituted or unsubstituted" refers to deuterium; halogen group; nitrile group; nitro group; hydroxyl group; carbonyl group; ester group; imid; amino group; phosphine oxide group; alkoxy group; aryloxy group; alkyl thiooxy group; arylthioxy group; an alkyl sulfoxy group; arylsulfoxy group; silyl group; boron group; an alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; aralkenyl group; an alkylaryl group; an alkylamine group; an aralkylamine group; heteroarylamine group; arylamine group; an aryl phosphine group; or N, O, and S atom means that it is substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing one or more, or substituted or unsubstituted, in which two or more substituents of the above-exemplified substituents are connected . For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.

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

In the present specification, in the ester group, the oxygen of the ester group may be substituted with a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms. Specifically, it may be a compound 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 from 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 specifically includes a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, and the like. However, the present invention is not limited thereto.

In the present specification, the boron group specifically includes a trimethylboron group, a triethylboron group, a t-butyldimethylboron group, a triphenylboron group, a phenylboron 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 number of carbon atoms in the alkyl group is 1 to 20. 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, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl and the like, but are not limited thereto.

In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to an exemplary embodiment, the carbon number of the alkenyl group is 2 to 20. According to another exemplary embodiment, the carbon number of the alkenyl group is 2 to 10. 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 carbon number of the cycloalkyl group is 3 to 20. 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 is not limited thereto.

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

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

etc. can be However, the present invention is not limited thereto.

In the present specification, the heterocyclic group is a heterocyclic group including 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 from 2 to 60 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazine group, an 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, thiadia and a jolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but is not limited thereto.

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

In Formula 1, preferably, L ₁ and L ₂ may each independently be a single bond, phenylene, or naphthalenediyl.

Preferably, Ar ₁ is any one selected from the group consisting of:

above,

A is a 6-membered heterocyclic ring comprising two N fused to an adjacent ring,

X is O or S;

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

Preferably, A is pyrimidine or pyrazine fused with adjacent rings.

Preferably, each Ar ₃ is independently phenyl, biphenylyl, naphthyl, phenylnaphthyl, naphthylphenyl, phenanthrenyl, dibenzofuranyl, dibenzothiophenyl, 9,9-dimethylfluorenyl , carbazolyl, N-phenylcarbazolyl, or N-(naphthylphenyl)carbazolyl.

Preferably, Ar ₂ may be phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, dibenzofuranyl, or dibenzothiophenyl.

Preferably, all R may be hydrogen.

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

The compound represented by Chemical Formula 1 may be prepared by a preparation method as shown in Scheme 1 below.

[Scheme 1]

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

Scheme 1 is an amine substitution reaction, preferably performed in the presence of a palladium catalyst and a base, and the reactor for the amine substitution reaction can be changed as known in the art. The manufacturing method may be more specific in Preparation Examples to be described later.

In addition, the present invention provides an organic light emitting device including the compound represented by the formula (1). In one example, the present invention provides a first electrode; a second electrode provided to face the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the compound represented by Formula 1 above. 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 multi-layer 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, etc. 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 layer may include an emission layer, and the emission layer includes the compound represented by Formula 1 above. In particular, the compound according to the present invention can be used as a host for the light emitting layer.

In addition, the organic layer may include a hole injection layer, a hole transport layer, or an electron blocking layer, the hole injection layer, the hole transport layer, or the electron blocking layer includes a compound represented by the formula (1).

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 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. Also, 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 the organic light emitting diode 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 including a substrate 1 , an anode 2 , an organic material layer 3 , and a cathode 4 . In such a structure, the compound represented by Formula 1 may be included in the organic material layer.

2 is a substrate (1), anode (2), hole injection layer (5), hole transport layer (6), electron blocking layer (7), light emitting layer (8), hole blocking layer (9), electron transport layer (10) , an example of an organic light emitting device including an electron injection layer 11 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 blocking layer, the light emitting layer, the hole blocking layer, the electron transport layer, and the electron injection layer. Preferably, the compound represented by Formula 1 may be included in the emission layer.

3 is 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 (8), a hole blocking layer (9), an electron injection and transport layer ( 12) and an example of an organic light emitting device including a cathode 4 are shown. 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. Preferably, the compound represented by Formula 1 may be included in the emission layer.

The organic light emitting device according to the present invention may be manufactured using materials and methods known in the art, except that at least one layer of the organic material layer includes the compound represented by Formula 1 above. Also, 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, by using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, a metal or conductive metal oxide or an alloy thereof is deposited on a substrate to form an anode. 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, spraying, roll coating, and the like, but is not limited thereto.

In addition to the above 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.

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

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

The hole injection layer is a layer for injecting holes from the electrode, and as a hole injection material, it has the ability to transport holes, so it has a hole injection effect at the anode, an excellent hole injection effect on the light emitting layer or the light emitting material, and is produced in the light emitting layer A compound which prevents the movement of excitons to the electron injection layer or the electron injection material and is excellent in the ability to form a thin film is preferable. It is preferable that the highest occupied molecular orbital (HOMO) 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 the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene-based organic material. of organic substances, anthraquinones, polyaniline and polythiophene-based conductive polymers, and the like, but are not limited thereto.

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

The electron suppression layer serves to improve the efficiency of the organic light emitting device by suppressing electrons injected from the cathode from being transferred to the anode without recombination in the light emitting layer.

The light emitting material is a material capable of emitting light in the visible ray region by receiving 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 include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); carbazole-based compounds; dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compounds; compounds of the benzoxazole, benzthiazole and benzimidazole series; Poly(p-phenylenevinylene) (PPV)-based polymers; spiro compounds; polyfluorene, rubrene, and the like, but is not limited thereto.

The emission layer may include a host material and a dopant material. The host material includes a condensed aromatic ring derivative or a heterocyclic compound containing compound. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc., and heterocyclic-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto. Preferably, the light emitting layer host material may include the compound of Formula 1 above.

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

The hole blocking layer serves to improve the efficiency of the organic light emitting device by suppressing the transfer of holes injected from the anode to the cathode without recombination in the light emitting layer.

The electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer. do. Specific examples include Al complex of 8-hydroxyquinoline; complexes comprising Alq ₃ ; organic radical compounds; hydroxyflavone-metal complexes, and the like, but are not limited thereto. The electron transport layer may be used with any desired cathode material as used in accordance with the prior art. In particular, examples of suitable cathode materials are conventional materials having a low work function and followed by a layer of aluminum or silver. Specifically cesium, barium, calcium, ytterbium and samarium, followed in each case by an aluminum layer or a silver layer.

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 on the light emitting layer or the light emitting material, and hole injection of excitons generated in the light emitting layer. A compound which prevents movement to a layer and is excellent in the ability to form a thin film is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, triazine, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, etc. derivatives, metal 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-crezolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtolato)gallium, etc. However, the present invention is not limited thereto.

According to one embodiment of the present invention, the electron transport material and the electron injection material may be simultaneously deposited to form a single layer of the electron injection and transport layer.

The organic light emitting device according to the present invention may be a top emission type, a back emission type, or a double side 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 compound represented by Formula 1 and the preparation of an organic light emitting device including the same will be described in detail in Examples below. However, the following examples are intended to illustrate the present invention, and the scope of the present invention is not limited thereto.

[Synthesis Example]

Synthesis Example 1

Formula A (10 g, 30.3 mmol), sub1 (12.2 g, 33.3 mmol), potassium phosphate (12.8 g, 60.5 mmol) were added to 200 ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.8 g of sub1-a. (Yield 64%, MS: [M+H]+= 662)

In a nitrogen atmosphere, sub5-a (10 g, 13.6 mmol), sub_d (2.3 g, 14.9 mmol), and sodiium-tert-butoxide (2.6 g, 27.1 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.6 g of Compound 1. (yield 69%, MS: [M+H]+= 814)

Synthesis Example 2

Formula A (10 g, 30.3 mmol), sub2 (14 g, 33.3 mmol), potassium phosphate (12.8 g, 60.5 mmol) were added to 200 ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.4 g of sub2-a. (Yield 53%, MS: [M+H]+= 714)

In a nitrogen atmosphere, sub2-a (10 g, 14 mmol), sub_b (4.4 g, 15.4 mmol), and sodiium-tert-butoxide (2.7 g, 28 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9 g of Compound 2. (Yield 70%, MS: [M+H]+= 916)

Synthesis Example 3

Formula A (10 g, 30.3 mmol), sub3 (14 g, 33.3 mmol), and potassium phosphate (12.8 g, 60.5 mmol) were added to 200 ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.7 g of sub3-a. (Yield 54%, MS: [M+H]+= 714)

In a nitrogen atmosphere, sub3-a (10 g, 14 mmol), sub_c (4.1 g, 15.4 mmol), and sodiium-tert-butoxide (2.7 g, 28 mmol) were added to 200 ml of Xylene, stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 8.8 g of Compound 3. (Yield 70%, MS: [M+H]+= 896)

Synthesis Example 4

Formula A (10 g, 30.3 mmol), sub4 (8.9 g, 33.3 mmol), and potassium phosphate (12.8 g, 60.5 mmol) were added to 200 ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 8.5 g of sub4-a. (Yield 50%, MS: [M+H]+= 562)

In a nitrogen atmosphere, sub4-a (10 g, 19.4 mmol), sub_d (3.3 g, 21.3 mmol), and sodiium-tert-butoxide (3.7 g, 38.7 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 8.4 g of compound 4. (Yield 68%, MS: [M+H]+= 638)

Synthesis Example 5

Formula A (10 g, 30.3 mmol), sub5 (14.8 g, 33.3 mmol), potassium phosphate (12.8 g, 60.5 mmol) were added to 200 ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.3 g of sub5-a. (Yield 64%, MS: [M+H]+= 738)

In a nitrogen atmosphere, sub5-a (10 g, 13.6 mmol), sub_d (2.3 g, 14.9 mmol), and sodiium-tert-butoxide (2.6 g, 27.1 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.6 g of compound 5. (yield 69%, MS: [M+H]+= 814)

Synthesis Example 6

Formula A (10 g, 30.3 mmol), sub6 (11.4 g, 33.3 mmol), potassium phosphate (12.8 g, 60.5 mmol) were added to 200 ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.4 g of sub6-a. (yield 59%, MS: [M+H]+= 638)

In a nitrogen atmosphere, sub6-a (10 g, 15.7 mmol), sub_d (2.7 g, 17.2 mmol), and sodiium-tert-butoxide (3 g, 31.4 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added thereto. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 5.7 g of compound 6. (Yield 51%, MS: [M+H]+= 714)

Synthesis Example 7

Formula A (10 g, 30.3 mmol), sub7 (11.9 g, 33.3 mmol), and potassium phosphate (12.8 g, 60.5 mmol) were added to 200 ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.1 g of sub7-a. (Yield 51%, MS: [M+H] + = 652)

In a nitrogen atmosphere, sub7-a (10 g, 15.3 mmol), sub_e (3.9 g, 16.9 mmol), and sodiium-tert-butoxide (2.9 g, 30.7 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added thereto. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 8.6 g of Compound 7. (Yield 70%, MS: [M+H]+= 804)

Synthesis Example 8

Formula A (10 g, 30.3 mmol), sub8 (15 g, 33.3 mmol), and potassium phosphate (12.8 g, 60.5 mmol) were added to 200 ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.6 g of sub8-a. (Yield 56%, MS: [M+H] + = 744)

In a nitrogen atmosphere, sub8-a (10 g, 13.4 mmol), sub_f (3.9 g, 14.8 mmol), and sodiium-tert-butoxide (2.6 g, 26.9 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.1 g of compound 8. (Yield 50%, MS: [M+H]+= 910)

Synthesis Example 9

Formula A (10 g, 30.3 mmol), sub9 (14.1 g, 33.3 mmol), potassium phosphate (12.8 g, 60.5 mmol) were added to 200 ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.3 g of sub9-a. (Yield 52%, MS: [M+H]+= 717)

In a nitrogen atmosphere, sub9-a (10 g, 13.9 mmol), sub_d (2.4 g, 15.3 mmol), and sodiium-tert-butoxide (2.7 g, 27.9 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7 g of compound 9. (Yield 63%, MS: [M+H]+=793)

Synthesis Example 10

Formula A (10 g, 30.3 mmol), sub10 (9.9 g, 33.3 mmol), and potassium phosphate (12.8 g, 60.5 mmol) were added to 200 ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 8.9 g of sub10-a. (Yield 50%, MS: [M+H] + = 591)

In a nitrogen atmosphere, sub10-a (10 g, 16.9 mmol), sub_d (2.9 g, 18.6 mmol), and sodiium-tert-butoxide (3.3 g, 33.9 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added thereto. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.9 g of compound 10. (Yield 61%, MS: [M+H]+= 667)

Synthesis Example 11

Formula A (10 g, 30.3 mmol), sub11 (12.9 g, 33.3 mmol), potassium phosphate (12.8 g, 60.5 mmol) were added to 200 ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13 g of sub11-a. (Yield 63%, MS: [M+H] + = 681)

In a nitrogen atmosphere, sub11-a (10 g, 14.7 mmol), sub_g (3.3 g, 16.2 mmol), and sodiium-tert-butoxide (2.8 g, 29.4 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added thereto. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 8.1 g of compound 11. (Yield 68%, MS: [M+H] + = 807)

Synthesis Example 12

Formula A (10 g, 30.3 mmol), sub12 (11.5 g, 33.3 mmol), and potassium phosphate (12.8 g, 60.5 mmol) were added to 200 ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.1 g of sub12-a. (Yield 52%, MS: [M+H] + = 641)

In a nitrogen atmosphere, sub12-a (10 g, 15.6 mmol), sub_h (4 g, 17.2 mmol), and sodiium-tert-butoxide (3 g, 31.2 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added thereto. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.7 g of compound 12. (Yield 54%, MS: [M+H] + = 793)

Synthesis Example 13

Formula A (10 g, 30.3 mmol), sub13 (15.4 g, 33.3 mmol), and potassium phosphate (12.8 g, 60.5 mmol) were added to 200 ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.2 g of sub13-a. (Yield 62%, MS: [M+H]+= 756)

In a nitrogen atmosphere, sub13-a (10 g, 13.2 mmol), sub_d (2.3 g, 14.6 mmol), and sodiium-tert-butoxide (2.5 g, 26.5 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.4 g of compound 13. (Yield 67%, MS: [M+H] + = 832)

Synthesis Example 14

Formula A (10 g, 30.3 mmol), sub14 (13.4 g, 33.3 mmol), potassium phosphate (12.8 g, 60.5 mmol) in a nitrogen atmosphere was added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.9 g of sub14-a. (Yield 66%, MS: [M+H]+= 698)

In a nitrogen atmosphere, sub14-a (10 g, 14.4 mmol), sub_i (5.1 g, 15.8 mmol), and sodiium-tert-butoxide (2.8 g, 28.7 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 8.3 g of compound 14. (Yield 62%, MS: [M+H]+= 939)

Synthesis Example 15

Formula A (10 g, 30.3 mmol), sub15 (12.8 g, 33.3 mmol), and potassium phosphate (12.8 g, 60.5 mmol) were added to 200 ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.8 g of sub15-a. (Yield 67%, MS: [M+H]+= 680)

In a nitrogen atmosphere, sub15-a (10 g, 14.7 mmol), sub_g (3.4 g, 16.2 mmol), and sodiium-tert-butoxide (2.8 g, 29.4 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added thereto. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 8.3 g of compound 15. (Yield 70%, MS: [M+H]+= 806)

Synthesis Example 16

Formula A (10 g, 30.3 mmol), sub16 (12.3 g, 33.3 mmol), and potassium phosphate (12.8 g, 60.5 mmol) were added to 200 ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.9 g of sub16-a. (yield 69%, MS: [M+H]+= 665)

In a nitrogen atmosphere, sub16-a (10 g, 15 mmol), sub_d (2.6 g, 16.5 mmol), and sodiium-tert-butoxide (2.9 g, 30.1 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added thereto. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.2 g of compound 16. (Yield 56%, MS: [M+H] + = 741)

Synthesis Example 17

Formula A (10 g, 30.3 mmol), sub17 (12.7 g, 33.3 mmol), potassium phosphate (12.8 g, 60.5 mmol) in a nitrogen atmosphere was added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.8 g of sub17-a. (Yield 53%, MS: [M+H] + = 675)

In a nitrogen atmosphere, sub17-a (10 g, 14.8 mmol), sub_d (2.6 g, 16.3 mmol), and sodiium-tert-butoxide (2.8 g, 29.6 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added thereto. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.4 g of compound 17. (Yield 67%, MS: [M+H]+= 751)

Synthesis Example 18

Formula A (10 g, 30.3 mmol), sub18 (13.5 g, 33.3 mmol), potassium phosphate (12.8 g, 60.5 mmol) were added to 200 ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.6 g of sub18-a. (Yield 64%, MS: [M+H]+= 701)

In a nitrogen atmosphere, sub18-a (10 g, 14.3 mmol), sub_b (4.4 g, 15.7 mmol), and sodiium-tert-butoxide (2.7 g, 28.5 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.8 g of compound 18. (Yield 62%, MS: [M+H]+= 883)

Synthesis Example 19

Formula A (10 g, 30.3 mmol), sub19 (12.7 g, 33.3 mmol), potassium phosphate (12.8 g, 60.5 mmol) were added to 200 ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.2 g of sub19-a. (Yield 55%, MS: [M+H] + = 675)

In a nitrogen atmosphere, sub19-a (10 g, 14.8 mmol), sub_d (2.6 g, 16.3 mmol), and sodiium-tert-butoxide (2.8 g, 29.6 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added thereto. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 5.6 g of compound 19. (Yield 50%, MS: [M+H]+= 751)

Synthesis Example 20

Formula A (10 g, 30.3 mmol), sub20 (12.3 g, 33.3 mmol), and potassium phosphate (12.8 g, 60.5 mmol) were added to 200 ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.7 g of sub20-a. (Yield 68%, MS: [M+H]+= 665)

In a nitrogen atmosphere, sub20-a (10 g, 15 mmol), sub_j (5.1 g, 16.5 mmol), and sodiium-tert-butoxide (2.9 g, 30.1 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added thereto. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.4 g of compound 20. (Yield 55%, MS: [M+H]+= 893)

Synthesis Example 21

Formula A (10 g, 30.3 mmol), sub21 (14.8 g, 33.3 mmol), potassium phosphate (12.8 g, 60.5 mmol) were added to 200 ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.7 g of sub21-a. (Yield 70%, MS: [M+H]+= 740)

In a nitrogen atmosphere, sub21-a (10 g, 13.5 mmol), sub_d (2.3 g, 14.9 mmol), and sodiium-tert-butoxide (2.6 g, 27 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.1 g of compound 21. (Yield 55%, MS: [M+H]+= 816)

Synthesis Example 22

Formula A (10 g, 30.3 mmol), sub22 (9.7 g, 33.3 mmol), and potassium phosphate (12.8 g, 60.5 mmol) were added to 200 ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.3 g of sub22-a. (Yield 58%, MS: [M+H]+=585)

In a nitrogen atmosphere, sub22-a (10 g, 17.1 mmol), sub_e (4.4 g, 18.8 mmol), and sodiium-tert-butoxide (3.3 g, 34.2 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added thereto. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 8.6 g of compound 22. (Yield 68%, MS: [M+H]+=737)

Synthesis Example 23

Formula A (10 g, 30.3 mmol), sub23 (9.7 g, 33.3 mmol), and potassium phosphate (12.8 g, 60.5 mmol) were added to 200 ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9 g of sub23-a. (Yield 51%, MS: [M+H]+=585)

In a nitrogen atmosphere, sub23-a (10 g, 17.1 mmol), sub_e (4.4 g, 18.8 mmol), and sodiium-tert-butoxide (3.3 g, 34.2 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added thereto. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.5 g of compound 23. (Yield 52%, MS: [M+H]+=737)

Synthesis Example 24

Formula A (10 g, 30.3 mmol), sub24 (11 g, 33.3 mmol), potassium phosphate (12.8 g, 60.5 mmol) were put in 200 ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.9 g of sub24-a. (Yield 63%, MS: [M+H]+= 625)

In a nitrogen atmosphere, sub24-a (10 g, 16 mmol), sub_j (5.4 g, 17.6 mmol), and sodiium-tert-butoxide (3.1 g, 32 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added thereto. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9 g of Compound 24. (Yield 66%, MS: [M+H]+= 853)

Synthesis Example 25

Formula A (10 g, 30.3 mmol), sub25 (11.5 g, 33.3 mmol), potassium phosphate (12.8 g, 60.5 mmol) were added to 200 ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.6 g of sub25-a. (Yield 70%, MS: [M+H]+= 641)

In a nitrogen atmosphere, sub25-a (10 g, 15.6 mmol), sub_k (4.2 g, 17.2 mmol), and sodiium-tert-butoxide (3 g, 31.2 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added thereto. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 8.6 g of compound 25. (Yield 68%, MS: [M+H] + = 807)

Synthesis Example 26

Formula A (10 g, 30.3 mmol), sub26 (11.5 g, 33.3 mmol), potassium phosphate (12.8 g, 60.5 mmol) were added to 200 ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9.9 g of sub26-a. (Yield 51%, MS: [M+H] + = 641)

In a nitrogen atmosphere, sub26-a (10 g, 15.6 mmol), sub_l (5.5 g, 17.2 mmol), and sodiium-tert-butoxide (3 g, 31.2 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added thereto. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.8 g of compound 26. (Yield 57%, MS: [M+H]+= 883)

Synthesis Example 27

Formula A (10 g, 30.3 mmol), sub27 (13.5 g, 33.3 mmol), potassium phosphate (12.8 g, 60.5 mmol) were added to 200 ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.2 g of sub27-a. (Yield 53%, MS: [M+H]+= 700)

In a nitrogen atmosphere, sub27-a (10 g, 14.3 mmol), sub_d (3.7 g, 15.7 mmol), and sodiium-tert-butoxide (2.7 g, 28.6 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.4 g of compound 27. (Yield 53%, MS: [M+H]+= 852)

Synthesis Example 28

Formula A (10 g, 30.3 mmol), sub28 (11 g, 33.3 mmol), and potassium phosphate (12.8 g, 60.5 mmol) were added to 200 ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.3 g of sub28-a. (Yield 60%, MS: [M+H]+= 624)

In a nitrogen atmosphere, sub28-a (10 g, 16 mmol), sub_m (5.9 g, 17.6 mmol), and sodiium-tert-butoxide (3.1 g, 32.1 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added thereto. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.7 g of compound 28. (Yield 55%, MS: [M+H] + = 876)

Synthesis Example 29

Formula A (10 g, 30.3 mmol), sub29 (10.5 g, 33.3 mmol), potassium phosphate (12.8 g, 60.5 mmol) were added to 200 ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.6 g of sub29-a. (Yield 68%, MS: [M+H]+= 611)

In a nitrogen atmosphere, sub29-a (10 g, 16.4 mmol), sub_d (2.8 g, 18 mmol), and sodiium-tert-butoxide (3.1 g, 32.7 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added thereto. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.3 g of compound 29. (Yield 56%, MS: [M+H]+= 687)

Synthesis Example 30

Formula A (10 g, 30.3 mmol), sub30 (15.2 g, 33.3 mmol), potassium phosphate (12.8 g, 60.5 mmol) were added to 200 ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12 g of sub30-a. (Yield 53%, MS: [M+H]+=750)

In a nitrogen atmosphere, sub30-a (10 g, 13.3 mmol), sub_g (3 g, 14.7 mmol), and sodiium-tert-butoxide (2.6 g, 26.7 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.2 g of compound 30. (Yield 53%, MS: [M+H] + = 876)

Synthesis Example 31

Formula A (10 g, 30.3 mmol), sub31 (13.2 g, 33.3 mmol), and potassium phosphate (12.8 g, 60.5 mmol) were added to 200 ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.5 g of sub31-a. (Yield 60%, MS: [M+H] + = 691)

In a nitrogen atmosphere, sub31-a (10 g, 14.5 mmol), sub_n (3.3 g, 15.9 mmol), and sodiium-tert-butoxide (2.8 g, 29 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.2 g of compound 31. (Yield 61%, MS: [M+H]+= 817)

Synthesis Example 32

Formula A (10 g, 30.3 mmol), sub32 (12.7 g, 33.3 mmol), potassium phosphate (12.8 g, 60.5 mmol) were added to 200 ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.2 g of sub32-a. (Yield 55%, MS: [M+H]+= 675)

In a nitrogen atmosphere, sub32-a (10 g, 14.8 mmol), sub_k (4 g, 16.3 mmol), and sodiium-tert-butoxide (2.8 g, 29.6 mmol) were added to 200 ml of Xylene, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added thereto. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.6 g of compound 32. (Yield 61%, MS: [M+H]+= 841)

Synthesis Example 33

Chemical formula A (10 g, 30.3 mmol), sub33 (13.2 g, 33.3 mmol), potassium phosphate (12.8 g, 60.5 mmol) were added to 200 ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was completed, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.9 g of sub33-a. (Yield 52%, MS: [M+H] + = 691)

In a nitrogen atmosphere, sub33-a (10 g, 14.5 mmol), sub_g (3.3 g, 15.9 mmol), and sodiium-tert-butoxide (2.8 g, 29 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.6 g of compound 33. (Yield 56%, MS: [M+H]+= 817)

Synthesis Example 34

Formula A (10 g, 30.3 mmol), sub34 (14.7 g, 33.3 mmol), potassium phosphate (12.8 g, 60.5 mmol) were added to 200 ml of Xylene in a nitrogen atmosphere, and stirred and refluxed. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12 g of sub34-a. (Yield 54%, MS: [M+H]+=737)

In a nitrogen atmosphere, sub34-a (10 g, 13.6 mmol), sub_d (2.3 g, 14.9 mmol), and sodiium-tert-butoxide (2.6 g, 27.1 mmol) were added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature and reducing the pressure. After that, the compound was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.8 g of compound 34. (Yield 62%, MS: [M+H]+= 813)

[Example]

Comparative Example 1

A glass substrate coated with indium tin oxide (ITO) to a thickness of 1,000 Å was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, a product manufactured by Fischer Co. was used as the detergent, and distilled water that was secondarily filtered with a filter manufactured by Millipore Co. was used as the distilled water. After washing ITO for 30 minutes, ultrasonic cleaning was performed for 10 minutes by repeating twice with distilled water. After washing with distilled water, ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, and after drying, it was 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 thus prepared ITO transparent electrode, the following HI-1 compound was formed as a hole injection layer to a thickness of 1150 Å, but the following A-1 compound 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. Then, the following EB-1 compound was vacuum-deposited to a thickness of 150 Å on the hole transport layer to form an electron blocking layer. Next, the following RH-1 compound and the following Dp-7 compound were vacuum-deposited in a weight ratio of 98:2 on the EB-1 deposited film to form a red light emitting layer having a thickness of 400 Å. A hole blocking layer was formed by vacuum-depositing the following HB-1 compound to a thickness of 30 Å on the light emitting layer. Then, the following ET-1 compound and the following LiQ compound were vacuum-deposited on the hole blocking layer in a weight ratio of 2:1 to form an electron injection and transport layer to a thickness of 300 Å. A cathode was formed by sequentially depositing lithium fluoride (LiF) to a thickness of 12 Å and aluminum to a thickness of 1,000 Å on the electron injection and transport layer.

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

Examples 1-34

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

Comparative Examples 2 to 9

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

Experimental example

When a current of 10 mA/cm ² was applied to the organic light emitting devices of Examples 1 to 34 and Comparative Examples 1 to 9, driving voltage, efficiency, and lifetime were measured, and the results are shown in Table 1 below. The lifetime T95 means the time (hr) required for the luminance to decrease from the initial luminance (6000 nit) to 95%.

division compound Driving voltage (V) Efficiency (cd/A) Life T95 (hr) luminous color Example 1 compound 1 3.65 26.3 173 Red Example 2 compound 2 3.60 27.7 177 Red Example 3 compound 3 3.62 28.3 175 Red Example 4 compound 4 3.64 28.8 161 Red Example 5 compound 5 3.60 28.5 202 Red Example 6 compound 6 3.54 28.3 234 Red Example 7 compound 7 3.59 28.0 205 Red Example 8 compound 8 3.61 27.3 193 Red Example 9 compound 9 3.82 25.3 184 Red Example 10 compound 10 3.72 26.5 194 Red Example 11 compound 11 3.85 27.4 173 Red Example 12 compound 12 3.88 25.2 Red Example 13 compound 13 3.74 26.7 194 Red Example 14 compound 14 3.73 27.1 182 Red Example 15 compound 15 3.72 26.4 174 Red Example 16 compound 16 3.74 27.6 186 Red Example 17 compound 17 3.71 26.5 167 Red Example 18 compound 18 3.79 27.4 191 Red Example 19 compound 19 3.73 25.3 164 Red Example 20 compound 20 3.74 26.5 196 Red Example 21 compound 21 3.69 27.7 188 Red Example 22 compound 22 3.75 28.2 202 Red Example 23 compound 23 3.76 27.0 185 Red Example 24 compound 24 3.64 26.7 197 Red Example 25 compound 25 3.79 27.4 172 Red Example 26 compound 26 3.71 26.5 195 Red Example 27 compound 27 3.79 27.6 187 Red Example 28 compound 28 3.78 28.3 182 Red Example 29 compound 29 3.76 27.5 194 Red Example 30 compound 30 3.73 25.4 167 Red Example 31 compound 31 3.61 23.3 182 Red Example 32 compound 32 3.60 25.1 Red Example 33 compound 33 3.79 24.0 198 Red Example 34 compound 34 3.69 26.3 201 Red Comparative Example 1 RH-1 4.14 21.3 139 Red Comparative Example 2 C-1 4.01 20.4 84 Red Comparative Example 3 C-2 4.05 19.2 62 Red Comparative Example 4 C-3 3.93 22.6 Red Comparative Example 5 C-4 4.37 19.3 131 Red Comparative Example 6 C-5 4.14 20.2 87 Red Comparative Example 7 C-6 4.03 20.9 113 Red Comparative Example 8 C-7 4.08 19.3 68 Red Comparative Example 9 C-8 4.12 20.8 107 Red

As shown in Table 1, the organic light emitting device manufactured by using the compound of the present invention as a light emitting layer host exhibited excellent characteristics in terms of driving voltage, efficiency, and lifespan.

1: Substrate 2: Anode
3: organic layer 4: cathode
5: hole injection layer 6: hole transport layer
7: electron suppression layer 8: light emitting layer
9: hole blocking layer 10: electron transport layer
11: electron injection layer 12: electron injection and transport layer

Claims (9)

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

In Formula 1,
L ₁ and L ₂ are each independently a single bond; Or a substituted or unsubstituted C _6-60 arylene,
Ar ₁ is C _2-60 heteroaryl including any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,
Ar ₂ is substituted or unsubstituted C _6-60 aryl; Or substituted or unsubstituted C _2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S,
each R is independently hydrogen; heavy hydrogen; halogen; substituted or unsubstituted C _1-60 alkyl; substituted or unsubstituted C _1-60 alkoxy; substituted or unsubstituted C _6-60 aryl; or C _2-60 heteroaryl containing at least one heteroatom selected from the group consisting of N, O and S;
However, the following compounds are excluded from the compounds represented by Formula 1 above.

According to claim 1,
L ₁ and L ₂ are each independently a single bond, phenylene, or naphthalenediyl,
compound.
According to claim 1,
Ar ₁ is any one selected from the group consisting of
compound:

above,
A is a 6-membered heterocycle comprising two N, fused to an adjacent ring,
X is O or S;
Ar ₃ are each independently, substituted or unsubstituted C _6-60 aryl; or C _2-60 heteroaryl including any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S.
4. The method of claim 3,
Ar ₃ is each independently, phenyl, biphenylyl, naphthyl, phenylnaphthyl, naphthylphenyl, phenanthrenyl, dibenzofuranyl, dibenzothiophenyl, 9,9-dimethylfluorenyl, carbazolyl, which is N-phenylcarbazolyl, or N-(naphthylphenyl)carbazolyl;
compound.
According to claim 1,
Ar ₂ is phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, dibenzofuranyl, or dibenzothiophenyl;
compound.
According to claim 1,
R is all hydrogen,
compound.
According to claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of
compound:

a first electrode; a second electrode provided to face the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers contains the compound according to any one of claims 1 to 7 which is an organic light emitting device.
9. The method of claim 8,
The organic material layer containing the compound is a light emitting layer,
organic light emitting device.

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