KR102413613B1 - 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 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 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. In the structure of the organic light emitting device, when a voltage is applied between the two electrodes, 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 When it falls back to the ground state, it lights up.

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,

each X is independently N, or CH, provided that at least two of X are N;

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

R ₁ to R ₄ are all hydrogen or deuterium; or two adjacent ones of R ₁ to R ₄ combine to form a benzene ring, and the remainder is hydrogen or deuterium;

R ₅ is hydrogen or deuterium,

R ₆ is each independently hydrogen, or deuterium,

n is an integer from 1 to 3.

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 an organic layer of an 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 Chemical Formula 1 described above 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.

FIG. 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.

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

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

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

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; a phosphine oxide group; alkoxy group; aryloxy group; an 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 arylphosphine 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, two or more of the above-exemplified substituents are linked. . 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 in the carbonyl group is not particularly limited, but 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, in the ester group, 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, but is not limited to, a trimethylboron group, a triethylboron group, a t-butyldimethylboron group, a triphenylboron group, a phenylboron group, and the like.

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 number of carbon atoms in the alkyl group is 1 to 10. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl 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 above-described examples of the alkenyl group. 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, all X are N.

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

More preferably, Ar ₁ and Ar ₂ are each independently selected from unsubstituted phenyl; phenyl substituted with 5 deuterium; biphenylyl; naphthyl; phenanthryl; dibenzofuranyl; dibenzothiophenyl; carbazolyl; or 9-phenylcarbazolyl.

Preferably, R ₅ is hydrogen.

Preferably, R ₆ is hydrogen.

On the other hand, that adjacent two of R ₁ to R ₄ combine to form a benzene ring, and the remainder is hydrogen or deuterium, specifically, R ₁ and R ₂ are bonded, R ₂ and R ₃ are bonded, or R It means that ₃ and R ₄ combine to form a benzene ring. For example, when R ₁ and R ₂ are combined to form a benzene ring, Chemical Formula 1 is represented by the following Chemical Formula 1-1.

[Formula 1-1]

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

In addition, the present invention provides a method for preparing a compound represented by Formula 1 as shown in Scheme 1 below.

[Scheme 1]

In the above, X, Ar ₁ , Ar ₂ , R ₁ to R ₆ , and n are as defined in Formula 1, X′ is halogen, preferably X′ is chloro or bromo.

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 a synthesis example to be described later.

In addition, the present invention provides an organic light emitting device comprising the compound represented by Formula 1 above. 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. 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 the organic light emitting diode according to an embodiment of the present invention is illustrated in FIGS. 1 and 2 .

FIG. 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 comprising 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.

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 diode 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 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 into 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 this 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 multilayer structure 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, and conductive polymers of polyaniline and polythiophene series, 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. As a hole transport material, a material capable of transporting holes from the anode or hole injection layer to the light emitting layer and transferring them to the light emitting layer. 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 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.

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, periflanthene, and the like, having an arylamino group. As the styrylamine compound, a substituted or unsubstituted As a compound in which at least one arylvinyl group is substituted in the arylamine, 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, 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 them to the light emitting layer. 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 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, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, etc., derivatives thereof, metals complex compounds and nitrogen-containing 5-membered ring derivatives, but are not limited thereto.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h] Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) ( o-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.

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

In a nitrogen atmosphere, sub6 (10 g, 20.7 mmol), compound B (6.1 g, 22.7 mmol), and sodium tert-butoxide (4 g, 41.3 mmol) were added to 200 ml of xylene, and the mixture was stirred and refluxed. Then, 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 under reduced pressure after cooling to room temperature. Then, the compound was completely dissolved in chloroform again, 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 1. (Yield 52%, MS: [M+H]+= 715)

Synthesis Example 2

In a nitrogen atmosphere, sub2 (10 g, 17.9 mmol), compound B (5.3 g, 19.6 mmol), and sodium tert-butoxide (3.4 g, 35.7 mmol) were added to 200 ml of xylene, followed by stirring and reflux. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. After 2 hours, the reaction was terminated, and the solvent was removed under reduced pressure after cooling to room temperature. Then, the compound was completely dissolved in chloroform again, 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 2. (Yield 61%, MS: [M+H] + = 791)

Synthesis Example 3

In a nitrogen atmosphere, sub3 (10 g, 16.9 mmol), compound A (4.1 g, 18.6 mmol), and sodium tert-butoxide (3.3 g, 33.9 mmol) were added to 200 ml of xylene, followed by stirring and reflux. Then, 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 under reduced pressure after cooling to room temperature. Then, the compound was completely dissolved in chloroform again, 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 8.7 g of Compound 3. (Yield 67%, MS: [M+H] + = 771)

Synthesis Example 4

In a nitrogen atmosphere, sub4 (10 g, 15.8 mmol), compound C (4.6 g, 17.3 mmol), and sodium tert-butoxide (3 g, 31.5 mmol) were added to 200 ml of xylene, followed by stirring and reflux. Then, 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 under reduced pressure after cooling to room temperature. Then, the compound was completely dissolved in chloroform again, 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 g of compound 4 . (yield 59%, MS: [M+H]+= 865)

Synthesis Example 5

In a nitrogen atmosphere, sub5 (10 g, 15.6 mmol), compound B (4.6 g, 17.2 mmol), and sodium tert-butoxide (3 g, 31.2 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, 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 under reduced pressure after cooling to room temperature. Then, the compound was completely dissolved in chloroform again, 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 8.7 g of compound 5. (Yield 64%, MS: [M+H] + = 871)

Synthesis Example 6

In a nitrogen atmosphere, sub6 (10 g, 14.3 mmol), compound A (3.4 g, 15.7 mmol), and sodium tert-butoxide (2.7 g, 28.6 mmol) were added to 200 ml of xylene, followed by stirring and reflux. Thereafter, 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 under reduced pressure after cooling to room temperature. Then, the compound was completely dissolved in chloroform again, 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 8.7 g of Compound 6. (yield 69%, MS: [M+H]+= 880)

Synthesis Example 7

In a nitrogen atmosphere, sub7 (10 g, 15.1 mmol), compound B (4.5 g, 16.7 mmol), and sodium tert-butoxide (2.9 g, 30.3 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, 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 under reduced pressure after cooling to room temperature. Then, the compound was completely dissolved in chloroform again, 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 Compound 7. (Yield 63%, MS: [M+H]+= 891)

Synthesis Example 8

In a nitrogen atmosphere, sub8 (10 g, 15 mmol), compound B (4.4 g, 16.5 mmol), and sodium tert-butoxide (2.9 g, 30 mmol) were added to 200 ml of xylene, followed by stirring and reflux. Then, 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 under reduced pressure after cooling to room temperature. Then, the compound was completely dissolved in chloroform again, 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 8. (Yield 62%, MS: [M+H]+= 897)

Synthesis Example 9

In a nitrogen atmosphere, sub9 (10 g, 15.4 mmol), compound B (4.5 g, 16.9 mmol), and sodium tert-butoxide (3 g, 30.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, 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 under reduced pressure after cooling to room temperature. Then, the compound was completely dissolved in chloroform again, 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 7.3 g of compound 9. (Yield 54%, MS: [M+H] + = 881)

Synthesis Example 10

In a nitrogen atmosphere, sub10 (10 g, 15 mmol), compound C (4.4 g, 16.5 mmol), and sodium tert-butoxide (2.9 g, 30 mmol) were added to 200 ml of xylene, followed by stirring and reflux. Then, 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 under reduced pressure after cooling to room temperature. Then, the compound was completely dissolved in chloroform again, 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 10. (Yield 52%, MS: [M+H] + = 897)

Synthesis Example 11

In a nitrogen atmosphere, sub11 (10 g, 16.4 mmol), compound D (4.8 g, 18 mmol), and sodium tert-butoxide (3.2 g, 32.8 mmol) were added to 200 ml of xylene, and the mixture was stirred and refluxed. Then, 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 under reduced pressure after cooling to room temperature. Then, the compound was completely dissolved in chloroform again, 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 11. (Yield 55%, MS: [M+H]+= 725)

Synthesis Example 12

In a nitrogen atmosphere, sub12 (10 g, 16.4 mmol), compound C (4.8 g, 18 mmol), and sodium tert-butoxide (3.2 g, 32.8 mmol) were added to 200 ml of xylene, followed by stirring and reflux. Then, 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 under reduced pressure after cooling to room temperature. Then, the compound was completely dissolved in chloroform again, 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 7.3 g of Compound 12. (Yield 55%, MS: [M+H]+= 815)

Synthesis Example 13

In a nitrogen atmosphere, sub13 (10 g, 16.4 mmol), compound A (3.9 g, 18 mmol), and sodium tert-butoxide (3.2 g, 32.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, 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 under reduced pressure after cooling to room temperature. Then, the compound was completely dissolved in chloroform again, 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 13. (Yield 54%, MS: [M+H] + = 771)

Synthesis Example 14

In a nitrogen atmosphere, sub14 (10 g, 16.4 mmol), compound A (3.9 g, 18 mmol), and sodium tert-butoxide (3.2 g, 32.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, 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 under reduced pressure after cooling to room temperature. Then, the compound was completely dissolved in chloroform again, 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 14. (Yield 60%, MS: [M+H] + = 791)

Synthesis Example 15

In a nitrogen atmosphere, sub15 (10 g, 16.4 mmol), compound A (3.9 g, 18 mmol), and sodium tert-butoxide (3.2 g, 32.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, 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 under reduced pressure after cooling to room temperature. Then, the compound was completely dissolved in chloroform again, 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 15. (Yield 57%, MS: [M+H] + = 791)

Synthesis Example 16

In a nitrogen atmosphere, sub16 (10 g, 16.4 mmol), compound D (4.8 g, 18 mmol), and sodium tert-butoxide (3.2 g, 32.8 mmol) were added to 200 ml of xylene, and stirred and refluxed. Then, 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 under reduced pressure after cooling to room temperature. Then, the compound was completely dissolved in chloroform again, 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 7.5 g of compound 16. (Yield 53%, MS: [M+H]+= 867)

Synthesis Example 17

In a nitrogen atmosphere, sub17 (10 g, 16.4 mmol), compound A (3.9 g, 18 mmol), and sodium tert-butoxide (3.2 g, 32.8 mmol) were added to 200 ml of xylene, followed by stirring and reflux. Then, 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 under reduced pressure after cooling to room temperature. Then, the compound was completely dissolved in chloroform again, 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 17. (Yield 52%, MS: [M+H]+= 906)

Synthesis Example 18

In a nitrogen atmosphere, sub18 (10 g, 16.4 mmol), compound C (4.8 g, 18 mmol), and sodium tert-butoxide (3.2 g, 32.8 mmol) were added to 200 ml of xylene, followed by stirring and reflux. Then, 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 under reduced pressure after cooling to room temperature. Then, the compound was completely dissolved in chloroform again, 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 9.1 g of compound 18. (Yield 58%, MS: [M+H]+=956)

Synthesis Example 19

In a nitrogen atmosphere, sub19 (10 g, 16.4 mmol), compound B (4.8 g, 18 mmol), and sodium tert-butoxide (3.2 g, 32.8 mmol) were added to 200 ml of xylene, and the mixture was stirred and refluxed. Then, 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 under reduced pressure after cooling to room temperature. Then, the compound was completely dissolved in chloroform again, 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 compound 19. (Yield 61%, MS: [M+H]+= 891)

Synthesis Example 20

In a nitrogen atmosphere, sub20 (10 g, 16.4 mmol), compound C (4.8 g, 18 mmol), and sodium tert-butoxide (3.2 g, 32.8 mmol) were added to 200 ml of xylene, followed by stirring and reflux. Then, 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 under reduced pressure after cooling to room temperature. Then, the compound was completely dissolved in chloroform again, 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 9.1 g of compound 20. (Yield 58%, MS: [M+H]+=956)

Synthesis Example 21

In a nitrogen atmosphere, sub21 (10 g, 16.4 mmol), compound A (3.9 g, 18 mmol), and sodium tert-butoxide (3.2 g, 32.8 mmol) were added to 200 ml of xylene, followed by stirring and reflux. Then, 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 under reduced pressure after cooling to room temperature. Then, the compound was completely dissolved in chloroform again, 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 5.9 g of compound 21. (Yield 54%, MS: [M+H]+= 665)

Synthesis Example 22

In a nitrogen atmosphere, sub22 (10 g, 16.4 mmol), compound C (4.8 g, 18 mmol), and sodium tert-butoxide (3.2 g, 32.8 mmol) were added to 200 ml of xylene, followed by stirring and reflux. Then, 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 under reduced pressure after cooling to room temperature. Then, the compound was completely dissolved in chloroform again, 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 7.1 g of Compound 22. (Yield 57%, MS: [M+H] + = 765)

Synthesis Example 23

In a nitrogen atmosphere, sub23 (10 g, 16.4 mmol), compound B (4.8 g, 18 mmol), and sodium tert-butoxide (3.2 g, 32.8 mmol) were added to 200 ml of xylene, followed by stirring and reflux. Then, 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 under reduced pressure after cooling to room temperature. Then, the compound was completely dissolved in chloroform again, 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 g of compound 23. (Yield 60%, MS: [M+H]+= 815)

Synthesis Example 24

In a nitrogen atmosphere, sub24 (10 g, 16.4 mmol), compound B (4.8 g, 18 mmol), and sodium tert-butoxide (3.2 g, 32.8 mmol) were added to 200 ml of xylene, followed by stirring and reflux. Then, 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 under reduced pressure after cooling to room temperature. Then, the compound was completely dissolved in chloroform again, 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 7.5 g of Compound 24. (Yield 52%, MS: [M+H]+=880)

Synthesis Example 25

In a nitrogen atmosphere, sub25 (10 g, 16.4 mmol), compound A (3.9 g, 18 mmol), and sodium tert-butoxide (3.2 g, 32.8 mmol) were added to 200 ml of xylene, and the mixture was stirred and refluxed. Then, 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 under reduced pressure after cooling to room temperature. Then, the compound was completely dissolved in chloroform again, 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 9.3 g of compound 25. (Yield 70%, MS: [M+H]+= 815)

Synthesis Example 26

In a nitrogen atmosphere, sub26 (10 g, 16.4 mmol), compound B (4.8 g, 18 mmol), and sodium tert-butoxide (3.2 g, 32.8 mmol) were added to 200 ml of xylene, followed by stirring and reflux. Then, 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 under reduced pressure after cooling to room temperature. Then, the compound was completely dissolved in chloroform again, 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 26. (Yield 52%, MS: [M+H]+= 871)

Synthesis Example 27

In a nitrogen atmosphere, sub27 (10 g, 16.4 mmol), compound A (3.9 g, 18 mmol), and sodium tert-butoxide (3.2 g, 32.8 mmol) were added to 200 ml of xylene, followed by stirring and reflux. Then, 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 under reduced pressure after cooling to room temperature. Then, the compound was completely dissolved in chloroform again, 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 7.9 g of compound 27. (Yield 60%, MS: [M+H]+= 805)

Synthesis Example 28

In a nitrogen atmosphere, sub28 (10 g, 16.4 mmol), compound B (4.8 g, 18 mmol), and sodium tert-butoxide (3.2 g, 32.8 mmol) were added to 200 ml of xylene, followed by stirring and reflux. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed under reduced pressure after cooling to room temperature. Then, 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 compound 28. (Yield 68%, MS: [M+H]+= 891)

Synthesis Example 29

In a nitrogen atmosphere, sub29 (10 g, 16.4 mmol), compound A (3.9 g, 18 mmol), and sodium tert-butoxide (3.2 g, 32.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, 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 under reduced pressure after cooling to room temperature. Then, the compound was completely dissolved in chloroform again, 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 g of compound 29. (Yield 58%, MS: [M+H] + = 841)

Synthesis Example 30

In a nitrogen atmosphere, sub30 (10 g, 16.4 mmol), compound D (4.8 g, 18 mmol), and sodium tert-butoxide (3.2 g, 32.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, 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 under reduced pressure after cooling to room temperature. Then, the compound was completely dissolved in chloroform again, 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 g of compound 30. (Yield 70%, MS: [M+H]+=956)

Synthesis Example 31

In a nitrogen atmosphere, sub31 (10 g, 16.4 mmol), compound B (4.8 g, 18 mmol), and sodium tert-butoxide (3.2 g, 32.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, 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 under reduced pressure after cooling to room temperature. Then, the compound was completely dissolved in chloroform again, 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 31. (Yield 67%, MS: [M+H]+= 715)

Synthesis Example 32

In a nitrogen atmosphere, sub32 (10 g, 16.4 mmol), compound D (4.8 g, 18 mmol), and sodium tert-butoxide (3.2 g, 32.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, 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 under reduced pressure after cooling to room temperature. Then, the compound was completely dissolved in chloroform again, 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 compound 32. (Yield 64%, MS: [M+H]+= 815)

Synthesis Example 33

In a nitrogen atmosphere, sub33 (10 g, 16.4 mmol), compound D (4.8 g, 18 mmol), and sodium tert-butoxide (3.2 g, 32.8 mmol) were added to 200 ml of xylene, followed by stirring and reflux. Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed under reduced pressure after cooling to room temperature. Then, 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 33. (Yield 54%, MS: [M+H]+= 815)

Synthesis Example 34

In a nitrogen atmosphere, sub34 (10 g, 16.4 mmol), compound D (4.8 g, 18 mmol), and sodium tert-butoxide (3.2 g, 32.8 mmol) were added to 200 ml of xylene, followed by stirring and reflux. Then, 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 under reduced pressure after cooling to room temperature. Then, 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 34. (Yield 64%, MS: [M+H] + = 855)

Synthesis Example 35

In a small atmosphere, sub35 (10 g, 16.4 mmol), compound B (4.8 g, 18 mmol), and sodium tert-butoxide (3.2 g, 32.8 mmol) were added to 200 ml of xylene, and the mixture was stirred and refluxed. Then, 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 under reduced pressure after cooling to room temperature. Then, the compound was completely dissolved in chloroform again, 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 35. (Yield 64%, MS: [M+H] + = 855)

Synthesis Example 36

In a nitrogen atmosphere, sub36 (10 g, 16.4 mmol), compound C (4.8 g, 18 mmol), and sodium tert-butoxide (3.2 g, 32.8 mmol) were added to 200 ml of xylene, followed by stirring and reflux. Then, 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 under reduced pressure after cooling to room temperature. Then, the compound was completely dissolved in chloroform again, 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 7.1 g of compound 36. (Yield 53%, MS: [M+H]+= 815)

Synthesis Example 37

In a nitrogen atmosphere, sub37 (10 g, 16.4 mmol), compound A (3.9 g, 18 mmol), and sodium tert-butoxide (3.2 g, 32.8 mmol) were added to 200 ml of xylene, followed by stirring and reflux. Then, 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 under reduced pressure after cooling to room temperature. Then, the compound was completely dissolved in chloroform again, 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 37. (Yield 54%, MS: [M+H]+=880)

Synthesis Example 38

In a nitrogen atmosphere, sub38 (10 g, 16.4 mmol), compound B (4.8 g, 18 mmol), and sodium tert-butoxide (3.2 g, 32.8 mmol) were added to 200 ml of xylene, followed by stirring and reflux. Then, 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 under reduced pressure after cooling to room temperature. Then, the compound was completely dissolved in chloroform again, 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 9.4 g of compound 38. (Yield 65%, MS: [M+H]+= 881)

Synthesis Example 39

In a nitrogen atmosphere, sub39 (10 g, 16.4 mmol), compound A (3.9 g, 18 mmol), and sodium tert-butoxide (3.2 g, 32.8 mmol) were added to 200 ml of xylene, followed by stirring and reflux. Then, 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 under reduced pressure after cooling to room temperature. Then, the compound was completely dissolved in chloroform again, 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 399. (Yield 65%, MS: [M+H] + = 841)

Synthesis Example 40

In a nitrogen atmosphere, sub40 (10 g, 16.4 mmol), compound D (4.8 g, 18 mmol), and sodium tert-butoxide (3.2 g, 32.8 mmol) were added to 200 ml of xylene, stirred and refluxed. Then, 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 under reduced pressure after cooling to room temperature. Then, the compound was completely dissolved in chloroform again, 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 40. (Yield 53%, MS: [M+H]+=956)

[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.

The following HI-1 compound was formed to a thickness of 1150 Å as a hole injection layer on the thus prepared ITO transparent electrode, but the following compound A-1 was p-doped at a concentration of 1.5%. The following HT-1 compound was vacuum-deposited on the hole injection layer to form a hole transport layer having a thickness of 800 Å. 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. Then, the following RH-1 compound and the following Dp-39 compound were vacuum-deposited in a weight ratio of 98:2 on the EB-1 deposited layer 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 diode was manufactured.

Comparative Examples 2 to 10

An organic light emitting diode was manufactured in the same manner as in Comparative Example 1, except that the following compounds RH-2 to RH-10 were respectively used instead of RH-1 as a host material for the red light emitting layer.

Examples 1 to 40

An organic light emitting diode was manufactured in the same manner as in Comparative Example 1, except that Compounds 1 to 40 of the Synthesis Example were respectively used instead of Comparative Example 1 as a host material for the red light emitting layer.

Experimental example

The organic light emitting devices of Comparative Examples 1 to 10 and Examples 1 to 40 were stored in an oven at 110° C. for 30 minutes and heat-treated, and then a current was applied to measure the driving voltage, current efficiency, and lifespan (T95), and the results were obtained. It is shown in Table 1 below. At this time, voltage and efficiency were measured by applying a current density of 10 mA/cm ² . In addition, T95 in Table 1 below means the time (hr) measured until the initial luminance decreases to 95% at a current density of 10 mA/cm ² .

Experimental example host material drive voltage
(V) current efficiency
(cd/A) life span
(T95%@10mA, hr) Comparative Example 1 RH-1 5.70 15.15 58 Comparative Example 2 RH-2 5.34 14.34 67 Comparative Example 3 RH-3 5.42 14.55 65 Comparative Example 4 RH-4 5.55 14.35 59 Comparative Example 5 RH-5 5.45 14.43 61 Comparative Example 6 RH-6 5.62 14.58 76 Comparative Example 7 RH-7 5.36 15.21 71 Comparative Example 8 RH-8 5.26 13.75 68 Comparative Example 9 RH-9 5.29 12.69 61 Comparative Example 10 RH-10 5.53 14.51 70 Example 1 compound 1 4.31 23.54 181 Example 2 compound 2 4.25 24.25 200 Example 3 compound 3 4.31 25.36 183 Example 4 compound 4 4.41 24.33 175 Example 5 compound 5 4.53 26.15 192 Example 6 compound 6 4.23 23.99 184 Example 7 compound 7 4.19 24.31 177 Example 8 compound 8 4.22 23.81 205 Example 9 compound 9 4.15 26.01 183 Example 10 compound 10 4.37 25.99 180 Example 11 compound 11 4.46 23.41 179 Example 12 compound 12 4.41 26.10 194 Example 13 compound 13 4.53 24.81 183 Example 14 compound 14 4.21 25.31 201 Example 15 compound 15 4.53 26.13 187 Example 16 compound 16 4.20 23.80 177 Example 17 compound 17 4.23 22.22 183 Example 18 compound 18 4.15 23.20 194 Example 19 compound 19 4.34 24.60 186 Example 20 compound 20 4.40 23.98 179 Example 21 compound 21 4.25 23.48 175 Example 22 compound 22 4.44 24.05 188 Example 23 compound 23 4.61 26.33 184 Example 24 compound 24 4.53 24.83 192 Example 25 compound 25 4.18 26.70 190 Example 26 compound 26 4.25 24.33 186 Example 27 compound 27 4.23 23.58 179 Example 28 compound 28 4.35 23.99 182 Example 29 compound 29 4.33 24.98 197 Example 30 compound 30 4.41 26.06 185 Example 31 compound 31 4.53 27.80 192 Example 32 compound 32 4.51 26.81 188 Example 33 compound 33 4.29 25.91 206 Example 34 compound 34 4.38 24.78 201 Example 35 compound 35 4.36 23.81 195 Example 36 compound 36 4.53 25.60 186 Example 37 compound 37 4.28 24.97 189 Example 38 compound 38 4.19 25.37 187 Example 39 compound 39 4.31 26.18 177 Example 40 compound 40 4.50 25.90 189

Referring to Table 1, it can be seen that the organic light emitting device using the compound of Formula 1 of the present invention as a red light emitting layer host material exhibits a low driving voltage and has excellent current efficiency and lifespan characteristics.

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

Claims (8)

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

In Formula 1,
each X is independently N, or CH, provided that at least two of X are N;
Ar ₁ and Ar ₂ are each independently, substituted or unsubstituted C _6-60 aryl; Or substituted or unsubstituted C _2-60 heteroaryl comprising any one or more selected from the group consisting of N, O and S,
R ₁ to R ₄ are all hydrogen or deuterium; or two adjacent ones of R ₁ to R ₄ combine to form a benzene ring, and the remainder is hydrogen or deuterium;
R ₅ is hydrogen or deuterium,
R ₆ is each independently hydrogen, or deuterium,
n is an integer from 1 to 3.
According to claim 1,
X is all N;
compound.
According to claim 1,
Ar ₁ and Ar ₂ are each independently, substituted or unsubstituted C _6-20 aryl; Or substituted or unsubstituted C _2-20 heteroaryl comprising any one or more selected from the group consisting of N, O and S,
compound.
According to claim 1,
Ar ₁ and Ar ₂ are each independently, unsubstituted phenyl; phenyl substituted with 5 deuterium; biphenylyl; naphthyl; phenanthryl; dibenzofuranyl; dibenzothiophenyl; carbazolyl; or 9-phenylcarbazolyl,
compound.
According to claim 1,
R ₅ is hydrogen;
compound.
The method of claim 1,
R ₆ is 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.

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