KR20100036961A - Novel aromatic derivatives and organic electroluminescent device comprising same - Google Patents

Abstract

PURPOSE: A compound is provided to ensure excellent heat resistance and thin film stability and to improve driving stability, luminous efficiency, color purity and lifetime property of an organic electroluminescent device. CONSTITUTION: A compound is represented by chemical formula (I), wherein Ri and R2 are each independently hydrogen, C1-50 alkyl, C3-50 cycloalkyl, C6-50 aryl, or heteroaryl having 5 to 50 ring atoms, Ri or R2 being optionally substituted with Ci-50 alkyl, C6-5O aryl, heteroaryl having 5 to 50 ring atoms, or C7-50 aralkyl, or Ri and R2 being optionally linked to form a C4-50 saturated or unsaturated ring moiety; Ar is an aromatic hydrocarbon moiety, optionally substituted with X, the aromatic hydrocarbon group being a fused ring of at least two benzenes; R3 and X are each independently hydrogen, halogen, cyano, nitro, amino, thio, phosphoryl, phosphinyl, carbonyl, silyl, boranyl, Ci-50 alkyl, C2-5O alkenyl, C2-50 alkynyl, Ci-50 alkoxy, C3-50 cycloalkyl, C6-50 aryl, or heteroaryl having 5 to 50 ring atoms; R3 or X being optionally substituted with amino, thio, phosphoryl, phosphinyl, carbonyl, silyl, boranyl, Ci-50 alkyl, C2-50 alkenyl, C2-50 alkynyl, Ci-50 alkoxy, C3-50 cycloalkyl, C6-50 aryl, or heteroaryl having 5 to 50 ring atoms, or C7-50 aralkyl, which optionally has a C^6 alkyl substituent, or each of R3 and X being optionally linked together with its adjacent group to form a C4-50 saturated or unsaturated ring moiety, with the proviso that X cannot be hydrogen; and n is an integer of 1 to 6.

Description

Novel aromatic derivatives and organic electroluminescent devices comprising the same {NOVEL AROMATIC DERIVATIVES AND ORGANIC ELECTROLUMINESCENT DEVICE COMPRISING SAME}

The present invention relates to a novel aromatic derivative having excellent luminous efficiency, heat resistance and the like and an organic electroluminescent device capable of exhibiting excellent lifespan characteristics and low voltage driving by including the same in one or more organic layers.

The organic electroluminescent device is a self-luminous type light emitting device. The structure is simpler than other flat panel display devices, and thus the manufacturing process is simple, has high luminance and excellent viewing angle characteristics, fast response speed and low driving voltage, Applicability is shown as a light source of a flat panel display or a back light of a display, an illumination, an advertisement board, etc. The organic electroluminescence phenomenon has been limited in practical terms since it was announced by Curnee in 1969 (US Pat. No. 3,172,862), but in 1987, an organic electroluminescent device was overcome by the researchers of Eastman Kodak. Has developed rapidly since then.

In general, the organic electroluminescent device has a structure including a cathode (electron injection electrode) and an anode (hole injection electrode), and at least one organic layer between the two electrodes. In this case, the organic electroluminescent device may be a hole injection layer (HIL), a hole transport layer (HTL), an electron transport layer (ETL), in addition to the light emitting layer (EML) as an organic layer. It may include an electron injection layer (EIL), and may further include an electron blocking layer (EBL) or a hole blocking layer (HBL) due to light emission characteristics of the light emitting layer. The organic electroluminescent device including all of these organic layers has a structure laminated in the order of anode / hole injection layer / hole transport layer / electron blocking layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode.

When an electric field is applied to the organic electroluminescent device of this structure, holes injected from the anode and electrons injected from the cathode are recombined to form an exciton, an electron-hole pair, and the energy of the excitons is applied to the light emitting material. As it is transmitted, light is emitted. The lifetime of stacked organic electroluminescent devices is related to the electrochemical stability and thin film stability of materials.

For example, when a light emitting material having poor thermal stability is used, the material is crystallized at a high temperature or a driving temperature, thereby shortening the life of the device. Anthracene derivatives have been used as typical organic electroluminescent device materials, including light emitting layers, hole transport layers and electron transport layers. For example, 9,10-di (naphthalen-2-yl) anthracene is used as a blue host material because of its excellent luminescence properties, but it has a disadvantage of shortening the life of the device because it is easily crystallized as the temperature of the device rises. . In order to secure thermal stability, fluorene derivatives and benzofluorene derivatives in which carbons are linked to aromatic cyclic compounds have been developed, but because of their wide bandgap, they can be used as blue host materials for driving voltage and energy transfer to dopants. A problem occurred. In order to overcome these drawbacks, various types of materials have been developed, but until now, various technologies have been urgently developed because they do not sufficiently satisfy characteristics such as luminous efficiency, driving stability, and lifetime.

Accordingly, an object of the present invention is to provide a novel compound having excellent heat resistance and thin film stability, which can significantly improve driving stability, luminous efficiency, color purity, and lifetime characteristics of an organic electroluminescent device, and an organic electroluminescent device comprising the same in an organic layer. To provide.

In order to achieve the above object, the present invention provides an aromatic derivative represented by the following formula (1):

Where

R ₁ and R ₂ are each independently hydrogen, C _1-50 alkyl, C _3-50 cycloalkyl, C _6-50 aryl or heteroaryl having 5 to 50 nuclear atoms, wherein R ₁ to R ₂ are optionally C _1-50 alkyl, C _6-50 aryl, 5 to 50 heteroaryl or C _7-50 aralkyl may be substituted, and R ₁ and R ₂ are optionally bonded to each other to C _4-50 saturated May form a ring or an unsaturated ring;

Ar is an aromatic hydrocarbon having two or more benzene rings conjugated or unsubstituted by X;

R ₃ and X are each independently hydrogen, halogen, cyano, nitro, amino, thio, phosphoryl, phosphinyl, carbonyl, silyl, boranyl, C _1-50 alkyl, C _2-50 alkenyl, C _2-50 alkynyl, C _1-50 alkoxy, C _3-50 cycloalkyl, C _6-50 aryl or heteroaryl having 5 to 50 nuclear atoms (where X is not hydrogen), wherein R ₃ and X are Amino, thio, phosphoryl, phosphinyl, carbonyl, silyl, boranyl, C _1-50 alkyl, C _2-50 alkenyl, C _2-50 , optionally substituted with C _1-6 alkyl Alkynyl, C _1-50 alkoxy, C _3-50 cycloalkyl, C _6-50 aryl, 5 to 50 heteroaryl or C _7-50 aralkyl, and each of R ₃ and X is Optionally combine with adjacent groups to form a C _4-50 saturated ring or unsaturated ring;

n is an integer of 1-6.

In addition, the present invention provides an organic electroluminescent device comprising the compound of Formula 1 in at least one organic layer.

The organic electroluminescent device using the aromatic derivative of the present invention has excellent heat resistance, high stability of the thin film constituting the device, long life, high color purity and luminous efficiency, and low voltage driving. For this reason, the organic electroluminescent device of the present invention can be used in various ways such as a flat panel display such as a wall-mounted TV, lighting or a backlight of a display.

In the present invention, in order to reduce the wide bandgap which is a disadvantage of fluorene and benzofluorene and to promote structural stability, an aromatic ring compound connected with naphthalene is introduced, and a compound in which two or more benzene rings are conjugated is introduced and the naphthalene and the aromatic The ring compounds were linked in the form of six membered rings, not five membered rings.

In the compound of Formula 1, Ar may be naphthalene, anthracene, phenanthrene or pyrene, preferably substituted with X.

The aromatic derivative represented by Formula 1 may be represented by the following Formula 1a to 1h as a representative example:

Where

R ₁ to R ₃ , X and n are as defined above;

m is an integer from 1 to 6;

z is an integer from 1 to 8.

More specifically, the aromatic derivative represented by the formula (1) of the present invention is exemplified below as compounds 1 to 383, but the present invention is not limited to these representative examples.

Compounds of formula 1 according to the invention can be prepared as shown in Scheme 1 (where R ₃ is hydrogen), schemes 2, 3 or 4 (when R ₃ is not hydrogen).

Where

R ₁ , R ₂ and Ar are as defined above;

R ₃ ′ and R ₃ ″ are each independently the same as defined above for R ₃ , provided that they are not hydrogen;

X ₁ and X ₂ are each independently trifluoromethanesulfonyl or halogen;

X ₃ is halogen;

Y ₁ and Y ₂ are each independently hydrogen or C _1-6 alkyl, and Y ₁ and Y ₂ may be bonded to each other to form a ring.

In Scheme 1, a compound of Formula 2 is prepared by reacting a compound of Formula 2 with a compound of Formula 3 in a mixed solvent of an organic solvent (for example, toluene, tetrahydrofuran, ethanol, or a mixture thereof), and then the compound of Formula 4 Compound 4 is dissolved in an organic solvent (e.g., tetrahydrofuran, ethyl ether, 1,4-dioxane, 1,2-dimethoxyethane, or mixtures thereof), such as n -butyllithium, t -butyllithium, etc. To react with a compound of formula (5) in the presence of a compound of formula (5), and then cyclize the compound of formula (6) in the presence of an acid (e.g., Lewis acid such as hydrochloric acid, nitric acid, sulfuric acid, By reacting, the compound of Formula 1i may be prepared. In this case, the reaction between the compound of Formula 2 and the compound of Formula 3 is at 25 to 110 ° C, the reaction of the compound of Formula 4 to the compound of Formula 5 is -78 to 50 ° C, and the cyclization reaction of the compound of Formula 6 is It may be carried out at 25 to 110 ℃. In addition, it is preferable to add a base and a catalyst in the reaction of the compound of Formula 2 with the compound of Formula 3, and as the base, potassium carbonate, sodium carbonate or a mixture thereof may be used, and various palladium complexes may be used as catalysts. Typically, tetrakis (triphenylphosphine) palladium (0) can be used.

In Scheme 2, the compound of Formula 1i prepared in Scheme 1 is reacted with (X ₃ ) ₂ in an organic solvent (eg, carbon tetrachloride, chloroform, methylene chloride, and mixtures thereof) to prepare a compound of Formula 7 The compound of formula 1j may be prepared by reacting the compound of formula 7 with a compound of formula 8 in a mixed solvent of an organic solvent (eg, toluene, tetrahydrofuran, ethanol or a mixture thereof) and water. In this case, the reaction of the compound of Formula 1i with (X ₃ ) ₂ may be performed at −30 to 60 ° C., and the reaction of the compound of Formula 7 to the compound of Formula 8 may be performed at 25 to 110 ° C. In addition, it is preferable to add a base and a catalyst in the reaction of the compound of Formula 7 with the compound of Formula 8, and as the base, potassium carbonate, sodium carbonate or a mixture thereof may be used, and various palladium complexes may be used as the catalyst. Typically, tetrakis (triphenylphosphine) palladium (0) can be used.

In Scheme 3, a compound of Formula 9 is reacted with a compound of Formula 10 in a mixed solvent of an organic solvent (for example, toluene, tetrahydrofuran, ethanol, or a mixture thereof) to prepare a compound of Formula 11, and then 11 compound in an organic solvent (e.g., tetrahydrofuran, ethyl ether, 1,4-dioxane, 1,2-dimethoxyethane, or mixtures thereof), such as n -butyllithium, t -butyllithium, etc. To react with a compound of formula (5) in the presence of an acid (e.g., hydrochloric acid, nitric acid, sulfuric acid, boric trifluoride, etc.) The compound of formula 1k can be prepared by the formation reaction. In this case, the reaction between the compound of Formula 9 and the compound of Formula 10 is at 25 to 110 ° C, the reaction of the compound of Formula 11 to the compound of Formula 5 is -78 to 50 ° C, and the cyclization reaction of the compound of Formula 12 is It may be carried out at 25 to 110 ℃. In addition, it is preferable to add a base and a catalyst in the reaction of the compound of Formula 9 with the compound of Formula 10. As the base, potassium carbonate, sodium carbonate or a mixture thereof can be used, and various palladium complexes can be used as the catalyst. Typically, tetrakis (triphenylphosphine) palladium (0) can be used.

In Scheme 4, the compound of Formula 1k prepared in Scheme 3 is reacted with (X ₃ ) ₂ in an organic solvent (eg, carbon tetrachloride, chloroform, methylene chloride, and mixtures thereof) to prepare a compound of Formula 13, In addition, the compound of Formula 1 may be prepared by reacting the compound of Formula 13 with the compound of Formula 14 in a mixed solvent of an organic solvent (eg, toluene, tetrahydrofuran, ethanol or a mixture thereof) and water. In this case, the reaction of the compound of Formula 1k and (X ₃ ) ₂ may be performed at -30 to 60 ° C, and the reaction of the compound of Formula 13 and the compound of Formula 14 may be performed at 25 to 110 ° C. In addition, it is preferable to add a base and a catalyst in the reaction of the compound of Formula 13 with the compound of Formula 14, and as the base, potassium carbonate, sodium carbonate or a mixture thereof can be used, and various palladium complexes can be used as catalysts. Typically, tetrakis (triphenylphosphine) palladium (0) can be used.

The compound of formula 3 used to prepare the compound of formula 1a is a naphthalene derivative having a -BOY ₁ OY ₂ substituent at the carbon position ₂ ; The compound of formula 3 used in the preparation of the compound of formula 1b is a naphthalene derivative having a -BOY ₁ OY ₂ substituent at the carbon position 2 and an alkyl or aryl substituent at the carbon position; The compound of formula 3 used in the preparation of the compound of formula 1c is a naphthalene derivative having a -BOY ₁ OY ₂ substituent at the carbon position ₁ ; The compound of formula 3 used in the preparation of the compound of formula 1d is an anthracene derivative having a -BOY ₁ OY ₂ substituent at the carbon position ₂ ; The compound of formula 3 used in the preparation of the compound of formula 1e is an anthracene derivative having a -BOY ₁ OY ₂ substituent at the carbon position 2 and an alkyl or aryl group substituent at the carbon position 1; The compound of formula 3 used to prepare the compound of formula 1f is an anthracene derivative having a -BOY ₁ OY ₂ substituent at position 1 carbon; The compound of formula 3 used to prepare the compound of formula 1g is a phenanthrene derivative having a -BOY ₁ OY ₂ substituent at the carbon position 9; The compound of formula 3 used in the preparation of the compound of formula 1h is a pyrene derivative having a -BOY ₁ OY ₂ substituent at the carbon position ₁ .

In addition, the present invention provides an organic electroluminescent device comprising the compound of Formula 1 in at least one organic layer. In this case, the organic layer may essentially include a light emitting layer, and may include a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, or a laminate thereof in addition to the light emitting layer.

The organic electroluminescent device of the present invention includes an anode, a cathode, and an organic layer consisting of a single layer or a multilayer containing at least one light emitting layer between the two electrodes, wherein at least one layer of the organic layer is a new compound of Formula 1 It contains. For example, the multilayer organic electroluminescent device is stacked in a multilayer structure of a substrate, an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode from below.

That is, the compound of Formula 1 may be applied to not only the light emitting layer but also the hole injection layer, the hole transport layer, the electron transport layer, and the electron injection layer, depending on the kind of the substituent to be introduced. The aromatic derivative of the present invention has excellent thermal evaporation characteristics, high solubility in organic solvents, high wet tablet yield, and wet film formation such as inkjet or spin coating.

The substrate, the anode, and the cathode of the organic electroluminescent device according to the present invention are made of a material used in a conventional organic electroluminescent device, and the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer and the electron injection layer are each a compound of Formula 1 It may be made of a commonly used material or a mixture thereof.

In particular, in the case of the light emitting layer, other light emitting dopant materials known by using the compound of formula 1 of the present invention alone or in combination of two or more, or as a light emitting host material or a dopant material, or Can be used with host materials. When the compound of Formula 1 is used as a single light emitting material or a host material, it may be added in an amount of 100 to 50% by weight relative to the light emitting layer, and when used as a dopant material, it may be added in an amount of 0.01 to 50% by weight relative to the light emitting layer. have. Specific examples of the light emitting material (host material or dopant material) that can be used in the light emitting layer with the compound of Formula 1 include anthracene derivative, naphthalene derivative, phenanthrene derivative, pyrene derivative Tetrane derivatives, coronene derivatives, chrysene derivatives, fluoranthene derivatives, perylene derivatives, phthaloperylene derivatives, stilbenene ), Distyrylarylene derivatives, perinone derivatives, phthaloperinone derivatives, naphthaloperinone derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives Tetraphenylbutadiene derivatives, coumarine derivatives, oxadiazole derivatives, bisbenzoxazoline derivatives, bisstyryl Conductors, pyrazine derivatives, cyclopentadiene derivatives, quinoline metal complex derivatives, aminoquinoline metal complex derivatives, benzoquinoline metal complex derivatives, imine derivatives, di Diphenylethylene Derivatives, Vinylanthracene Derivatives, Diaminocarbazole Derivatives, Pyrane Derivatives, Thiopyrane Derivatives, Quinacridone Derivatives, Rubrene Derivatives, other fluorescent dyes, and mixtures thereof, but are not limited thereto. When selecting a dopant material, it is desirable to have a high efficiency of fluorescence or phosphorescence and have a bandgap equal to or less than the bandgap of the host material.

Each layer constituting the organic electroluminescent device is formed by applying any conventional method such as dry deposition method such as vacuum deposition, sputtering, plasma, ion plating, or wet deposition method such as radiation coating, immersion coating, and flow coating. You can. The film thickness is not particularly limited, but if the film thickness is too thick, a high applied voltage is required to obtain a constant light output, resulting in poor efficiency. If the film thickness is too thin, a pin hole or the like is generated to apply an electric field. Also, sufficient light emission luminance cannot be obtained. Typical film thickness is preferably in the range of 5 nm to 10 μm, but more preferably in the range of 10 nm to 0.2 μm.

Thus, since the aromatic derivative of the present invention has excellent heat resistance and thin film stability, the organic electroluminescent device containing the same exhibits significantly improved driving voltage, luminous efficiency, color purity and lifespan characteristics.

Hereinafter, the present invention will be described in more detail based on the following examples. However, the following examples are not intended to limit the invention only.

EXAMPLE

Synthesis of Compound

Example 1 Synthesis of Compounds 1, 59, 60, 208, 255, 302 of the Invention (See Scheme 5 below)

1-1) Synthesis of Intermediate 1

In a 250 ml three-necked round bottom flask, 1,8-dibromonaphthalene (6 g), 2-naphthalene boronic acid (4 g), tetrahydrofuran (120 ml), potassium carbonate (6.5 g) and water (50 ml) Was added and stirred. Tetrakis (triphenylphosphine) palladium (0) (1.3 g) was added to this mixed solution, and it heated to 80 degreeC. The reaction solution was separated into layers to remove water, and the organic layer was washed twice with water. The organic layer was dried over magnesium sulfate and concentrated under reduced pressure to remove the solvent. The material produced by concentration was separated by column using hexane to give 5.5 g of the title compound.

1-2) Synthesis of Intermediate 2

In a 250 ml three-neck round bottom flask, 1,8-dibromonaphthalene (10 g), phenanthrene-9-yl boronic acid (8.5 g), tetrahydrofuran (100 ml), potassium carbonate (10.6 g) and water ( 50 ml) was added and stirred. Tetrakis (triphenylphosphine) palladium (0) (2.2 g) was added to this mixed solution, and it heated to 80 degreeC. The reaction solution was separated and the water was removed, and the organic layer was washed twice with water. The organic layer was dried over magnesium sulfate and concentrated under reduced pressure to remove the solvent. The material produced by concentration was separated by column using hexane to give 10.5 g of the title compound.

1-3) Synthesis of Intermediate 3

In a 2000 ml three-necked round bottom flask, 1,8-dibromonaphthalene (58 g), 6-phenylnaphthalen-2-yl boronic acid (50 g), tetrahydrofuran (500 ml), potassium carbonate (42 g) and Water (250 ml) was added and stirred. Tetrakis (triphenylphosphine) palladium (0) (11.7 g) was added to this mixed solution and heated to 80 占 폚. The reaction solution was separated and the water was removed, and the organic layer was washed twice with water. The organic layer was dried over magnesium sulfate and concentrated under reduced pressure to remove the solvent. The material produced by concentration was separated by column using hexane to give 50 g of the title compound.

1-4) Synthesis of Intermediate 4

In a 2000 ml three-necked round bottom flask, 1,8-dibromonaphthalene (58 g), 2,2'-binaphthyl-6-yl boronic acid (60 g), tetrahydrofuran (500 ml), potassium carbonate ( 42 g) and water (250 ml) were added and stirred. Tetrakis (triphenylphosphine) palladium (0) (11.7 g) was added to this mixed solution and heated to 80 占 폚. The reaction solution was separated and the water was removed, and the organic layer was washed twice with water. The organic layer was dried over magnesium sulfate and concentrated under reduced pressure to remove the solvent. The material produced by concentration was separated by column using hexane to give 71 g of the title compound.

1-5) Synthesis of Intermediate 5

Intermediate 1 (5.5 g) and tetrahydrofuran (40 ml) were added to a 100 ml three-necked round bottom flask, and the mixture was stirred under an argon atmosphere and the temperature of the mixed solution was lowered to -78 ° C. N -butyllithium (12 ml) was slowly added thereto, followed by stirring for 2 hours. A solution of fluorenone (3 g) dissolved in tetrahydrofuran (12 ml) was slowly added to the mixture, and the temperature of the mixture was raised to room temperature, followed by stirring for 12 hours. Water (20 ml) was added to the reaction solution and stirred for 2 hours. The reaction solution was separated and the water was removed, the organic layer was cooled, and the crystals were filtered to yield 3.8 g of the title compound.

1-6) Synthesis of Intermediate 6

Intermediate 2 (10.5 g) and tetrahydrofuran (80 ml) were added to a 250 ml three-necked round bottom flask, and the mixture was stirred under an argon atmosphere and the temperature of the mixed solution was lowered to -78 ° C. N -butyllithium (20 ml) was slowly added thereto, followed by stirring for 2 hours. A solution of fluorenone (4.9 g) dissolved in tetrahydrofuran (20 ml) was slowly added to the mixed solution, and the temperature of the mixed solution was raised to room temperature, followed by stirring for 12 hours. Water (50 ml) was added to the reaction solution and stirred for 2 hours. The reaction solution was separated and the water was removed, the organic layer was cooled, and the crystals were filtered to obtain 9.7 g of the title compound.

1-7) Synthesis of Intermediate 7

Intermediate 3 (35 g) and tetrahydrofuran (550 ml) were added to a 2000 ml three-neck round bottom flask, and the mixture was stirred under an argon atmosphere and the temperature of the mixed solution was lowered to -78 ° C. N -butyllithium (60 ml) was slowly added thereto and stirred for 2 hours. A solution of fluorenone (17 g) dissolved in tetrahydrofuran (65 ml) was slowly added to the mixed solution, and the temperature of the mixed solution was raised to room temperature, followed by stirring for 12 hours. Water (500 ml) was added to the reaction solution and stirred for 2 hours. The reaction solution was separated and the water was removed, the organic layer was cooled, and the crystals were filtered to obtain 43 g of the title compound.

1-8) Synthesis of Intermediate 8

6.5 g of intermediate 3 and 45 ml of tetrahydrofuran were added to a 100 ml three-necked round bottom flask, and the mixture was stirred under an argon atmosphere and the temperature of the mixed solution was lowered to -78 ° C. N -butyllithium (11 ml) was slowly added thereto, followed by stirring for 2 hours. A solution of 2,7-di- t -butyl fluorenone (3.0 g) dissolved in tetrahydrofuran (12 ml) was slowly added to the mixed solution, and the temperature of the mixed solution was raised to room temperature, followed by stirring for 12 hours. Water (70 ml) was added to the reaction solution and stirred for 2 hours. The reaction solution was separated and the water was removed, the organic layer was cooled, and the crystals were filtered to obtain 3.5 g of the title compound.

1-9) Synthesis of Intermediate 9

Intermediate 3 (6.5 g) and tetrahydrofuran (45 ml) were added to a 100 ml three-necked round bottom flask, and the mixture was stirred under an argon atmosphere and the temperature of the mixed solution was lowered to -78 ° C. N -butyllithium (11 ml) was slowly added thereto, followed by stirring for 2 hours. A solution of benzophenone (3.0 g) dissolved in tetrahydrofuran (12 ml) was slowly added to the mixed solution, and the temperature of the mixed solution was raised to room temperature, followed by stirring for 12 hours. Water (70 ml) was added to the reaction solution and stirred for 2 hours. The reaction solution was separated and the water was removed, the organic layer was cooled and the crystals were filtered to yield 3.9 g of the title compound.

1-10) Synthesis of Intermediate 10

Intermediate 4 (71 g) and tetrahydrofuran (700 ml) were added to a 2000 ml three-necked round bottom flask, and the mixture was stirred under an argon atmosphere and the temperature of the mixed solution was lowered to -78 ° C. N -butyllithium (107 ml) was slowly added thereto and stirred for 2 hours. A solution of fluorenone (28 g) dissolved in tetrahydrofuran (120 ml) was slowly added to the mixed solution, and the temperature of the mixed solution was raised to room temperature, followed by stirring for 12 hours. Water (710 ml) was added to the reaction solution and stirred for 2 hours. The reaction solution was separated and the water was removed, the organic layer was cooled, and the crystals were filtered to give 86 g of the title compound.

1-11) Synthesis of Compound 1

Intermediate 5 (3.8 g), acetic acid (70 ml) and hydrochloric acid (4 ml) were added to a 100 ml three-necked round bottom flask, which was then stirred at 110 ° C. for 8 hours and then cooled. The reaction solution was filtered, washed sequentially with water and methanol, and dried to obtain 3.6 g of the title compound as a white powder.

¹ H-NMR (CDCl ₃ , 500 MHz) (1H, d, 8.42775, 8.40987), (1H, d, 8.316, 8.301), (2H, d, 7.98059, 7.96553), (1H, d, 7.89538, 7.87761), (1H, d, 7.80064, 7.78440), (1H, d, 7.68838, 7.67250), (1H, t, 7.62878-7.59755), (1H, d, 7.58013, 7.56439), (2H, t, 7.38501-7.35506), (2H, m, 7.17714-7.10432), (3H, m, 7.07895-7.03997), (2H, d, 6.94997, 6.93483), (1H, t, 6.82012-6.78612), (1H, d, 6.55999, 6.54491)

EI-MS: m / z 416 (M +)

1-12) Synthesis of Compound 302

Intermediate 6 (9.7 g), acetic acid (200 ml) and hydrochloric acid (8 ml) were added to a 250 ml three-neck round bottom flask, followed by stirring at 110 ° C. for 8 hours and then cooling. The reaction solution was filtered, washed sequentially with water and methanol and dried to obtain 9.1 g of the title compound as a white powder.

¹ H-NMR (CDCl ₃ , 500 MHz) (2H, d, 8.93082, 8.89066), (1H, d, 8.41952, 8.40354), (2H, d, 8.12165, 8.10496), (1H, d, 8.01093, 8.00163), (6H, m, 7.92376-7.87063), (3H, m, 7.58264-7.55027), (4H, m, 7.42365-7.8121), (2H, t, 7.31384-7.8132), (1H, d, 7.00163-6.98575)

EI-MS: m / z 467 (M +)

1-13) Synthesis of Compound 59

Intermediate 7 (43 g), acetic acid (800 ml) and hydrochloric acid (40 ml) were added to a 100 ml three-necked round bottom flask, which was then stirred at 110 ° C. for 8 hours and then cooled. The reaction solution was filtered, washed sequentially with water and methanol, and dried to obtain 40 g of the title compound as a white powder.

¹ H-NMR (CDCl ₃ , 500 MHz) (1H, d, 8.45317-8.43528), (1H, d, 8.32603, 8.31116), (2H, d, 7.99765, 7.98240), (1H, d, 7.95173-7.93396), (1H, s, 7.88883), (1H, d, 7.80715, 7.79085), (1H, t, 7.63564-77.60448), (1H, d, 7.58855, 7.57266), (2H, d, 7.54821, 7.53275), (2H , d, 7.39860, 7.38346), (2H, d, 7.36412, 7.34842), (1H, d, 7.29392-7.27912), (5H, m, 7.15040-7.05950), (2H, d, 6.98521, 6.97011), (1H , d, 6.57606-6.56095)

EI-MS: m / z 492 (M +)

1-14) Synthesis of Compound 255

Intermediate 8 (3.5 g), acetic acid (80 ml) and hydrochloric acid (4 ml) were added to a 100 ml three-necked round bottom flask, followed by stirring at 110 ° C. for 8 hours and then cooling. The reaction solution was filtered, washed sequentially with water and methanol, and dried to obtain 2.5 g of the title compound as a white powder.

¹ H-NMR (CDCl ₃ , 500MHz) 1H (d, 8.46103 ~ 8.44316), 1H (d, 8.34260 ~ 8.32779), 1H (d, 7.95108 ~ 7.93330), 1H (s, 7.89272), 2H (d, 7.84917 ~ 7.83304), 1H (d, 7.81230 ~ 7.79609), 1H (t, 7.64684 ~ 7.61571), 3H (d, 7.58065 ~ 7.56486), 4H (m, 7.39828 ~ 7.35988), 1H (d, 7.29775 ~ 7.28321), 3H ( m, 7.13826-7.08150), 2H (s, 6.91532), 1H (d, 6.58715-6.57213), 18H (s, 1.02374)

EI-MS: m / z 604 (M +)

1-15) Synthesis of Compound 208

Intermediate 9 (3.9 g), acetic acid (80 ml) and hydrochloric acid (4 ml) were added to a 100 ml three-necked round bottom flask, followed by stirring at 110 ° C. for 8 hours and then cooling. The reaction solution was filtered, washed sequentially with water and methanol, and dried to obtain 3.5 g of the title compound as a white powder.

¹ H-NMR (CDCl ₃ , 500 MHz) 1H (d, 8.27492-8.25722), 1H (d, 8.12335-8.10880), 2H (d, 7.98997-7.97181), 1H (d, 7.79700-7.8094), 2H (d, 7.68960 ~ 7.67000), 2H (d, 7.65107 ~ 7.64882), 1H (t, 7.56945 ~ 7.53826), 3H (m, 7.43582 ~ 7.37401), 5H (m, 7.33843 ~ 7.31328), 1H (d, 7.24848 ~ 7.22573), 7H (m, 7.17432-7.08918)

EI-MS: m / z 494 (M +)

1-16) Synthesis of Compound 60

Intermediate 10 (86 g), acetic acid (860 ml) and hydrochloric acid (65 ml) were added to a 2000 ml three-necked round bottom flask, which was then stirred at 110 ° C. for 8 hours and then cooled. The reaction solution was filtered, washed sequentially with water and methanol and dried to give 73 g of the title compound as a white powder.

¹ H-NMR (CDCl ₃ , 500 MHz) 1H (d, 8.47328-8.45531), 1H (8.33741-8.32272), 5H (m, 8.02071-7.97134), 4H (m, 7.84917-7.79753), 1H (d, 7.72216- 7.71878), 1H (t, 7.64235 ~ 7.60942), 1H (d, 7.59455 ~ 7.57882), 2H (m, 7.46937 ~ 7.27417), 2H (t, 7.41111 ~ 7.37974), 1H (d, 7.24121 ~ 7.22491), 1H ( d, 7.19883 ~ 7.18285) 1H (t, 7.15221 ~ 7.11999), 2H (t, 7.10141 ~ 7.07155), 2H (d, 7.00241 ~ 6.98724), 1H (d, 6.58911 ~ 6.57411)

EI-MS: m / z 543 (M +)

Example 2 Synthesis of Compounds 30 and 35 of the Invention (See Scheme 6 below)

2-1) Synthesis of Intermediate 11

Compound 1 (3.6 g) and carbon tetrachloride (350 ml) were added to a 500 ml round bottom flask, and bromine (1.4 ml) was slowly added at room temperature, followed by stirring for 12 hours. An aqueous sodium hydrogen carbonate solution was added to the reaction solution, the mixture was stirred for 1 hour, and the layers were separated to remove water. The organic layer was washed twice with water, and then the solvent was concentrated under reduced pressure to obtain 3.5 g of the title compound.

2-2) Synthesis of Compound 30

In a 100 ml three-necked round bottom flask, intermediate 11 (2.5 g), phenanthrene-9-boronic acid (1.2 g), tetrahydrofuran (30 ml), potassium carbonate (1.2 g) and water (12 ml) were added and stirred. . Tetrakis (triphenylphosphine) palladium (0) (0.31 g) was added to this mixed solution, and it heated to 80 degreeC. The reaction solution was cooled, filtered and the crystals were washed with acetone and recrystallized with methylene chloride to obtain 2.8 g of the title compound.

¹ H-NMR (CDCl ₃ , 500 MHz) (2H, t, 8.80632-8.76906), (1H, d, 8.51897, 8.50110), (1H, d, 8.45247, 8.43721), (3H, m, 7.99857-7.73160), (1H, d, 7.90403, 7.88842), (1H, s, 7.82223), (3H, t, 7.72569-77.65858), (2H, m, 7.66060-77.64545), (1H, d, 7.58735, 7.57104), (2H , t, 7.43138-7.39448), (1H, t, 7.38109-7.34908), (2H, m, 7.23078-7.17798), (4H, m, 7.15621-7.09810), (1H, d, 7.08400, 7.07189), (1H , t, 6.93138 to 6.89953), (1H, t, 6.85192 to 6.81964), (1H, d, 6.57207, 6.55711)

EI-MS: m / z 592 (M +)

2-3) Synthesis of Compound 35

In a 100 ml three-necked round bottom flask, intermediate 11 (4 g), 4- (1-naphthalene) -1-phenylboronic acid (2.3 g), tetrahydrofuran (40 ml), potassium carbonate (2.5 g) and water (20 ml) was added and stirred. Tetrakis (triphenylphosphine) palladium (0) (0.53 g) was added to this mixed solution, and it heated at 80 degreeC. The reaction solution was cooled, filtered and the crystals were washed with acetone and recrystallized with methylene chloride to obtain 2 g of the title compound.

¹ H-NMR (CDCl ₃ , 500 MHz) (1H, d, 8.48532, 8.46735), (1H, d, 8.41562, 8.40007), (1H, d, 8.07572, 8.05957), (2H, d, 7.99909, 7.98380), (3H, m, 7.94149-7.88387), (1H, d, 7.83335, 7.81698), (6H, m, 7.71184-7.61582), (4H, m, 7.56625-7.48845), (2H, t, 7.4.551-7.7579 ), (1H, t, 7.19805 to 7.16625), (1H, t, 7.15543 to 7.72234), (3H, t, 7.10562 to 7.07492), (2H, d, 7.02127 to 7.00615), (1H, t, 6.84303 to 6.71196 ), (1H, d, 6.62948, 6.61470)

EI-MS: m / z 618 (M +)

Example 3 Synthesis of Compounds 94, 105, 106, 107, 110, 112 of the Invention (See Scheme 7 below)

3-1) Synthesis of Intermediate 12

Compound 59 (40 g) and carbon tetrachloride (4000 ml) were added to a 10 L three-neck reactor, and bromine (14 ml) was slowly added at room temperature, followed by stirring for 12 hours. An aqueous sodium hydrogen carbonate solution was added to the reaction solution, the mixture was stirred for 1 hour, and the layers were separated to remove water. The organic layer was washed twice with water, and then the solvent was concentrated under reduced pressure to obtain 36 g of the title compound.

3-2) Synthesis of Compound 105

In a 100 ml three-necked round bottom flask, intermediate 12 (1.6 g), naphthalen-1-yl boronic acid (0.65 g), tetrahydrofuran (20 ml), potassium carbonate (1 g) and water (10 ml) were added and stirred. . Tetrakis (triphenylphosphine) palladium (0) (0.2 g) was added to this mixed solution, and it heated at 80 degreeC. The reaction solution was cooled, filtered and the crystals were washed with acetone and recrystallized with methylene chloride to obtain 1.6 g of the title compound.

¹ H-NMR (CDCl ₃ , 500 MHz) 1H (d, 8.53529-8.51727), 1H (d, 8.44197-8.42649), 3H (t, 8.01437-7.83325), 3H (m, 7.94330-7.82101), 1H (d, 7.65249 ~ 7.63733), 5H (m, 7.60906 ~ 7.53009), 1H (t, 7.48996 ~ 7.4596), 4H (m, 7.43566 ~ 7.36620), 2H (m, 7.32983 ~ 7.27914), 6H (m, 7.18386 ~ 7.09477), 1H (d, 7.04772 ~ 7.03182), 1H (t, 6.95497 ~ 6.92397), 1H (d, 6.58601 ~ 6.57122)

EI-MS: m / z 618 (M +)

3-3) Synthesis of Compound 106

In a 100 ml three-necked round bottom flask, intermediate 12 (1.6 g), naphthalen-1-yl boronic acid (0.65 g), tetrahydrofuran (20 ml), potassium carbonate (1 g) and water (10 ml) were added and stirred. . Tetrakis (triphenylphosphine) palladium (0) (0.2 g) was added to this mixed solution, and it heated at 80 degreeC. The reaction solution was cooled, filtered and the crystals were washed with acetone and recrystallized with methylene chloride to obtain 1.3 g of the title compound.

¹ H-NMR (CDCl ₃ , 500MHz) 1H (d, 8.511-8.489), 1H (d, 8.422-8.403), 3H (d, 8.013 ~ 7.993), 1H (s, 7.968), 4H (m, 7.968 ~ 7.885), 3H (m, 7.709 ~ 7.670), 4H (m, 7.572 ~ 7.523), 2H (d, 7.420 ~ 7.401), 2H (d, 7.379 ~ 7.359), 1H (d, 7.309 ~ 7.291), 5H ( m, 7.155 ~ 7.083), 2H (t, 7.072 ~ 7.034), 1H (d, 6.622 ~ 6.603)

EI-MS: m / z 618 (M +)

3-4) Synthesis of Compound 107

In a 100 ml three-necked round bottom flask, intermediate 12 (1.6 g), phenanthrene-9-yl boronic acid (0.8 g), tetrahydrofuran (20 ml), potassium carbonate (1 g) and water (10 ml) were added and stirred. It was. Tetrakis (triphenylphosphine) palladium (0) (0.2 g) was added to this mixed solution, and it heated at 80 degreeC. The reaction solution was cooled, filtered and the crystals were washed with acetone and recrystallized with methylene chloride to obtain 1.7 g of the title compound.

¹ H-NMR (CDCl ₃ , 500 MHz) 2H (t, 8.81288-8.77500), 1H (d, 8.55131-8.53321), 1H (d, 8.46897-8.45351), 3H (m, 8.01953-7.8434), 2H (m, 7.93261 ~ 7.89642), 1H (s, 7.83116), 2H (t, 7.72631 ~ 7.7013), 2H (m, 7.7652 ~ 7.62284), 3H (t, 7.59702 ~ 7.56190), 5H (m, 7.42695 ~ 7.37036), 1H ( d, 7.3153 ~ 7.29849), 1H (d, 7.24387 ~ 7.22756), 5H (m, 7.16763 ~ 7.09821), 1H (d, 7.05443 ~ 7.03867), 1H (d, 6.93049 ~ 6.91430), 1H (d, 6.59103 ~ 6.57612 )

EI-MS: m / z 669 (M +)

3-5) Synthesis of Compound 110

In a 100 ml three-necked round bottom flask, Intermediate 12 (1.6 g), 4- (1-naphthalene) -1-phenylboronic acid (0.86 g), tetrahydrofuran (20 ml), potassium carbonate (1 g) and water (10 ml) was added and stirred. Tetrakis (triphenylphosphine) palladium (0) (0.2 g) was added to this mixed solution, and it heated at 80 degreeC. The reaction solution was cooled, filtered and the crystals were washed with acetone and recrystallized with methylene chloride to obtain 1.5 g of the title compound.

¹ H-NMR (CDCl ₃ , 500 MHz) (1H, d, 8.50970-8.49168), (1H, d, 8.42353, 8.4.794), (1H, d, 8.07996, 8.06194), (2H, d, 8.01643, 8.00113 ), (1H, d, 7.98321, 7.96542), (3H, m, 7.94593-7.89355), (1H, d, 7.84365, 7.82718), (5H, m, 7.69204-7.7.61719), (6H, d, 7.58142-7.47368 ), (4H, m, 7.41957-7.5884), (1H, t, 7.30467-7.27303), (5H, m, 7.16011-7.09383), (2H, d, 7.05529, 7.04019), (1H, d, 6.64619, 6.63128 )

EI-MS: m / z 695 (M +)

3-6) Synthesis of Compound 112

In a 100 ml three-necked round bottom flask, intermediate 12 (1.6 g), 3,5-diphenyl-1-benzeneboronic acid (1.0 g), tetrahydrofuran (20 ml), potassium carbonate (1 g) and water (10 ml) ) Was added and stirred. Tetrakis (triphenylphosphine) palladium (0) (0.2 g) was added to this mixed solution, and it heated at 80 degreeC. The reaction solution was cooled, filtered and the crystals were washed with acetone and recrystallized with methylene chloride to obtain 1.6 g of the title compound.

¹ H-NMR (CDCl ₃ , 500 MHz) 1H (d, 8.510-8.487), 1H (d, 8.421-8.401), 3H (t, 8.013-7.967), 2H (d, 7.914-7.880), 1H (d, 7.826 ~ 7.809), 2H (s, 7.764), 5H (m, 7.724 ~ 7.687), 2H (d, 7.567 ~ 7.549), 4H (m, 7.484 ~ 7.447), 6H (m, 7.394 ~ 7.358), 1H ( d, 7.275 ~ 7.290), 1H (d, 7.135 ~ 7.155), 4H (m, 7.131 ~ 7.088), 2H (d, 7.049 ~ 7.030), 1H (d, 6.647 ~ 6.631)

EI-MS: m / z 721 (M +)

3-7) Synthesis of Compound 94

Argon gas for 30 minutes after adding Intermediate 12 (2 g), p, p'-ditolylamine (0.83 g), sodium t-butoxide (0.5 g) and toluene (30 ml) in a 100 ml three-necked round bottom flask It stirred under atmosphere. Then, palladium acetate (0.01 g) and tri (t-butyl) phosphine (0.03 g) were added thereto, and the mixture was stirred under reflux for 24 hours. After cooling the reaction solution, the mixture was extracted with distilled water and methylene chloride and column purified with a developing solvent having a ratio of methylene chloride / hexane of 1/10 to obtain 1.3 g of the title compound.

¹ H-NMR (CDCl ₃ , 500 MHz) 1H (d, 8.40662-8.38865), 1H (d, 8.27474-8.25850), 2H (d, 7.98672-7.97146), 1H (d, 7.94144-7.92362), 1H (s, 7.88668), 1H (d, 7.70756 ~ 7.69126), 2H (d, 7.55254 ~ 7.53757), 5H (m, 7.40997 ~ 7.35293), 1H (d, 7.29707 ~ 7.28230), 74H (t, 7.11244 ~ 7.08420), 11H ( m, 7.02547-6.95006), 1H (d, 6.54138-6.52653), 6H (s, 2.27060)

EI-MS: m / z 688 (M +)

Example 4 Synthesis of Compounds 79, 127, 135, 136, 142, 149 of the Invention (See Scheme 8 below)

  4-1) Synthesis of Intermediate 13

Compound 60 (73 g) and chloroform (3000 ml) were added to a 5000 ml three-necked round bottom flask, and bromine (22 g) was slowly added at room temperature and stirred for 12 hours. An aqueous sodium hydrogen carbonate solution was added to the reaction solution, the mixture was stirred for 1 hour, and the layers were separated to remove water. The organic layer was washed twice with water, and then the solvent was concentrated under reduced pressure to obtain 69 g of the title compound.

4-2) Synthesis of Compound 127

In a 100 ml three-necked round bottom flask, intermediate 13 (3 g), phenylboronic acid (0.65 g), tetrahydrofuran (30 ml), potassium carbonate (1.5 g) and water (15 ml) were added and stirred. Tetrakis (triphenylphosphine) palladium (0) (0.3 g) was added to this mixed solution, and it heated at 80 degreeC. The reaction solution was cooled, filtered and the crystals were washed with acetone and recrystallized with methylene chloride to obtain 1.9 g of the title compound.

¹ H-NMR (CDCl ₃ , 500 MHz) 1H (d, 8.51199-8.49398), 1H (d, 8.39795-8.38243), 5H (m, 8.04242-7.99982), 3H (m, 7.86489-7.81868), 1H (d, 7.74021 ~ 7.72496), 1H (d, 7.67810 ~ 7.66162), 1H (d, 7.59553 ~ 7.58028), 2H (d, 7.54640 ~ 7.53246), 2H (d, 7.51086 ~ 7.48617), 5H (m, 7.48102 ~ 7.39640), 1H (d, 7.29018 ~ 7.27476), 3H (m, 7.09912 ~ 7.07372), 2H (d, 7.05356 ~ 7.03849), 1H (d, 6.62035 ~ 6.60552)

EI-MS: m / z 619 (M +)

4-3) Synthesis of Compound 142

In a 100 ml three-necked round bottom flask, intermediate 13 (3 g), naphthalen-1-yl boronic acid (0.86 g), tetrahydrofuran (30 ml), potassium carbonate (1.5 g) and water (15 ml) were added and stirred. . Tetrakis (triphenylphosphine) palladium (0) (0.3 g) was added to this mixture, and it heated at 80 degreeC. The reaction solution was cooled, filtered and the crystals were washed with acetone and recrystallized with methylene chloride to obtain 2.5 g of the title compound.

¹ H-NMR (CDCl ₃ , 500 MHz) 1H (d, 8.55194 to 8.53389), 1H (d, 8.44938 to 8.43389), 5H (m, 8.05377 to 7.9422), 2H (m, 7.94290 to 7.72670), 3H (m, 7.86461 ~ 7.81818), 1H (d, 7.75609 ~ 7.73974), 1H (d, 7.65462 ~ 7.63952), 1H (t, 7.60321) ~ 7.57434), 2H (d, 7.54678 ~ 7.53262), 5H (m, 7.47213 ~ 7.37454) , 2H (m. 7.32543 ~ 7.26461), 1H (d, 7.22727 ~ 7.21276), 4H (d, 7.17476 ~ 7.10074), 1H (d, 7.06149 ~ 7.04726), 1H (t, 6.95780 ~ 6.92682), 1H (d, 6.59686-6.58235)

EI-MS: m / z 669 (M +)

4-4) Synthesis of Compound 79

In a 100 ml three-necked round bottom flask, intermediate 13 (3 g), naphthalen-2-yl boronic acid (0.86 g), tetrahydrofuran (30 ml), potassium carbonate (1.5 g) and water (15 ml) were added and stirred. . Tetrakis (triphenylphosphine) palladium (0) (0.3 g) was added to this mixed solution, and it heated at 80 degreeC. The reaction solution was cooled, filtered and the crystals were washed with acetone and recrystallized with methylene chloride to obtain 2.8 g of the title compound.

¹ H-NMR (CDCl ₃ , 500 MHz) 1H (d, 8.52948-8.51151), 1H (d, 8.43140-8.41591), 6H (m, 8.04919-8.00992), 1H (d, 7.96729-7.91745), 2H (m, 7.93395-7.88795), 3H (m, 7.86613-7.81975), 4H (m, 7.73449-7.6229), 2H (m, 7.54594-7.52709), 2H (m, 7.4775-7.44520) 2H (t, 7.43037-7.40046), 1H (d, 7.28198-7.26668), 1H (d, 7.22398-7.20838), 5H (m, 7.13732-7.05340), 1H (d, 6.63504-6.62016)

EI-MS: m / z 669 (M +)

 4-5) Synthesis of Compound 149

In a 100 ml three-necked round-bottom flask, intermediate 13 (3 g), 3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) pyridine (1.2 g), toluene (60 ml), ethanol (20 ml), potassium carbonate (3.2 g) and water (12 ml) were added thereto and stirred. Tetrakis (triphenylphosphine) palladium (0) (0.3 g) was added to this mixed solution, and it heated at 80 degreeC. The reaction solution was cooled and filtered to obtain 1.9 g of the title compound.

¹ H NMR (CDCl ₃ , 500 MHz) 1H (s, 8.80024), 1H (d, 8.68563-8.67595), 1H (d, 8.49616-8.47943), 1H (d, 8.40828-8.39219), 5H (m, 8.04083-8.00097 ), 4H (m, 7.85855-7.81232), 1H (d, 7.73003-7.713519), 2H (t, 7.58126-7.56067), 5H (m, 7.46237-7.39811), 1H (d, 7.26325-7.25291), 1H (d , 7.21617 ~ 7.19845), 3H (m, 7.12127 ~ 7.09455), 2H (d, 7.03732 ~ 7.02221), 1H (d, 6.65279 ~ 6.63799)

EI-MS: m / z 620 (M +)

4-6) Synthesis of Compound 135

Intermediate 13 (3 g) and tetrahydrofuran (60 ml) were added to a 100 ml three-necked round bottom flask, and the mixture was stirred under an argon atmosphere and the temperature of the mixed solution was lowered to -78 ° C. N-butyllithium (1.6 M) (3.6 ml) was slowly added thereto, followed by stirring for 2 hours. A solution of diphenylchlorophosphine (1.2 g) dissolved in 10 ml of tetrahydrofuran was slowly added to the mixture, the mixture was stirred at -78 ° C for 12 hours, and then heated to room temperature to react for 2 hours. Distilled water and ethyl acetate were added to the reaction solution and extracted. 3 g of the title compound was obtained by column purification using a developing solvent having an ethyl acetate / methylene chloride ratio of 1/1.

¹ H-NMR (CDCl ₃ , 500 MHz) 1H (d, 8.39612-8.38187), 1H (d, 8.32135-8.21172),

1H (d, 8.19516 ~ 8.17332), 5H (t, 8.00601 ~ 7.97697), 9H (m, 7.85797 ~ 7.81232), 2H (t, 7.72558 ~ 7.70863), 7H (m, 7.49221 ~ 7.44267), 2H (t, 7.41666 ~ 7.37143), 1H (d, 7.19087 ~ 7.15188), 3H (t, 7.11421 ~ 7.08367), 2H (d, 7.00232 ~ 6.96912), 1H (d, 6.63155 ~ 6.59686)

EI-MS: m / z 727 (M +)

 4-7) Synthesis of Compound 136

Compound 135 (3 g), methylene chloride (30 ml) and 30% hydrogen peroxide (6 ml) were added to a 100 ml round bottom flask, followed by stirring at room temperature for about 3 hours. Water (30 ml) was added to the reaction mixture, followed by washing several times with 5% aqueous NaOH solution. The organic layer was dried over anhydrous magnesium sulfate. 2.4 g of the title compound was obtained by column purification using a developing solvent having an ethyl acetate / methylene chloride ratio of 1/1.

¹ H-NMR (CDCl ₃ , 500 MHz): 1H (d, 8.39612-8.37866), 1H (d, 8.3480-8.32321),

1H (d, 8.21835 ~ 8.20331), 5H (t, 8.02985 ~ 7.98276), 9H (m, 7.86041 ~ 7.70444), 2H (t, 7.58578 ~ 7.55606), 7H (m, 7.50613 ~ 7.43728), 2H (t, 7.41221 ~ 7.38188), 1H (d, 7.21632 ~ 7.19818), 3H (t, 7.10778 ~ 7.07620), 2H (d, 6.94427 ~ 6.92934), 1H (d, 6.61311 ~ 6.59815)

EI-MS: m / z 743 (M +)

Example 5 Synthesis of Compounds 257, 259, 260 of the Invention (See Scheme 9 below)

Wherein OTf is trifluoromethanesulfonyl.

5-1) Synthesis of Intermediate 14

2-methylnaphthalen-1-yl boronic acid (15 g), 1-bromo-6-phenylnaphthalen-2-yl trifluoromethanesulfonate (35.5 g), tetrahydrofuran in a 250 ml three-necked round bottom flask (100 ml), potassium carbonate (13 g) and water (50 ml) were added thereto and stirred. Tetrakis (triphenylphosphine) palladium (0) (4.7 g) was put into this mixed solution, and it heated at 80 degreeC. After cooling the reaction solution, washed twice with distilled water (100 ml) and then again with ethanol (200 ml) to give 22g of the title compound.

5-2) Synthesis of Intermediate 15

Intermediate 14 (22 g) and tetrahydrofuran (220 ml) were added to a 500 ml three-necked round bottom flask, and the mixture was stirred under an argon atmosphere and the temperature of the mixed solution was lowered to -78 ° C. N -butyllithium (1.6M) (36 ml) was slowly added thereto, followed by stirring for 2 hours. A solution of fluorenone (9.4 g) dissolved in tetrahydrofuran (30 ml) was slowly added to the mixed solution, and the temperature of the mixed solution was raised to room temperature, followed by stirring for 12 hours. Water (20 ml) was added to the reaction solution and stirred for 2 hours. The reaction solution was separated and the water was removed, the organic layer was cooled, and the crystals were filtered to obtain 29 g of the title compound.

5-3) Synthesis of Compound 257

Intermediate 15 (29 g), acetic acid (300 ml) and hydrochloric acid (25 ml) were added to a 100 ml three-necked round bottom flask, followed by stirring at 110 ° C. for 8 hours and then cooling. The reaction solution was filtered, washed sequentially with water and methanol and dried to obtain 21 g of the title compound as a white powder.

¹ H NMR (CDCl ₃ , 500MHz): 1H (d, 8.32543 ~ 8.30754), 1H (d, 8.19886 ~ 8.18065), 3H (t, 8.01560 ~ 7.96865), 3H (m, 7.94767 ~ 7.88628), 2H (d, 7.54172 ~ 7.52680), 4H (m, 7.40576 ~ 7.34870), 2H (m, 7.29556 ~ 7.21832), 4H (m, 7.14566 ~ 7.04327), 2H (d, 6.94548 ~ 6.93466), 1H (d, 6.65264 ~ 6.63758), 3H (s, 2.68356)

EI-MS: m / z 507 (M +)

5-4) Synthesis of Intermediate 16

Compound 257 (21 g) and chloroform (1200 ml) were added to a 2000 ml three-necked round bottom flask, and bromine (9.2 g) was slowly added at room temperature and stirred for 12 hours. An aqueous sodium hydrogen carbonate solution was added to the reaction solution, the mixture was stirred for 1 hour, and the layers were separated to remove water. The organic layer was washed twice with water, and then the solvent was concentrated under reduced pressure to obtain 18 g of the title compound.

5-5) Synthesis of Compound 259

In a 250 ml three-necked round bottom flask, intermediate 16 (10 g), phenanthrene-9-yl boronic acid (4.2 g), tetrahydrofuran (100 ml), potassium carbonate (3.9 g) and water (40 ml) were added and stirred. It was. Tetrakis (triphenylphosphine) palladium (0) (1.1 g) was added to this mixed solution, and it heated at 80 degreeC. The reaction solution was cooled, filtered, and the crystals were washed with acetone and recrystallized with methylene chloride to obtain 13 g of the title compound.

¹ H NMR (CDCl ₃ , 500 MHz): 2H (t, 8.79652-8.75836), 1H (d, 8.43321-8.41521), 1H (d, 8.39897-8.38319), 3H (m, 7.99875-7.94919), 2H (m, 7.91587-7.87968), 1H (s, 7.84221), 2H (t, 7.75157 ~ 7.71635), 2H (m, 7.69022 ~ 7.66037), 3H (t, 7.59199 ~ 7.55978), 5H (m, 7.43712 ~ 7.38316), 1H ( d, 7.33532 ~ 7.30987), 1H (d, 7.28712 ~ 7.25621), 4H (m, 7.17623 ~ 7.10643), 1H (d, 7.03213 ~ 7.01556), 1H (d, 6.98097 ~ 6.96463), 1H (d, 6.58013 ~ 6.56302 ), 3H (s, 2.75243)

EI-MS: m / z 683 (M +)

5-6) Synthesis of Compound 260

In a 100 ml three-necked round bottom flask, intermediate 16 (10 g), 4- (1-naphthalene) -1-phenylboronic acid (4.7 g), tetrahydrofuran (100 ml), potassium carbonate (3.9 g) and water (40) ml) was added and stirred. Tetrakis (triphenylphosphine) palladium (0) (1.1 g) was added to this mixed solution, and it heated at 80 degreeC. The reaction solution was cooled, filtered and the crystals were washed with acetone and recrystallized with methylene chloride to obtain 12 g of the title compound.

¹ H NMR (CDCl ₃ , 500 MHz): 1H (d, 8.48257-8.46562), 1H (d, 8.40254-8.38596), 1H (d, 8.05832-88.04220), 2H (d, 8.00324-7.98666), 1H (d, 7.97954 ~ 7.96394), 3H (m, 94291 ~ 7.88471), 1H (d, 7.86588 ~ 7.84936), 5H (m, 7.60124 ~ 7.61055), 6H (m, 7.56555 ~ 7.48242), 4H (m, 7.44577 ~ 7.38305), 1H (t, 7.31357 ~ 7.29255), 4H (7.18356 ~ 7.12363), 1H (d, 7.09144 ~ 7.07529), 1H (d, 6.65264 ~ 6.63775), 3H (s, 2.68341)

EI-MS: m / z 709 (M +)

Maximum absorption wavelength (UV-Vis spectrum), maximum emission wavelength (PL: Photoluminescence), glass transition temperature (T _g ), melting point (T _m ), band gap (in the solution of the compounds obtained in Examples 1 to 5) Bg: bandgap), and HOMO and LUMO levels were measured and the results are shown in Table 1 below. In addition, the absorption and emission spectra of Compound 1 obtained in Example 1 are shown in FIG. 1, and ¹ H-NMR, mass spectrometry, absorption and emission spectra, and thermal analysis graphs of Compound 110 obtained in Example 3 are shown in FIGS. 5 is shown respectively.

<Production of Organic Electroluminescent Device>

Example 6

A glass substrate of size 40 mm × 40 mm × 0.7 mm, having an ITO (indium tin oxide) transparent electrode line having a thin film thickness of 150 nm, was ultrasonically cleaned in distilled water with detergent for 10 minutes and 10 minutes in distilled water. The wash was repeated twice. After the distilled water was washed, the substrate was sequentially ultrasonically cleaned and dried using a solvent such as isopropyl alcohol, acetone, and methanol. Subsequently, after dry cleaning using oxygen / argon plasma, the glass substrate having the transparent electrode lines was mounted on the substrate holder of the vacuum deposition apparatus, and the film thickness 60 was formed so as to cover the transparent electrodes on the surface where the transparent electrode lines were formed. Holes in nm N, N' -diphenyl- N, N' -bis- [4- (phenyl- m -tolylamino) phenyl] -biphenyl-4,4'-diamine membrane (hereinafter DNTPD membrane) It formed into a film as an injection layer. Next, a 4,4'-bis [ N- (1-naphthyl) -N -phenylamino] biphenyl film (hereinafter referred to as NPB film) having a thickness of 30 nm was formed on the DNTPD film as a hole transport layer. Next, Compound 30 and BD-1 having a film thickness of 20 nm on NPB film [4- (2- (4,4'-phenylbiphenyl) vinyl) -N, N-diphenylbenzeneamine, see Structural Formula below] Was deposited as a light emitting host material and a dopant material at a weight ratio of 100 to 5, respectively, to form a light emitting layer. A tris (8-quinolinol) aluminum film (hereinafter, Alq film) having a film thickness of 20 nm was formed on the film as an electron transporting layer. Subsequently, LiF was deposited thereon to form an electron injection layer. Metal aluminum was deposited on the LiF film to form a metal cathode, thereby manufacturing an organic electroluminescent device.

In the organic electroluminescent device manufactured as described above, a current density of 31.5 mA / cm ² was measured using a voltage of 7 V, and light emission was 1229 corresponding to x = 0.13 and y = 0.14 based on a 1931 CIE color coordinate. A spectrum of cd / m ² brightness was observed and the luminous efficiency was 3.9 cd / A.

BD-1

BD-1

Examples 7-20 and Comparative Example 1

An organic electroluminescent device was manufactured in the same manner as in Example 6, except that the material shown in Table 2 was used instead of the compound 30 as a light emitting host material. Β-ADN, the host material used in Comparative Example 1, is 9,10-di (naphthalen-2-yl) anthracene (see Structural Formula below).

The physical property measurement results of the fabricated organic electroluminescent device are shown in Table 2 below.

β-ADN

β-ADN

Example 21

An organic electroluminescent device was manufactured in the same manner as in Example 6, except that β-ADN was used instead of Compound 30 as a light emitting host material and Compound 94 was used instead of BD-1 as a light emitting dopant material. .

The physical property measurement results of the fabricated organic electroluminescent device are shown in Table 2 below.

As can be seen from the results of Table 2, the organic electroluminescent device of the present invention prepared in Examples 6 to 21 has improved driving voltage, luminous efficiency, color purity and lifespan characteristics compared to the case of Comparative Example 1 using a conventional light emitting material Indicates.

Example 22

An organic electroluminescent device was manufactured in the same manner as in Comparative Example 1, except that Compound 149 was used instead of Alq when forming the ETL.

In the organic electroluminescent device manufactured as described above, a current density of 42.1 mA / cm ² was measured using a voltage of 7 V, and light emission was 1895 corresponding to x = 0.13 and y = 0.14 based on a 1931 CIE color coordinate. A spectrum of cd / m ² brightness was observed and the luminous efficiency was 4.5 cd / A. These results show that Compound 149 can play a role as an excellent electron transport layer material as being significantly superior to Comparative Example 1.

1 is an absorption and emission spectrum of Compound 1 obtained in Example 1,

2 to 5 are ¹ H-NMR, mass spectrometry, absorption and emission spectra, and thermal analysis graphs of Compound 110 obtained in Example 3, respectively.

Claims (14)

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

Where R ₁ and R ₂ are each independently hydrogen, C _1-50 alkyl, C _3-50 cycloalkyl, C _6-50 aryl or heteroaryl having 5 to 50 nuclear atoms, wherein R ₁ to R ₂ are optionally C _1-50 alkyl, C _6-50 aryl, 5 to 50 heteroaryl or C _7-50 aralkyl may be substituted, and R ₁ and R ₂ are optionally bonded to each other to C _4-50 saturated May form a ring or an unsaturated ring; Ar is an aromatic hydrocarbon having two or more benzene rings conjugated or unsubstituted by X; R ₃ and X are each independently hydrogen, halogen, cyano, nitro, amino, thio, phosphoryl, phosphinyl, carbonyl, silyl, boranyl, C _1-50 alkyl, C _2-50 alkenyl, C _2-50 alkynyl, C _1-50 alkoxy, C _3-50 cycloalkyl, C _6-50 aryl or heteroaryl having 5 to 50 nuclear atoms (where X is not hydrogen), wherein R ₃ and X are Amino, thio, carbonyl, silyl, boranyl, C _1-50 alkyl, C _2-50 alkenyl, C _2-50 alkynyl, C _1- , optionally substituted with C _1-6 alkyl ₅₀ alkoxy, C _3-50 cycloalkyl, C _6-50 aryl, 5 to 50 heteroaryl or C _7-50 aralkyl, and each of R ₃ and X may optionally be bonded to an adjacent group. To form a C _4-50 saturated ring or unsaturated ring; n is an integer of 1-6. The method of claim 1, A compound according to claim 1, wherein the compound of Formula 1 is any one of the following Formulas 1a to 1h: [Formula 1a]

[Chemical Formula 1b]

[Formula 1c]

&Lt; RTI ID = 0.0 &

[Formula 1e]

[Formula 1f]

[Formula 1g]

[Formula 1h]

Where R ₁ to R ₃ , X and n are as defined in claim 1; m is an integer from 1 to 6; z is an integer from 1 to 8. The method of claim 1, A compound according to claim 1, wherein the compound of Formula 1 is a compound of Formula 1a: [Formula 1a]

Where R ₁ to R ₃ , X and n are as defined in claim 1; m is an integer of 1-6. The method of claim 1, A compound according to claim 1, wherein the compound of formula 1 is a compound of formula 1g: [Formula 1g]

Where R ₁ to R ₃ , X and n are as defined in claim 1; z is an integer from 1 to 8. (1) In a mixed solvent of an organic solvent and water, a compound of formula 2 is reacted with a compound of formula 3 to prepare a compound of formula 4, (2) reacting a compound of formula 4 with a compound of formula 5 in an organic solvent in the presence of a base to prepare a compound of formula 6 (3) cyclizing the compound of formula 6 in the presence of an acid, Method for preparing a compound of Formula 1i

Where R ₁ and R ₂ are each independently hydrogen, C _1-50 alkyl, C _3-50 cycloalkyl, C _6-50 aryl or heteroaryl having 5 to 50 nuclear atoms, wherein R ₁ to R ₂ are optionally C _1-50 alkyl, C _6-50 aryl, 5 to 50 heteroaryl or C _7-50 aralkyl may be substituted, and R ₁ and R ₂ are optionally bonded to each other to C _4-50 saturated May form a ring or an unsaturated ring; Ar is an aromatic hydrocarbon having two or more benzene rings conjugated or unsubstituted by X; X is halogen, cyano, nitro, amino, thio, phosphoryl, phosphinyl, carbonyl, silyl, boranyl, C _1-50 alkyl, C _2-50 alkenyl, C _2-50 alkynyl, C _{1 -50} alkoxy, C _3-50 cycloalkyl, C _6-50 aryl or heteroaryl having 5 to 50 nuclear atoms, wherein X is optionally substituted with C _1-6 alkyl, amino, thio, Carbonyl, silyl, boranyl, C _1-50 alkyl, C _2-50 alkenyl, C _2-50 alkynyl, C _1-50 alkoxy, C _3-50 cycloalkyl, C _6-50 aryl, nuclear atom May be substituted with 5 to 50 heteroaryl or C _7-50 aralkyl, and X may optionally combine with adjacent groups to form a C _4-50 saturated or unsaturated ring; X ₁ and X ₂ are each independently trifluoromethanesulfonyl or halogen; Y ₁ and Y ₂ are each independently hydrogen or C _1-6 alkyl, and Y ₁ and Y ₂ may be bonded to each other to form a ring. (1) In a mixed solvent of an organic solvent and water, a compound of formula 2 is reacted with a compound of formula 3 to prepare a compound of formula 4, (2) reacting a compound of formula 4 with a compound of formula 5 in an organic solvent in the presence of a base to prepare a compound of formula 6 (3) a compound of formula 6i is prepared by cyclization of a compound of formula 6 in the presence of an acid, (4) reacting a compound of Formula 1i with (X ₃ ) ₂ in an organic solvent to produce a compound of Formula 7 (5) comprising reacting a compound of formula 7 with a compound of formula 8 in a mixed solvent of an organic solvent and water, To prepare a compound of Formula 1j: [Formula 2]

(3)

[Formula 4]

[Chemical Formula 5]

[Formula 6]

Formula 1i]

Where R ₁ and R ₂ are each independently hydrogen, C _1-50 alkyl, C _3-50 cycloalkyl, C _6-50 aryl or heteroaryl having 5 to 50 nuclear atoms, wherein R ₁ to R ₂ are optionally C _1-50 alkyl, C _6-50 aryl, 5 to 50 heteroaryl or C _7-50 aralkyl may be substituted, and R ₁ and R ₂ are optionally bonded to each other to C _4-50 saturated May form a ring or an unsaturated ring; Ar is an aromatic hydrocarbon having two or more benzene rings conjugated or unsubstituted by X; R ₃ ′ and X are each independently halogen, cyano, nitro, amino, thio, phosphoryl, phosphinyl, carbonyl, silyl, boranyl, C _1-50 alkyl, C _2-50 alkenyl, C _{2 -50} alkynyl, C _1-50 alkoxy, C _3-50 cycloalkyl, C _6-50 aryl or heteroaryl having 5 to 50 nuclear atoms, wherein R ₃ ′ and X are optionally C _1-6 alkyl Substituted or unsubstituted amino, thio, carbonyl, silyl, boranyl, C _1-50 alkyl, C _2-50 alkenyl, C _2-50 alkynyl, C _1-50 alkoxy, C _3-50 cyclo Alkyl, C _6-50 aryl, heteroaryl having 5 to 50 nuclear atoms, or C _7-50 aralkyl, each of R ₃ ′ and X optionally bonded to one another with an adjacent group to form a C _4-50 saturated ring Or may form an unsaturated ring; X ₁ and X ₂ are each independently trifluoromethanesulfonyl or halogen; X ₃ is halogen; Y ₁ and Y ₂ are each independently hydrogen or C _1-6 alkyl, and Y ₁ and Y ₂ may be bonded to each other to form a ring. (1) In a mixed solvent of an organic solvent and water to react the compound of formula 9 with a compound of formula 10 to prepare a compound of formula 11 (2) preparing a compound of formula 12 by reacting a compound of formula 11 with a compound of formula 5 in an organic solvent in the presence of a base: (3) cyclizing the compound of formula 12 in the presence of an acid, Method for preparing a compound of Formula 1k

[Chemical Formula 5]

Where R ₁ and R ₂ are each independently hydrogen, C _1-50 alkyl, C _3-50 cycloalkyl, C _6-50 aryl or heteroaryl having 5 to 50 nuclear atoms, wherein R ₁ to R ₂ are optionally C _1-50 alkyl, C _6-50 aryl, 5 to 50 heteroaryl or C _7-50 aralkyl may be substituted, and R ₁ and R ₂ are optionally bonded to each other to C _4-50 saturated May form a ring or an unsaturated ring; Ar is an aromatic hydrocarbon having two or more benzene rings conjugated or unsubstituted by X; R ₃ ′ and X are each independently halogen, cyano, nitro, amino, thio, phosphoryl, phosphinyl, carbonyl, silyl, boranyl, C _1-50 alkyl, C _2-50 alkenyl, C _{2 -50} alkynyl, C _1-50 alkoxy, C _3-50 cycloalkyl, C _6-50 aryl or heteroaryl having 5 to 50 nuclear atoms, wherein R ₃ ′ and X are optionally C _1-6 alkyl Substituted or unsubstituted amino, thio, carbonyl, silyl, boranyl, C _1-50 alkyl, C _2-50 alkenyl, C _2-50 alkynyl, C _1-50 alkoxy, C _3-50 cyclo Alkyl, C _6-50 aryl, heteroaryl having 5 to 50 nuclear atoms, or C _7-50 aralkyl, each of R ₃ ′ and X optionally bonded to one another with an adjacent group to form a C _4-50 saturated ring Or may form an unsaturated ring; X ₁ and X ₂ are each independently trifluoromethanesulfonyl or halogen; Y ₁ and Y ₂ are each independently hydrogen or C _1-6 alkyl, and Y ₁ and Y ₂ may be bonded to each other to form a ring. (1) In a mixed solvent of an organic solvent and water to react the compound of formula 9 with a compound of formula 10 to prepare a compound of formula 11 (2) preparing a compound of formula 12 by reacting a compound of formula 11 with a compound of formula 5 in an organic solvent in the presence of a base: (3) preparing a compound of formula 1k by cyclizing the compound of formula 12 in the presence of an acid, (4) reacting a compound of Formula 1k with (X ₃ ) ₂ in an organic solvent to prepare a compound of Formula 13 (5) comprising reacting a compound of formula 13 with a compound of formula 14 in a mixed solvent of an organic solvent and water, To prepare a compound of formula [Formula 9]

[Formula 10]

[Formula 11]

[Chemical Formula 5]

[Formula 12]

[Formula 1k]

Where R ₁ and R ₂ are each independently hydrogen, C _1-50 alkyl, C _3-50 cycloalkyl, C _6-50 aryl or heteroaryl having 5 to 50 nuclear atoms, wherein R ₁ to R ₂ are optionally C _1-50 alkyl, C _6-50 aryl, 5 to 50 heteroaryl or C _7-50 aralkyl may be substituted, and R ₁ and R ₂ are optionally bonded to each other to C _4-50 saturated May form a ring or an unsaturated ring; Ar is an aromatic hydrocarbon having two or more benzene rings conjugated or unsubstituted by X; R ₃ ′, R ₃ ″ and X are each independently halogen, cyano, nitro, amino, thio, phosphoryl, phosphinyl, carbonyl, silyl, boranyl, C _1-50 alkyl, C _2-50 al Kenyl, C _2-50 alkynyl, C _1-50 alkoxy, C _3-50 cycloalkyl, C _6-50 aryl or heteroaryl having 5 to 50 nuclear atoms, wherein R ₃ ′, R ₃ ″ and X are Amino, thio, carbonyl, silyl, boranyl, C _1-50 alkyl, C _2-50 alkenyl, C _2-50 alkynyl, C _1- , optionally substituted with C _1-6 alkyl ₅₀ alkoxy, C _3-50 cycloalkyl, C _6-50 aryl, 5 to 50 heteroaryl or C _7-50 aralkyl, and R ₃ ′, R ₃ ″ and X are each adjacent May optionally be combined with one another to form a C _4-50 saturated ring or unsaturated ring; X ₁ and X ₂ are each independently trifluoromethanesulfonyl or halogen; X ₃ is halogen; Y ₁ and Y ₂ are each independently hydrogen or C _1-6 alkyl, and Y ₁ and Y ₂ may be bonded to each other to form a ring. An organic electroluminescent device comprising an anode, a cathode, and at least one organic layer containing the compound of claim 1 between the two electrodes. The method of claim 9, And the organic layer is a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer or a laminate thereof. The method of claim 9, The organic electroluminescent device, characterized in that the organic layer is a light emitting layer. The method of claim 11, An organic electroluminescent device according to claim 1, wherein the compound of claim 1 is used as a light emitting host material or a dopant material. The method of claim 9, The organic electroluminescent device, characterized in that the organic layer is an electron transport layer. The method of claim 10, An organic electroluminescent device comprising a structure in which an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode are sequentially stacked.

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