KR101324150B1 - Organic compounds for organic electro luminescente device and organic electro luminescent device using same - Google Patents

Abstract

상기 화학식 1에서 Ar1은 탄소수 5 내지 20의 2가의 아릴기이며, m은 0 또는 1이다. Ar2 내지 Ar5는 서로 같은 구조이거나, 그 중 적어도 하나가 다른 구조를 갖는 것으로 각각 독립적으로 탄소수 6 내지 탄소수 30의 아릴기이다.
본 발명에 따른파이렌-바이나프탈렌을 포함하는 유기전계 발광 재료는 새로운 구조의 유기 전계 발광 재료로서, OLED 디스플레이와 조명을 비롯한 유기전자소자에서 발광재료의 역할은 물론, 정공주입, 정공 수송, 전자 주입 및 수송의 역할을 하며, OLED 소자에서 높은 효율 특성과 우수한 열적 안정성을 갖는다. The present invention relates to a pyrene-binaphthalene compound for an organic electroluminescent material and an organic electroluminescent material comprising the same, wherein the aryl for an organic electroluminescent device is characterized by the following Chemical Formula 1 having no symmetry in the structure of the molecule. For amine derivatives.
[Chemical Formula 1]

Ar 1 in Formula 1 is a divalent aryl group having 5 to 20 carbon atoms, and m is 0 or 1. Ar2 to Ar5 have the same structure or at least one of them has a different structure, each independently represent an aryl group having 6 to 30 carbon atoms.
The organic electroluminescent material including pyrene-binaphthalene according to the present invention is a novel organic electroluminescent material, and the role of the light emitting material in organic electronic devices including OLED display and lighting, as well as hole injection, hole transport, electron It plays a role of injection and transport, and has high efficiency characteristics and excellent thermal stability in OLED devices.

Description

Arylamine derivatives for organic electroluminescent materials, methods for manufacturing the same, and organic electroluminescent materials including arylamine derivatives for organic electroluminescent materials

The present invention relates to an arylamine derivative for an organic electroluminescent material and an organic electroluminescent material comprising the same, and more particularly, to a pyrene-binaphthalene compound for an organic electroluminescent material and an organic electroluminescent material comprising the same. .

In recent years, as the development of the display industry is accelerated, a display element having a high performance function is required. The display device is generally classified into a light emitting display device and a non-light emitting display device, and examples of the light emitting display device include a cathode ray tube (CRT) and a light emitting diode (LED), and as a non-light emitting display device, a liquid crystal display device ( LCD).

Criteria for indicating the basic performance of the display device include driving voltage, power consumption, efficiency, brightness, contrast, response time, lifetime, display color (color coordinates), and color purity. One of the non-luminous display devices, LCD, is the most widely used because of its light weight, low power consumption. However, the characteristics such as response time, contrast, viewing angle, etc. have not reached a satisfactory level, and there is still much room for improvement. Therefore, organic electroluminescent devices (hereinafter, referred to as OLEDs) are attracting attention as next generation display devices that can compensate for these problems. OLEDs are self-luminous display devices that have wide viewing angles, excellent contrast, and fast response times.

In general, OLED is composed of an organic material layer between the cathode and the anode.

The overall structure of the device is a transparent ITO anode, a hole injection layer (HIL), a hole transport layer (HTL), a light emitting layer (EL), a hole blocking layer (HBL), an electron transport layer (ETL), an electron injection layer (EIL) LiAl It is formed with a cathode such as, and one or two of the organic material layers may be omitted if necessary.

When an electric field is applied between the electrodes, electrons are injected from the cathode side and holes are injected from the anode side. In addition, a phenomenon in which the injected holes and electrons recombine in the emission layer to generate an excited state, and emits energy as light when the excited state returns to the ground state.

These light emitting materials are largely divided into fluorescence and phosphorescence, and a light emitting layer forming method includes a method of doping phosphorescent dopants in a fluorescent host, a method of increasing quantum efficiency by doping a fluorescent dopant in a fluorescent host, and a dopant in a light emitting body. (DCM, Rubrene, DCJTB, etc.), there is a method for moving the light emission wavelength to a long wavelength. Through such doping, the emission wavelength, efficiency, driving voltage, lifespan, etc. are being improved. Below, examples of asymmetric materials of blue OLED and materials showing high-performance emission efficiency of the emission wavelength in an OLED device of an asymmetric material.

In general, the light emitting layer forming materials have structures such as anthracene, pyrene, florene, spiroflorene and the like.

As a prior invention on this, invention of the pyrene structure which has an asymmetric structure is following [Document 1]-[Document 4], etc.,

[Document 1] KR20067024933

[Document 2] KR20080133717

[Reference 3] KR20090071884

Document 4 KR20090124172

Anthracene structures include the following Documents 5 to 10,

[Reference 5] KR20107009408

[Document 6] KR20080068226

Document 7 KR20080044369

[Document 8] KR20070098919

Document 9 KR20070019149

Document 10 KR20070009973

Regarding the structure of a fluorene, Literature 11 to Literature 17 are disclosed.

Document 11 KR20080049927

Document 12 KR20097009883

Document 13 KR20057013051

Document 14 KR20067010637

Document 15 KR20070008160

Document 16 KR20077015342

Document 17 KR20080011491

However, the light emitting materials according to the related arts still have problems in thermal stability and are not reaching satisfactory levels in efficiency, and thus, continuous research on these light emitting materials is required.

The present invention has been made to solve the above problems of the prior art, the present invention is a arylamine derivative for organic electroluminescent material of a new structure having a high efficiency and high thermal stability compared to the prior art, that is, pyrene-by One object is to provide a naphthalene compound and a method for preparing the same.

It is another object of the present invention to provide an organic electroluminescent material comprising the arylamine derivative for the organic electroluminescent material, that is, pyrene-binaphthalene.

The present invention to solve the conventional problems as described above

Provided is an arylamine derivative for an organic light emitting device, which is represented by the following Chemical Formula 1 having no symmetry plane in the structure of the molecule.

[Formula 1]

Ar 1 in Formula 1 is a divalent aryl group having 5 to 20 carbon atoms, and m is 0 or 1. Ar2 to Ar5 have the same structure or at least one of them has a different structure, each independently represent an aryl group having 6 to 30 carbon atoms.

Ar1 in the compound represented by Formula 1 is characterized in that any one or more divalent aryl group selected from the group consisting of benzene, naphthalene, pyrene, perylene or pentacene.

Ar1 of the compound represented by Formula 1 is characterized in that any one or two or more selected from the group consisting of Formula 2 to Formula 7 is an aryl group connected to each other.

[화학식 2]

(2)

(In Formula 2, J is an integer of 1 to 3.)

[화학식 3]

(3)

(K in Formula 3 is 1 or 2.)

[화학식 4]

[Chemical Formula 4]

(In Formula 4, L is an integer of 1 to 2.)

[화학식 5]

[Chemical Formula 5]

(In Formula 5, M is an integer of 1 to 2.)

[화학식 6]

[Chemical Formula 6]

(N in Formula 6 is 1 or 2.)

[화학식 7]

(7)

(O in Formula 7 is 1 or 2.)

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Formula 1 is characterized in that represented by the following [Formula 15].

[화학식 15]

[Chemical Formula 15]

Ar2 to Ar5 have the same structure or at least one of them has a different structure, each independently represent an aryl group having 6 to 30 carbon atoms.

Formula 1 is preferably an arylamine derivative for an organic EL device, characterized in that represented by the following [Formula 16].

[화학식 16]

[Chemical Formula 16]

Ar2 to Ar5 have the same structure or at least one of them has a different structure, each independently represent an aryl group having 6 to 30 carbon atoms.

Ar 2 to Ar 5 of Formula 1 is any one or more selected from the group consisting of aryl groups represented by the following formula (8) to (13) is characterized in that the same or at least one or more different from each other.

[화학식 8]

[Chemical Formula 8]

[화학식 9]

[Chemical Formula 9]

[화학식 10]

[Formula 10]

[화학식 11]

(11)

[화학식 12]

[Chemical Formula 12]

[화학식 13]

[Chemical Formula 13]

The present invention, on the other hand,

Synthesis by Suzuki coupling reaction using a pyrene compound according to [Formula A] to synthesize [Formula C] and an amination reaction to produce [Formula B]; Preparing a compound of the following Chemical Formula 1 by Suzuki coupling reaction of the Chemical Formula B prepared by the above step, or an amination reaction of the Chemical Formula C; It provides a method for producing an arylamine derivative for an organic electroluminescent device comprising a.

In [Formula 1], Ar1 is a divalent aryl group having 5 to 20 carbon atoms, and may include a hetero element in the ring. m is 0 or 1, and Ar2 to Ar5 have the same structure, or at least one of them has a different structure, and Ar2 to Ar5 may be each independently an aryl group having 6 to 30 carbon atoms. In addition, in [Formula A], X and Y may each be any one of a halogen element or boronic acid.

The present invention further provides an organic thin film material for an organic light emitting device, comprising the arylamine derivative for the organic light emitting device.

The present invention further includes an anode, a cathode and a plurality of organic thin film layers positioned between the anode and the cathode, wherein at least one layer of the plurality of organic thin film layers includes an arylamine derivative for the organic light emitting device. An organic electroluminescent device is provided.

The organic thin film layer may include at least one selected from a hole injection layer, a hole transport layer, a light emitting layer, an electron injection layer, and an electron transport layer.

In addition, the organic thin film is characterized in that the light emitting layer.

In addition, the organic thin film layer is characterized in that it contains a host compound and a dopant compound.

The organic electroluminescent material including pyrene-binaphthalene according to the present invention is a novel organic electroluminescent material, and the role of the light emitting material in organic electronic devices including OLED display and lighting, as well as hole injection, hole transport, electron It plays a role of injection and transport, and has high efficiency characteristics and excellent thermal stability in OLED devices.

1 is a schematic diagram of a configuration of a simple OLED.
2 is a schematic diagram of a configuration of an OLED having a multilayer structure.
3 is a schematic diagram of an OLED multilayer structure without a hole blocking layer in the configuration of the OLED having a multilayer structure as shown in FIG.
4 is a spectrum of the arylamine derivative derivatives according to Synthesis Example 1, Synthesis Example 2, Synthesis Example 4, Synthesis Example 5, and Synthesis Example 9 of the present invention.

Hereinafter, the present invention will be described in more detail.

The arylamine derivative for organic electroluminescent material according to the present invention is characterized in that the pyrene-binaphthalene compound represented by the following formula (1).

[Formula 1]

Ar 1 in Formula 1 is a divalent aryl group having 5 to 20 carbon atoms, and m is 0 or 1. In addition, Ar 2 to Ar 5 may be the same structure, or at least any one of them have a different structure may be each independently an aryl group having 6 to 30 carbon atoms.

Of the compounds represented by Formula 1, Ar1 is not particularly limited as long as it is a divalent aryl group having 5 to 20 carbon atoms as described above. Specifically, for example, Ar1 may be any one selected from the group consisting of Formulas 2 to 7 below or Two or more may be an aryl group connected to each other, but is not limited thereto.

(2)

(In Formula 2, J is an integer of 1 to 3.)

      (3)

(K in Formula 3 is 1 or 2.)

[Formula 4]

(In Formula 4, L is an integer of 1 to 2.)

[Chemical Formula 5]

(In Formula 5, M is an integer of 1 to 2.)

[Chemical Formula 6]

(N in Formula 6 is 1 or 2.)

[Formula 7]

(O in Formula 7 is 1 or 2.)

Preferably, Formula 1 may be represented by Formula 15 or Formula 16 below.

[화학식 15]

[Chemical Formula 15]

[화학식 16]

[Chemical Formula 16]

In Formula 15 or Formula 16, Ar 2 to Ar 5 may have the same structure, or at least one of them may have a different structure, and may be each independently an aryl group having 6 to 30 carbon atoms.

Furthermore, in Chemical Formula 1, Ar2 to Ar5 may each form at least two or more aryl groups selected from the group represented by Chemical Formulas 8 to 13 below to form an asymmetric structure.

[화학식 8]

[Chemical Formula 8]

[화학식 9]

[Chemical Formula 9]

[화학식 10]

[Formula 10]

[화학식 11]

(11)

[화학식 12]

[Chemical Formula 12]

[화학식 13]

[Chemical Formula 13]

The pyrene-binaphthalene compound of Chemical Formula 1 according to the present invention includes an asymmetric structure containing an aryl group as described above, thereby improving the hole mobility and increasing the glass transition temperature by improving the hole mobility by increasing the hole transition. To increase the effect.

Meanwhile, the pyrene-binaphthalene compound represented by Chemical Formula 1 may be prepared by the following method.

According to one embodiment of the present invention, as shown in Scheme 1 below, in order to prepare a pyrene-binaphthalene compound of Chemical Formula 1, first, using a pyrene compound according to [Formula A], a Suzuki coupling reaction Synthesizing to the compound of Formula [C] or an amination reaction to produce [Formula B]; And suzuki coupling reaction of [Formula B] prepared by the above step or amination reaction of [formula C] to prepare a compound of the following [Formula 1]; It may be performed including.

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[Reaction Scheme 1]

In Formula 1, Ar1 is a divalent aryl group having 5 to 20 carbon atoms, m is 0 or 1, and Ar2 to Ar5 have the same structure or at least one of them has a different structure, and Ar2 to Ar5 are each It may be independently an aryl group having 6 to 30 carbon atoms.

In addition, in Formula A, X and Y are the same as or different from each other, and may be each selected from halogen or boronic acid. Specifically, for example, Formula A may be any one or more selected from the group consisting of pyrene compounds substituted with bromine which is a halogen group.

As shown in Scheme 1, using a pyrene compound (Chemical Formula A) having a central structure which is disubstituted with different functional groups as a starting material, an aryl amination reaction or a Suzuki coupling reaction, and each Through a step of suzuki coupling reaction or aryl amination reaction to the reactant, the asymmetric structure represented by the formula (1) having no symmetry axis and symmetry plane in the structure of the molecule by sequentially replacing the functional groups with tertiary amine groups It may be to prepare a compound of.

The pyrene-binaphthalene compound of Chemical Formula 1 prepared through such a method has an asymmetric structure, and as described above, provides an effect of improving hole mobility and increasing glass transition temperature to increase thermal stability.

On the other hand, the present invention further provides an organic thin film material for an organic electroluminescent device comprising the pyrene-binaphthalene compound of the formula (1) as described above.

The organic thin film material for an organic EL device is not particularly limited except for forming one or more organic material layers using the pyrene-binaphthalene compound of Chemical Formula 1 described above. It can be prepared by.

In particular, the organic thin film material for an organic EL device may be used as a light emitting material or a dopant material.

The organic electronic device of the present invention includes a first electrode, a second electrode, and one or more organic material layers disposed between the electrodes, and at least one of the organic material layers is pyrene-binaphthalene represented by Chemical Formula 1 of the present invention. Compound.

In addition, in the organic electronic device of the present invention, the organic material layer includes a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, and an electron transport layer, and one or two hole injection layers, hole transport layers, hole blocking layers, and electron transport layers as necessary. It can be used with the layers omitted.

For example, in the organic electronic device of the present invention, the organic material layer may include a hole layer, a light emitting layer, or an electronic layer, and the hole layer, the light emitting layer, or the electronic layer may include a pyrene-binaphthalene compound represented by Formula 1 of the present invention. Can be.

The organic electronic device of the present invention may be any one of an organic light emitting diode (OLED), an organic solar cell (OSC), an electronic paper (e-Paper), an organic photoconductor (OPC) or an organic transistor (OTFT).

In an exemplary embodiment of the present invention, the organic light emitting diode may have a structure including an anode of a first electrode and a cathode of a second electrode and an organic material layer disposed therebetween, as shown in FIG. 1 or 2. Except that the pyrene-binaphthalene compound according to the present invention is used in at least one layer of the organic material layer of the organic light emitting device, it can be prepared using a conventional method and material for manufacturing an organic light emitting device.

The organic layer in the organic light emitting device of the present invention may have a single layer structure of one layer or a multilayer structure of two or more layers including a light emitting layer.

When the organic material layer of the organic light emitting device of the present invention has a multi-layer structure, it is, for example, a hole injection layer (Hole Injection Layer), a hole transport layer (Hole Transport Layer), an emission layer (Electroluminescence Layer), a hole blocking layer, (Hole Blocking Layer), an electron transport layer (Electron Transport Layer) may be a stacked structure.

However, the structure of the organic light emitting device according to the present invention is not limited thereto, and may include a smaller number of organic material layers.

The compound represented by Formula 1 in the organic layer of the multi-layer structure can be used in a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, a hole transport layer, a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, a hole injection It may be included in a layer for simultaneously transporting holes and emitting light, a layer for simultaneously transporting holes and emitting light, or a layer for simultaneously transporting electrons and emitting light, an electron transport layer, an electron injection and transport layer, and the like.

In addition, as described above, the method of manufacturing the organic light emitting device of the present invention is not particularly limited in the present invention and may be manufactured using a known method.

For example, the organic light emitting device according to the present invention is a metal oxide or a metal oxide or alloy thereof having a conductivity on a substrate by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation It can be prepared by depositing an anode to form an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer and an electron transport layer thereon, and then depositing a material that can be used as a cathode thereon.

In addition to the above 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.

The organic material layer may have a multi-layer structure including a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, and an electron transport layer, but is not limited thereto and may have a single layer structure.

The organic material layer may be formed using a variety of polymer materials by a method such as a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, .

As the cathode material, a material having a large work function is generally preferred to facilitate hole injection into the organic material layer.

Specific examples of the cathode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), titanium oxide (TiO), and indium zinc oxide (IZO); ZnO: Al or SnO _2: a combination of a metal and an oxide such as Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline.

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

The hole injection material is a material capable of well injecting holes from the anode at low voltage, and the highest occupied molecular orbital (HOMO) of the hole injection material is preferably between the work function of the positive electrode material and the HOMO of the surrounding organic material layer.

In addition, a material having good surface adhesion with the positive electrode and having a planarization ability that can alleviate the surface roughness of the positive electrode is preferable. In addition, a material having a larger HOMO and LUMO value than the band gap of the light emitting layer is preferable, and a material having high thermal stability in chemical structure is more preferable.

Specific examples of the hole injecting material include metal porphyrine, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene-based organic materials, quinacridone-based organic materials, perylene , Anthraquinone, polyaniline and polythiophene-based conductive polymers, but the present invention is not limited thereto.

The hole transport material is a material that can transport holes from an anode or a hole injection layer to a light emitting layer, and is suitable for a material having high mobility for holes, and a material having a HOMO and LUMO value larger than the band gap of the light emitting layer, and also a chemical structure. The higher the thermal stability material is advantageous.

Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion together, but are not limited thereto.

As the light emitting material, a material capable of emitting light in the visible light region by transporting and combining holes and electrons from the hole transporting layer and the electron transporting layer, respectively, is preferably a material having good quantum efficiency.

Specific examples include fluorene, carbazole, benzoxazole, benzthiazole and benzimidazole with blue ADN or MADN and DPVBi, BAlq and green Alq3 and other anthracenes, pyrenes, fluorenes, spiros, etc. Compounds represented by the series, and polymeric poly (p-phenylenevinylene), polypyro, polyfluorene, and the like, but are not limited thereto.

As the hole blocking layer material, a material larger than the HOMO value of light emission is suitable, and a material having high thermal stability in chemical structure is suitable.

Specifically, TPBi and BCP are mainly used, and CBP, PBD, PTCBI, BPhen, and the like can be used, but not limited thereto.

As an electron transport material, a material capable of injecting electrons well from a cathode and transferring the electrons to a light emitting layer is suitable. A material having high mobility to electrons is suitable, and a material having high chemical stability and thermal stability is suitable.

Specific examples include an Al complex of 8-hydroxyquinoline; Complexes containing Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto.

The organic light emitting device according to the present invention may be a front emission type, a back emission type, or a both-sided emission type, depending on the material used. The compound according to the present invention may act on a principle similar to that applied to organic light emitting devices in organic electronic devices including organic solar cells, organic photoconductors, organic transistors, electronic paper (e-Paper) and the like.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited thereto.

Synthetic example  1: Preparation of Compound-101

A compound represented by Chemical Formula 101 was synthesized according to the following Scheme route.

Synthesis Step of Compound [101-1]

1 g (4.560 mmol) of N-phenyl naphthalene-1-amine, 1.97 g (5.472 mmol) of 1,6-dibromopyrene, and 100 mg of tris (dibenzylideneacetone) dipalladium (0) in a dried round flask 0.109 mmol), 631 mg (0.657 mmol) of sodium butoxide, 66 mg (0.328 mmol) of tri-talt-butylphosphine, 60 ml of anhydrous toluene, and sufficiently charged with nitrogen, and the reaction mixture was refluxed at 110 ° C. for 24 hours. After cooling to room temperature, toluene was removed using a vacuum condenser, extracted with dichloromethane and distilled water, and the organic layer was dried over anhydrous magnesium sulfate and filtered.

The filtered organic layer was concentrated under reduced pressure, reprecipitated with dichloromethane and hexane, and the filtrate layer was separated by a column. Compound 6-bromo-N- (naphthalen-1-yl) -N-phenylpyrene-1-amine 1.36 g (60%) was obtained.

Anhydrous tetrahydrofuran was added to 3 g (6.02 mmol) of 6-bromo-N- (naphthalen-1-yl) -N-phenylpyrene-1-amine, and n-butyllithium was maintained at -78 ° C. After slowly adding ml (2.5M, 9.015 mmol) for 1 hour, 2.26 g (12.02 mmol) of triisopropyl borate was added dropwise and stirred while gradually raising the temperature to room temperature for 12 hours. Then, the pH was adjusted to about 2 by adding 1N aqueous hydrochloric acid at room temperature. After the reaction was completed, the mixture was extracted with ethyl acetate and distilled water, and then the organic layer was dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. Crystals were precipitated with n-hexane in the concentrate and the solid was filtered under reduced pressure to obtain 1.9 g (69%) of compound [101-1].

Synthesis Step of Compound [101-2]

1 g (2.948 mmol) of 4- (naphthalen-1-yl (phenyl) methyl-phenylboronic acid), 9.719 g (23.58 mmol) of 4,4'-dibromo-1,1'-binaphthalene in a dried round flask After adding 136mg (0.118mmol) of tetrakis (triphenylphosphine) palladium (0), fill it with enough nitrogen, then add 35ml of sodium carbonate solution (2M) and 300ml of anhydrous tetrahydrofuran and fill with nitrogen. The reaction mixture is refluxed at 100 ° C. for 24 hours.

After cooling to room temperature, toluene was removed using a vacuum condenser, extracted with dichloromethane and distilled water, and the organic layer was dried over anhydrous magnesium sulfate and filtered. The filtered organic layer was concentrated under reduced pressure, reprecipitated with dichloromethane and hexane, and the filtrate layer was separated by a column to obtain 1.49 g (60%) of compound [101-2].

Synthesis step of compound [101]

5 g (10.791 mmol) of compound [101-1], 6.784 g (10.791 mmol) of compound [101-2] and 62.350 mg (0.054 mmol) of tetrakis (triphenylphosphine) palladium (0) were added to the dried round flask. Afterwards, it is sufficiently charged with nitrogen.

Then, 15 ml (2M) of sodium carbonate solution and 100 ml of anhydrous tetrahydrofuran were added thereto, and the mixture was stirred under reflux at 100 ° C. for 24 hours. After completion of the reaction, distillation under reduced pressure was carried out to remove anhydrous tetrahydrofuran, and extracted with purified water and dichloromethane. The organic layer was removed with anhydrous magnesium sulfate, and then distilled under reduced pressure. The mixture was distilled off under reduced pressure to obtain 4.175 g (40%) of a compound.

1 H NMR (300 MHz, CDCl 3): δ 6.52 (d, 4H) 6.78 (t, 2H), 6.88 (d, 4H), 7.12 (t, 4H), 7.29 ~ 7.59 (m, 14H), 7.69 ~ 7.77 ( m, 12H), 7.84-7.97 (m, 4H), 8.02 (d, 2H), 8.24 (t, 2H)

Synthetic example  2: Preparation of Compound-102

Synthesis Step of Compound [102-1]

In the same manner as in Synthesis of Synthesis Example 101-1, 1.000 g (3.713 mmol) of N- (naphthalen-2-yl) naphthalene-1-amine, 1.604 g (4.455 mmol) of 1,6-dibromopyrene, and Tris ( Dibenzylideneacetone) dipalladium (0) 81.6 mg (0.089 mmol), sodium butoxide 514 mg (0.267 mmol), tri-talt-butylphosphine 54.1 mg (267 mmol), to 1 g (1.823 mmol) of the product obtained. 1.180 mL (2.5M, 2.735 mmol) of n-butyllithium and 0.514 g (2.735 mmol) of triisopropylborate were added dropwise to obtain 0.580 g (62%) of Compound [102-1].

Synthesis Step of Compound [102-2]

4- (naphthalen-1-yl (naphthalen-2-yl) methyl) phenylboronic acid 1.000 g (2.276 mmol), 4,4′-dibromo-1 in the same manner as in Synthesis of Synthesis Example 101-2 8.491 g (20.604 mmol) of 1'-binafryl, tetrakis (triphenylphosphine) palladium (0) 119 mg (0.103 mmol), 31 ml of aqueous sodium carbonate solution (2 M), 250 ml of anhydrous tetrahydrofuran -2] 0.878 g (57%) was obtained.

Synthesis step of Compound [102]

5.000 g (9.739 mmol) of compound [102-1], 3.781 g (9.739 mmol) of compound [102-2] and 0.057 mg of tetrakis (triphenylphosphine) palladium (0) in the same manner as in Synthesis of Synthesis Example 101 0.049 mmol), 15.0 ml (2 M) of sodium carbonate aqueous solution and 100 ml of tetrahydrofuran were added to obtain 6.847 g (66%) of the compound [102].

1 H NMR (300 MHz, CDCl 3): δ 7.14 (t, 4H), 7.32-7.74 (m, 28H), 7.68-7.72 (m, 12H), 7.83-7.95 (m, 4H), 8.04 (d, 2H) , 8.24 (t, 2 H)

Synthetic example  3: Preparation of Compound-103

Synthesis Step of Compound [103-1]

1.000 g (3.713 mmol) of dynaphthalen-2-yl amine, 1.604 g (4.455 mmol) of 1,6-dibromopyrene, and tris (dibenzylideneacetone) die in the same manner as in Synthesis of Synthesis Example 101-1 Palladium (0) 82 mg (0.089 mmol), sodium butoxide 514 mg (5.346 mmol), tri-talt-butylphosphine 54 mg (0.267 mmol), 1 g (1.823 mmol) of the product obtained using 1.1 ml (2.5 ml) M, 2.735 mmol) and 0.514 g (2.735 mmol) of triisopropylborate were added dropwise to obtain 0.600 g (64%) of the compound [103-1].

Synthesis Step of Compound [103-2]

1.000 g (2.269 mmol), 4,4'-dibromo-1,1'-binaph 4- (dynaphthalen-2-ylamino) phenylboronic acid in the same manner as in the synthesis of Synthesis Example 101-2 Teal 7.481 g (18.152 mmol), tetrakis (triphenylphosphine) palladium (0) 105 mg (0.091 mmol), 28 ml (2 M) of aqueous sodium carbonate solution, 250 ml of anhydrous tetrahydrofuran was added to compound [103-2] 1.060 g ( 69%).

Synthesis step of Compound [103]

5.000 g (9.739 mmol) of Compound [103-1], 6.590 g (9.739 mmol) of Compound [103-2] and 0.056 mg of tetrakis (triphenylphosphine) palladium (0) in the same manner as in Synthesis of Synthesis Example 101 0.049 mmol), 7.5 ml (2 M) of sodium carbonate aqueous solution, and 100 ml of tetrahydrofuran were added to obtain 5.602 g (54%) of the compound.

1 H NMR (300 MHz, CDCl3): δ 7.15 (t, 4H), 7.32-7.60 (m, 24H), 7.62 (d, 4H), 7.66-7.72 (m, 12H), 7.81-7.74 (m, 4H) , 8.04 (d, 2H), 8.24 (t, 2H)

Synthetic example  4: Preparation of Compound-104

Synthesis Step of Compound [104-1]

1.000 g (3.111 mmol) of dibiphenyl-4-yl amine, 1.344 g (3.734 mmol) of 1,6-dibromopyrene, and tris (dibenzylideneacetone) in the same manner as in Synthesis of Synthesis Example 101-1 Dipalladium (0) 68.4 mg (0.075 mmol), sodium butoxide 0.431 mg (4.481 mmol), tri-talt-butylphosphine 45 mg (0.224 mmol), n-butyllithium 1.3 in 1 g (1.665 mmol) of the product obtained. ml (2.5M, 2.498 mmol) and 0.470 g (2.498 mmol) of triisopropylborate were added dropwise to obtain 0.519 g (55%) of the compound.

Synthesis Step of Compound [104-2]

4- (dibiphenyl-4-ylamino) phenylboronic acid 1.000 g (2.266 mmol), 4,4'-dibromo-1,1'-bi by the same method as the synthesis of Synthesis Example 101-2 7.470 g (18.127 mmol) of naphthyl, tetrakis (triphenylphosphine) palladium (0) 105 mg (0.091 mmol), 28 ml (2M) of aqueous sodium carbonate solution, 250 ml of anhydrous tetrahydrofuran was added to the compound [104-2] 1.172 g (71%) was obtained.

Synthesis step of Compound [104]

5.000 g (8.842 mmol) of compound [104-1], 6.443 g (8.842 mmol) of compound [104-2] and 51.1 mg of tetrakis (triphenylphosphine) palladium (0) in the same manner as in Synthesis of Synthesis Example 101 0.044 mmol), 5.3 ml (2 M) of aqueous sodium carbonate solution and 100 ml of tetrahydrofuran were added to obtain 6.514 g (63%) of the compound.

1 H NMR (300 MHz, CDCl 3): δ 7.13 (t, 4H), 7.18 (d, 4H), 7.22 to 7.28 (m, 16H), 7.33 to 7.60 (m, 16H), 7.68 to 7.76 (m, 12H) , 7.81-7.73 (m, 4H), 8.03 (d, 2H), 8.24 (t, 2H)

Synthetic example  5: Preparation of Compound-105

Synthesis Step of Compound [105-1]

In the same manner as in Synthesis of Synthesis Example 101-1, 1.000 g (2.972 mmol) of triphenylbenzene-1,4-diamine, 1.284 g (3.566 mmol) of 1,6-dibromopyrene, and tris (dibenzylidene Acetone) dipalladium (0) 65 mg (0.071 mmol), sodium butoxide 411 mg (4.279 mmol), tri-talt-butylphosphine 43 mg (0.214 mmol), n-butyllithium 1.0 g (1.625 mmol) ml (2.5M, 2.438 mmol) and 0.458 g (2.438 mmol) of triisopropylborate were added dropwise to obtain 0.913 g (49%) of the compound [105-1].

Synthesis Step of Compound [105-2]

Triphenylamine 1.000 g (4.076 mmol), 4,4'-dibromo-1,1'-binafryl 13.438 g (32.608 mmol) and tetrakis (triphenyl) in the same manner as in Synthesis of Synthesis Example 101-2 188 mg (0.163 mmol) of phosphine) palladium (0), 48.9 ml (2 M) of aqueous sodium carbonate solution and 250 ml of anhydrous tetrahydrofuran were added to obtain 1.490 g (63%) of the compound [105-2].

Synthesis step of compound [105]

In the same manner as in Synthesis of Synthesis Example 101, 5.000 g (8.614 mmol) of compound [105-1], 4.966 g (8.614 mmol) of compound [105-2], and 50 mg (0.043) of tetrakis (triphenylphosphine) palladium (0) mmol), 12.9 ml (2 M) aqueous sodium carbonate solution and 100 ml tetrahydrofuran were added to obtain 6.921 g (77%) of the compound [105].

1H NMR (300MHz, CDCl3) 6.52 (d, 4H), 6.78 (t, 2H), 6.89 (d, 4H), 6.95 (t, 2H), 7.03 (t, 1H) 7.14 (t, 4H,) 7.33 ~ 7.50 (m, 16H), 7.66 ~ 7.76 (m, 12H), 7.83 ~ 7.95 (m, 4H), 8.04 (d, 2H), 8.24 (t, 2H)

Synthetic example  6: Preparation of Compound-106

Synthesis Step of Compound [106-1]

1.000 g (2.587 mmol) of N1- (naphthalen-1-yl) -N4, N4-iphenylbenzene-1,4-diamine and 1,6-dibromopy in the same manner as in Synthesis of Synthesis Example 101-1 Lene 1.118 g (3.104 mmol), tris (dibenzylideneacetone) dipalladium (0) 57 mg (0.062 mmol), sodium butoxide 358 mg (3.725 mmol), tri-talt-butylphosphine 38 mg (0.186 mmol), use 0.9 g (2.5 M, 2.253 mmol) of n-butyllithium and 0.424 g (2.253 mmol) of triisopropyl borate were added dropwise to 1 g (1.502 mmol) of the obtained product to obtain 0.824 g (48%) of the compound [106-1]. .

Synthesis Step of Compound [106-2]

In the same manner as in Synthesis of Synthesis Example 101-2, 1.000 g (4.076 mmol) of triphenylamine, 13.438 g (32.608 mmol) of 4,4'-dibromo-1,1'-binaphthyl, tetrakis (tri 188 mg (0.163 mmol) of phenylphosphine) palladium (0), 48.9 ml (2M) of aqueous sodium carbonate solution and 250 ml of anhydrous tetrahydrofuran were added to obtain 1.490 g (63%) of the compound [106-2].

Synthesis step of Compound [106]

In the same manner as in the synthesis of Synthesis Example 101, 5.000 g (7.930 mmol) of compound [106-1], 4.572 g (7.930 mmol) of compound [106-2], 46 mg (0.040) of tetrakis (triphenylphosphine) palladium (0) mmol), 11.9 ml (2 M) aqueous sodium carbonate solution and 100 ml tetrahydrofuran were added to obtain 5.471 g (63%) of compound [106].

1H NMR (300MHz, CDCl3) 7.13 (t, 4H), 7.32 ~ 7.50 (m, 25H), 7.62 (d, 6H), 7.64 ~ 7.75 (m, 12H), 7.80 ~ 7.92 (m, 4H), 8.04 ( d, 2H), 8.24 (t, 2H)

Synthetic example  7: Preparation of Compound-107

Synthesis Step of Compound [107-1]

1.000 g (2.601 mmol) of N- (naphthalen-1-yl) -9-phenyl-9H-carbazole-3-amine and 1.124 1,6-dibromopyrene in the same manner as in Synthesis of Synthesis Example 101-1 g (3.121 mmol), tris (dibenzylideneacetone) dipalladium (0) 57 mg (0.062 mmol), sodium butoxide 360 mg (3.745 mmol), tri-talt-butylphosphine 379 mg (0.187 mmol), obtained and used 0.9 g (2.5 M, 2.261 mmol) of n-butyllithium and 0.425 g (2.261 mmol) of triisopropyl borate were added dropwise to 1 g (1.507 mmol) of the product to obtain 0.713 g (41%) of the compound [107-1].

Synthesis Step of Compound [107-2]

Triphenylamine triphenylamine 1.000 g (4.076 mmol), 4,4'-dibromo-1,1'-binaphthyl 13.438 g (32.608 mmol), tetrakis 188 mg (0.163 mmol) of phenylphosphine) palladium (0), 48.9 ml (2M) of aqueous sodium carbonate solution and 250 ml of anhydrous tetrahydrofuran were added to obtain 1.490 g (63%) of compound [107-2].

Synthesis step of Compound [107]

In the same manner as in the synthesis of Synthesis Example 101, 5.000 g (7.955 mmol) of compound [107-1], 4.586 g (7.955 mmol) of compound [107-2], 46 mg (0.040) of tetrakis (triphenylphosphine) palladium (0) mmol), 11.9 ml (2 M) aqueous sodium carbonate solution and 100 ml tetrahydrofuran were added to obtain 5.242 g (61%) of the compound [107].

1H NMR (300MHz, CDCl3) 7.14 (t, 4H), 7.18 (d, 4H), 7.20 ~ 7.26 (m, 4H), 7.31 ~ 7.58 (m, 16H), 7.64 (t, 1H) 7.66 ~ 7,75 (m, 12H), 7.76 ~ 7.81 (m, 4H), 7.84 ~ 7.92 (m, 4H), 8.04 (d, 2H), 8.23 (t, 2H)

Synthetic example  8: Preparation of Compound-108

Synthesis Step of Compound [108-1]

1.000 g (2.601 mmol) of N- (naphthalen-1-yl) -9-phenyl-9H-carbazole-3-amine and 1.124 1,6-dibromopyrene in the same manner as in Synthesis of Synthesis Example 101-1 g (3.121 mmol), tris (dibenzylideneacetone) dipalladium (0) 57 mg (0.062 mmol), sodium butoxide 360 mg (3.745 mmol), tri-talt-butylphosphine 379 mg (0.187 mmol), obtained and used 0.9 g (2.5 M, 2.261 mmol) of n-butyllithium and 0.425 g (2.261 mmol) of triisopropyl borate were added dropwise to 1 g (1.507 mmol) of the product to obtain 0.713 g (41%) of the compound [108-1].

Synthesis Step of Compound [108-2]

1.000 g (3.385 mmol) of N, N-diphenylnaphthalene-1-amine, 12.809 g of 4,4'-dibromo-1,1'-binaphthyl (31.080) in the same manner as in Synthesis of Synthesis Example 101-2 mmol), tetrakis (triphenylphosphine) palladium (0) 180 mg (0.155 mmol), 46.6 ml (2M) of aqueous sodium carbonate solution and 250 ml of anhydrous tetrahydrofuran were added to compound 1.108 g (57%). Could get

Synthesis step of Compound [108]

In the same manner as in the synthesis of Synthesis Example 101, 5.000 g (7.955 mmol) of compound [108-1], 4.984 g (7.955 mmol) of compound [108-2], 46 mg (0.040) of tetrakis (triphenylphosphine) palladium (0) mmol), 11.9 ml (2 M) aqueous sodium carbonate solution and 100 ml tetrahydrofuran were added to obtain 4.341 g (48%) of the compound [108].

1H NMR (300MHz, CDCl3) 7.13 (t, 4H), 7.16 (d, 4H), 7.21 ~ 7.26 (m, 12H), 7.29 ~ 7.56 (m, 14H), 7.60 (t, 1H), 7.66 ~ 7.77 ( m, 12H), 7.82-7.73 (m, 4H), 8.02 (d, 2H), 8.26 (t, 2H)

Synthetic example  9: Preparation of Compound-109

Synthesis Step of Compound [109-1]

In a dried round flask, 1 g (2.424 mmol) of N-1- (biphenyl-4-yl) -N1, N4-diphenylbenzene-1,4-diamine and 1.20 g of 1,6-dibromopyrene ( 2.908 mmol), Tris (dibenzylideneacetone) dipalladium (0) Pd2 (dba) 3 0.053g (0.058mmol), sodium butoxide 0.335g (3.49mmol), tri-talt-butylphosphine 0.035g (0.174 mmol) and 60 ml of anhydrous toluene were added, and nitrogen was sufficiently charged, and the reaction mixture was refluxed at 110 ° C. for 24 hours. After cooling to room temperature, toluene was removed using a vacuum condenser, extracted with dichloromethane and distilled water, and the organic layer was dried over anhydrous magnesium sulfate and filtered. The filtered organic layer was concentrated under reduced pressure, reprecipitated with dichloromethane and hexane, and then the filtrate layer was separated by a column. The compound N1- (biphenyl-4-yl) -N4- (6-bromopyren-1-yl)- 0.78 g (46.5%) of N1, N4-diphenylbenzene-1,4-diamines were obtained.

1 g (1.446 mmol) of N1- (biphenyl-4-yl) -N4- (6-bromopyren-1-yl) -N1, N4-diphenylbenzene-1,4-diamine at −78 ° C. 1.5 ml (2.5M, 3.636mmol) of n-butyllithium was slowly added for 1 hour while maintaining the solution, followed by dropwise addition of 0.684g (3.636mmol) of triisopropyl borate, and the mixture was stirred while gradually raising the temperature to room temperature for 12 hours. Then, the pH was adjusted to about 2 by adding 1N aqueous hydrochloric acid at room temperature. After the reaction was completed, the mixture was extracted with ethyl acetate and distilled water, and then the organic layer was dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. Crystals were precipitated with n-hexane in the concentrate and the solid was filtered under reduced pressure to obtain 0.83 g (52%) of compound [109-1].

Synthesis Step of Compound [109-2]

1 g (2.738 mmol) of 4- (biphenyl-4-yl (phenyl) amino) phenylboronic acid, 9.03 g of 4,4'-dibromo-1,1'-binaphthalene (21.904) in a dried round flask. mmol) and tetrakis (triphenylphosphine) palladium (0) 0.127g (0.110mmol), followed by sufficient nitrogen loading. Then, 33 ml (2 M) of sodium carbonate solution and 300 ml of anhydrous tetrahydrofuran were sufficiently charged with nitrogen, and the reaction mixture was refluxed at 100 ° C. for 24 hours. After cooling to room temperature, toluene was removed using a vacuum condenser, extracted with dichloromethane and distilled water, and the organic layer was dried over anhydrous magnesium sulfate and filtered. The filtered organic layer was concentrated under reduced pressure, reprecipitated with dichloromethane and hexane, and the filtrate layer was separated by a column to obtain 0.92 g (51%) of the compound [109-2].

Synthesis step of compound [109]

5 g (7.615 mmol) of compound [109-1], 4.97 g (7.615 mmol) of compound [109-2] and 0.044 g (0.038 mmol) of tetrakis (triphenylphosphine) palladium (0) were added to a dried round flask. After filling with enough nitrogen. Then, 11 ml (2 M) of sodium carbonate solution and 100 ml of anhydrous tetrahydrofuran were added thereto, followed by stirring at reflux for 24 hours at 100 ° C. After the reaction was completed, distillation under reduced pressure was carried out to remove anhydrous tetrahydrofuran, and extracted with purified water and dichloromethane. The organic layer was distilled under reduced pressure after removing water with anhydrous magnesium sulfate. The distillation under reduced pressure was separated by a column to obtain 4.27 g (47%) of the compound.

1 H NMR (300 MHz, CDCl 3): δ 6.48 (q, 4H), 6.50 (d, 6H), 6.74 (t, 3H), 6.86 (d, 6H), 7.18 (t, 4H), 7.20 (d, 2H ), 7.22 ~ 7.30 (m, 8H), 7.33 ~ 7.62 (m, 8H), 7.69 ~ 7.82 (m, 12H), 7.84 ~ 7.97 (m, 4H), 8.11 (d, 2H), 8.26 (t, 2H )

Synthetic example  10: Preparation of Compound-110

Synthesis Step of Compound [110-1]

1.000 g (2.290 mmol) of N1, N4-di (naphthalen-1-yl) -N1-phenylbenzene-1,4-diamine and 1,6-dibromopy in the same manner as in Synthesis of Synthesis Example 109-1 0.989 g (2.748 mmol), tris (dibenzylideneacetone) dipalladium (0) 0.050 g (0.055 mmol), sodium butoxide 0.317 g (3.298 mmol), tri-talt-butylphosphine 0.033 g (0.165 mmol) ), 1.4 g (1.33 mmol) of n-butyllithium and 0.646 g (3.435 mmol) of triisopropylborate were added dropwise to 1 g (1.397 mmol) of the obtained product. %) Obtained.

Synthesis Step of Compound [110-2]

4- (naphthalen-2-yl (phenyl) amino) phenylboronic acid 1.000 g (2.948 mmol), 4,4'-dibromo-1,1'- in the same manner as in the synthesis of Synthesis Example 109-2 Binaphthyl 9.719 g (23.584 mmol), tetrakis (triphenylphosphine) palladium (0) 0.136 g (0.118 mmol), 35.376 ml (2 M) aqueous sodium carbonate solution, 250 ml of anhydrous tetrahydrofuran was added to the compound [110-2 0.812 g (44%) was obtained.

Synthesis step of Compound [110]

5.000 g (7.346 mmol) of Compound [110-1], 4.603 g (7.346 mmol) of Compound [110-2] and 0.043 g of tetrakis (triphenylphosphine) palladium (0) in the same manner as in Synthesis of Synthesis Example 109 0.037 mmol), 11 ml (2 M) of sodium carbonate aqueous solution and 100 ml of tetrahydrofuran were added to obtain 5.1 g (57.6%) of Compound [110].

1 H NMR (300 MHz, CDCl 3): δ 6.44 (q, 4H), 6.52 (d, 4H), 6.78 (t, 2H), 6.88 (d, 4H), 7.15 (t, 4H), 7.29 ~ 7.59 (m , 21H), 7.69-7.77 (m, 12H), 7.84-7.97 (m, 4H), 8.02 (d, 2H), 8.24 (t, 2H)

Synthetic example  11: Preparation of Compound-111

Synthesis Step of Compound [111-1]

1.000 g (2.972 mmol) of N1, N1, N4-triphenylbenzene-1,4-diamine, 1.284 g (3.566 mmol) of 1,6-dibromopyrene in the same manner as in the synthesis of Synthesis Example 109-1, Tris (dibenzylideneacetone) dipalladium (0) 0.065 g (0.071 mmol), sodium butoxide 0.411 g (4.279 mmol), tri-talt-butyl phosphine 0.0432 g (0.214 mmol), 1 g of product obtained using 1.625 mmol) was added dropwise 1.8 ml (2.5 M, 4.458 mmol) of n-butyllithium and 0.838 g (4.458 mmol) of triisopropyl borate to obtain 0.83 g (48%) of the compound [111-1].

Synthesis Step of Compound [111-2]

4-((4- (diphenylamino) phenyl) (phenyl) amino) phenylboronic acid 1.000 g (2.191 mmol), 4,4'-dibromo- in the same manner as in the synthesis of Synthesis Example 109-2 7.224 g (17.528 mmol) of 1,1'-binaphthyl, tetrakis (triphenylphosphine) palladium (0) 0.10 g (0.088 mmol), 26.30 ml (2 M) aqueous sodium carbonate solution, 250 ml of anhydrous tetrahydrofuran 0.86 g (53%) of compound [111-2] was obtained.

Synthesis step of Compound [111]

In the same manner as in the synthesis of Synthesis Example 109, 5.000 g (8.614 mmol) of compound [111-1], 6.406 g (8.614 mmol) of compound [111-2], and 0.05 g (0) of tetrakis (triphenylphosphine) palladium (0) 0.043 mmol), 13 ml (2 M) of sodium carbonate aqueous solution and 100 ml of tetrahydrofuran were added to obtain 6.8 g (66%) of the compound [111].

1 H NMR (300 MHz, CDCl 3): δ 6.38 (q, 8H), 6.55 (d, 12H), 6.79 (t, 6H), 6.83 (d, 12H), 7.22 (t, 4H), 7.52 ~ 7.78 (m , 12H), 7.80 ~ 8.0 (m, 4H), 8.07 (d, 2H), 8.24 (t, 2H)

Synthetic example  12: Preparation of Compound-112

Synthesis Step of Compound [112-1]

1.000 g (2.424 mmol) of N1- (biphenyl-4-yl) N4, N4-diphenylbenzene-1,4-diamine and 1,6-dibromopy in the same manner as in Synthesis of Synthesis Example 109-1 Lene 1.047 g (2.909 mmol), tris (dibenzylideneacetone) dipalladium (0) 0.053 g (0.058 mmol), sodium butoxide 0.335 g (3.49 mmol), tri-talt-butyl phosphine 0.035 g (0.175 mmol) ), 1.5 g (2.5 M, 3.636 mmol) of n-butyllithium and 0.684 g (3.636 mmol) of triisopropyl borate were added dropwise to 1 g (1.446 mmol) of the obtained product. %) Obtained.

Synthesis Step of Compound [112-2]

4- (biphenyl-4-yl (4- (diphenylamino) phenyl) amino) phenylboronic acid 1.000 g (1.878 mmol), 4,4'-di in the same manner as in the synthesis of Synthesis Example 109-2 Bromo-1,1'-binaphthyl 6.19 g (15.024 mmol), tetrakis (triphenylphosphine) palladium (0) 0.087 g (0.075 mmol), aqueous sodium carbonate solution 23 ml (2M), 250 ml anhydrous tetrahydrofuran 0.92 g (59.7%) of Compound [112-2] was obtained.

Synthesis step of Compound [112]

5.000 g (7.615 mmol) of compound [112-1], 6.24 g (7.615 mmol) of compound [112-2] and 0.044 g of tetrakis (triphenylphosphine) palladium (0) in the same manner as in Synthesis of Synthesis Example 109 0.038 mmol), 11.ml (2M) of aqueous sodium carbonate solution and 100 ml of tetrahydrofuran were added to obtain 7.08 g (69%) of the compound [112].

1 H NMR (300 MHz, CDCl 3): δ 6.56 (q, 8H), 6.69 to 6.68 (m, 12H), 6.79 to 7.02 (m, 6H), 7.05 to 7.18 (m, 12H), 7.24 (t, 4H) , 7.28 ~ 7.46 (m, 8H), 7.49 ~ 7.65 (m, 12H), 7.74 ~ 7.99 (m, 4H), 8.05 (d, 2H), 8.19 (t, 2H)

Example  One: ITO  Of ELM200  Of NPB  Compound-101 Alq ₃  Of LiF  Of Al

Compound-101 prepared in Synthesis Example 1 was used as a light emitting material, HIL was ELM200, HTL was NPB, ETL was Alq3, and EIL was LiF.

Specifically, a glass substrate coated with a thin film of ITO (indium tin oxide) at a thickness of 1500 에 was placed in secondary distilled water in which Fischer's detergent was dissolved, and ultrasonically cleaned. The ITO was washed for 30 minutes and then washed twice with distilled water and ultrasonically cleaned for 10 minutes. After the distilled water was washed, it was ultrasonically washed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transferred to a plasma cleaner. The substrate was cleaned using oxygen plasma for 5 minutes, and then the substrate was transferred to a vacuum evaporator.

The amine-based ELM200 was thermally vacuum deposited to a thickness of 500 kPa on the prepared ITO transparent electrode to form a hole injection layer. NPB (300 kV), which is a material for transporting holes, was vacuum deposited thereon, and then Compound-101 prepared by Synthesis Example 1 was vacuum deposited to a thickness of 300 kPa as a light emitting layer, and an Alq3 compound was deposited to a thickness of 300 kPa as an electron transport layer. After vacuum deposition, lithium fluoride (LiF) 7 Å and 1000 Å thick aluminum were deposited sequentially to form a cathode.

In the above process, the deposition rate of the organic material was maintained at 1 Å / sec, the deposition rate of lithium fluoride was maintained at 0.2 Å / sec, and the deposition rate of aluminum was maintained at 3 to 7 Å / sec. Table 1 shows the electroluminescence characteristics of the organic light-emitting device prepared above.

Example  2: ITO  Of ELM200  Of NPB  Compound-102 Alq ₃  Of LiF  Of Al

In the same manner as in Example 1, an OLED was manufactured using the compound-102 prepared in Synthesis Example 2 as a light emitting layer, and the electroluminescent properties are shown in Table 1 below.

Example  3: ITO  Of ELM200  Of NPB  Compound-104 Alq ₃  Of LiF  Of Al

In the same manner as in Example 1, an OLED was manufactured using the compound-104 prepared in Synthesis Example 4 as a light emitting layer, and the electroluminescent properties are shown in Table 1.

Example  4: ITO  Of ELM200  Of NPB  Compound-105 Alq ₃  Of LiF  Of Al

In the same manner as in Example 1, an OLED was manufactured using the compound-105 prepared in Synthesis Example 5 as an emission layer, and the electroluminescence properties are shown in Table 1.

Comparative Example  : ITO  Of ELM200  Of NPB  Of MADN  Of Alq3  Of LiF  Of Al

HIL is ELM200, HTL is NPB, and the light emitting material uses MADN of the above formula, ETL is Alq3 and EIL is LiF. Other than that, the OLED was manufactured in the same manner as in Example 1, and the electroluminescent properties are shown in Table 1.

Characterization was performed using the organic electroluminescent devices prepared in Examples 1 to 4 and Comparative Examples, and the results are shown in Table 1. Here, the unit of current density is mA / cm ² , the unit of color coordinate is CIE 1931 (x, y), the efficiency is calculated by using luminance and current density, the unit is cd / A, and the lifetime is 1000nit.

Current density
(mA / cm ² ) Color coordinates
(x, y) efficiency
(cd / A) life span
(hrs) Example 1 20 (0.18, 0.29) 3.12 200 Example 2 20 (0.17, 0.29) 4.08 450 Example 3 20 (0.18, 0.32) 3.56 380 Example 4 20 (0.20, 0.38) 3.71 320 Comparative Example 20 (0.17, 0.35) 2.98 340

As can be seen from the results of Table 1, a binaphthyl group is attached to the center of pyrene represented by the formula (1) according to the present invention, and an aryl having an asymmetric structure at the two bondable halogen (dibromo) positions Alternatively, the compound structure in which the substituent of the arylamine derivative is introduced can be used to form an OLED thin film layer, and when used as a light emitting layer, the device emits light in the greenish blue wavelength region, and it is confirmed that color purity, luminous efficiency, and lifetime characteristics are improved. there was.

In particular, Examples 1 to 4 using the aryl / arylamine derivative having a symmetrical / asymmetrical structure according to the present invention shows the luminous efficiency and lifespan characteristics by significantly improved the ability to move holes and electrons compared to the anthracene compound of the comparative example can confirm.

Claims (13)

An arylamine derivative for an organic light emitting device, characterized in that it does not have a symmetry plane in the structure of the molecule.
[Chemical Formula 1]

In Formula 1,
Ar1 is a divalent aryl group having 5 to 20 carbon atoms,
m is 0 or 1,
Ar2 to Ar5 have the same structure or at least one of them has a different structure, each independently represent an aryl group having 6 to 30 carbon atoms.
The method of claim 1,
Ar1 in the compound represented by Formula 1 is an arylamine derivative for an organic light emitting device, characterized in that any one or more divalent aryl group selected from the group consisting of benzene, naphthalene, pyrene, perylene or pentacene.
The method of claim 1,
Ar 1 of the compound represented by Chemical Formula 1 is an arylamine derivative for an organic light emitting device, characterized in that any one or two or more selected from the group consisting of Chemical Formulas 2 to 7 are connected to each other.

(2)
(In Formula 2, J is an integer of 1 to 3.)

(3)
(K in Formula 3 is 1 or 2.)

[Chemical Formula 4]
(In Formula 4, L is an integer of 1 to 2.)

[Chemical Formula 5]
(In Formula 5, M is an integer of 1 to 2.)

[Chemical Formula 6]
(N in Formula 6 is 1 or 2.)

(7)
(O in Formula 7 is 1 or 2.)
The method of claim 1,
Formula 1 is an arylamine derivative for an organic electroluminescent device, characterized in that represented by the following [Formula 15].
[Chemical Formula 15]

In Chemical Formula 15,
Ar2 to Ar5 have the same structure or at least one of them has a different structure, each independently represent an aryl group having 6 to 30 carbon atoms.
The method of claim 1,
Formula 1 is an arylamine derivative for an organic light emitting device, characterized in that represented by the following formula (16).
[Chemical Formula 16]

In Chemical Formula 16,
Ar2 to Ar5 have the same structure or at least one of them has a different structure, each independently represent an aryl group having 6 to 30 carbon atoms.
delete The method of claim 1,
Ar 2 to Ar 5 of Formula 1 is any one or more selected from the group consisting of aryl groups represented by the following formula (8) to (13) for the organic light emitting device, characterized in that the same or at least one different from each other. Arylamine derivatives.

[Chemical Formula 8]

[Chemical Formula 9]

[Formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]
Using a pyrene compound according to [Formula A], but synthesizing by an amination reaction to prepare [Formula B]; And
Preparing the compound of [Formula 1] using the Formula [B] prepared by the above step using a Suzuki coupling reaction; Method for producing an arylamine derivative for an organic electroluminescent device comprising a.
[Reaction Scheme 1]

In this case, in [Formula 1], Ar1 is a divalent aryl group having 5 to 20 carbon atoms, m is 0 or 1, Ar2 to Ar5 are the same structure or at least one of them have a different structure each independently Aryl group having 6 to 30 carbon atoms,
In Formula [A], X and Y are each one of a halogen element or boronic acid.
An organic thin film material for an organic light emitting device comprising an arylamine derivative for an organic light emitting device according to any one of claims 1 to 5.
Claims 1 to 5 comprising an anode, a cathode and a plurality of organic thin film layers positioned between the anode and the cathode, the organic light emitting device according to any one of claims 1 to 5 An organic electroluminescent device comprising an arylamine derivative.
The method of claim 10,
The organic thin film layer comprises at least one selected from a hole injection layer, a hole transport layer, a light emitting layer, an electron injection layer and an electron transport layer.
12. The method of claim 11,
The organic light emitting device, characterized in that the organic thin film layer is a light emitting layer.
The method of claim 10,
The organic thin film layer is an organic light emitting device, characterized in that it contains a host compound and a dopant compound.

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