KR20110087768A - Aromatic amine compund and organic electroric element using the same, terminal thererof - Google Patents

Abstract

PURPOSE: An aromatic amine compound is provided to ensure excellent electrical characteristics and light-emitting property, thereby enabling the use of a hole injection material and a hole transport material under the low driving voltage when applied to the organic electronic device and the terminal. CONSTITUTION: An aromatic amine compound is represented by chemical formula 1. An organic electronic device comprises a monolayered organic material layer including the compound. The organic electronic device includes a first electrode, a monolayered organic material layer and a second electrode in a successively laminated form. The organic material layer includes a hole injection layer, a hole transport layer, and an electron injection layer.

Description

Aromatic amine compound and organic electronic device using same, and terminal thereof {AROMATIC AMINE COMPUND AND ORGANIC ELECTRORIC ELEMENT USING THE SAME, TERMINAL THEREROF}

The present invention relates to an aromatic amine compound, an organic electronic device using the same, and a terminal thereof.

In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy. An organic electronic device using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween. In this case, the organic material layer is often formed of a multi-layered structure composed of different materials to increase the efficiency and stability of the organic electronic device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer.

Materials used as the organic material layer in the organic electronic device may be classified into light emitting materials and charge transport materials such as hole injection materials, hole transport materials, electron transport materials, electron injection materials and the like depending on their functions. The light emitting material may be classified into a polymer type and a low molecular type depending on the molecular weight, and may be classified into a phosphorescent material derived from singlet excited state of electrons and a phosphorescent material derived from the triplet excited state of electrons . In addition, the light emitting material may be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to achieve a better natural color according to the light emitting color.

On the other hand, when only one material is used as a light emitting material, there arises a problem that the maximum light emission wavelength shifts to a long wavelength due to intermolecular interaction, the color purity decreases, or the efficiency of the device decreases due to the light emission attenuating effect. A host / dopant system may be used as the light emitting material in order to increase the light emitting efficiency through the light emitting layer. The principle is that when a small amount of dopant having an energy band gap smaller than that of a host forming the light emitting layer is mixed in the light emitting layer, excitons generated in the light emitting layer are transported to the dopant, thereby producing high-efficiency light. At this time, since the wavelength of the host is shifted to the wavelength band of the dopant, the desired wavelength light can be obtained depending on the type of the dopant used.

In order to fully exhibit the excellent characteristics of the organic electronic device described above, a material forming the organic material layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, etc., is supported by a stable and efficient material. Although this should be preceded, the development of a stable and efficient organic material layer for an organic electronic device has not been sufficiently achieved, and therefore, the development of a new material is still required.

The inventors have discovered a novel aromatic amine compound, which also has excellent electrical properties and light emitting properties, and thus has excellent hole injection and hole transport ability under low driving voltage when applied to organic electronic devices. It has been found to be useful as a transport material.

Accordingly, an object of the present invention is to provide an aromatic amine compound having various substituents, an organic electronic device using the same, and a terminal thereof.

In one aspect, the present invention provides a compound of the formula

At this time, the compound according to an embodiment of the present invention provides an aromatic amine compound.

The present invention can play a variety of roles in the aromatic amine compound and organic electronic device using the same, the terminal, and has excellent electrical characteristics and light emission characteristics when applied to the organic electronic device and the terminal excellent hole injection and hole transport under a low driving voltage It is useful as a hole injection material and a hole transport material having the ability. In the case of employing the organic film using the organic electroluminescent compound described above, an organic electronic device having high efficiency, low voltage, high brightness, and long life based on superior current density characteristics can be manufactured.

1 to 5 show examples of organic electronic devices to which the compounds of the present invention can be applied.

Hereinafter, with reference to the accompanying drawings, the specific content for the practice of the present invention will be described.

Hereinafter, some embodiments of the present invention will be described in detail through exemplary drawings. In adding reference numerals to the components of each drawing, it should be noted that the same reference numerals are assigned to the same components as much as possible even though they are shown in different drawings. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

In describing the components of the present invention, terms such as first, second, A, B, (a), and (b) may be used. These terms are only for distinguishing the components from other components, and the nature, order or order of the components are not limited by the terms. If a component is described as being "connected", "coupled" or "connected" to another component, that component may be directly connected to or connected to that other component, but there may be another configuration between each component. It should be understood that the elements may be "connected", "coupled" or "connected".

The present invention provides a compound of Formula 1 below.

In the above formula,

(1) L ₁ to L ₂ independently mean a single bond, a substituted or unsubstituted alkyl group of C1-C50, a substituted or unsubstituted alkenyl group of C1-C50, a substituted or unsubstituted aryl of C5-C60 A benzene group, a substituted or unsubstituted aryl group of C5-C60, a substituted or unsubstituted C1-C50 alkyl group containing at least one hetero atom, S, N, O, P, and Si, S, N, O, P And substituted or unsubstituted C5-C60 alkenyl groups containing at least one hetero atom, S, N, O, P and Si containing substituted or unsubstituted C5-C60 containing at least one hetero atom; Arylene group, S, N, O, P and Si may be one selected from the group consisting of a substituted or unsubstituted C5-C60 aryl group containing at least one hetero atom, wherein a or b is an integer from 0 to 3 to be.

(2) R ₁ may be independently defined by different substituents when c is 1 or more, and different R ₁ may be bonded to each other to form a ring. R ₁ as defined above is each independently a hydrogen atom, a halogen atom, a cyano group, an alkoxy group, a thiol group, a substituted or unsubstituted C1-C50 alkyl group, a substituted or unsubstituted C1-C50 alkoxy group, C1 -C50 substituted or unsubstituted alkenyl group, C5-C60 substituted or unsubstituted arylene group, substituted or unsubstituted C5-C60 aryl group, substituted or unsubstituted C5-C60 aryloxy group, S, Substituted or unsubstituted C1-C50 alkyl group containing at least one hetero atom, N, O, P and Si, Substituted or unsubstituted containing at least one hetero atom, S, N, O, P and Si C1-C50 alkoxy group, S, N, O, P and Si at least one substituted or unsubstituted C5-C60 alkenyl group containing at least one hetero atom, S, N, O, P and Si At least one substituted or unsubstituted C5-C60 arylene group containing a hetero atom, S, N, O, P and Si; A substituted or unsubstituted C5-C60 aryl group containing a hetero atom of S, N, O, P and Si comprising a substituted or unsubstituted C5-C60 aryloxy group containing at least one hetero atom It may be one selected from where c is an integer of 1 to 3.

(3) R ₂ may be independently defined with different substituents when d is 1 or more, and different R ₂ may be bonded to each other to form a ring. R ₂ as defined above is each independently a hydrogen atom, a halogen atom, a cyano group, an alkoxy group, a thiol group, a substituted or unsubstituted C1-C50 alkyl group, a substituted or unsubstituted C1-C50 alkoxy group, C1 -C50 substituted or unsubstituted alkenyl group, C5-C60 substituted or unsubstituted arylene group, substituted or unsubstituted C5-C60 aryl group, substituted or unsubstituted C5-C60 aryloxy group, S, Substituted or unsubstituted C1-C50 alkyl group containing at least one hetero atom, N, O, P and Si, Substituted or unsubstituted containing at least one hetero atom, S, N, O, P and Si C1-C50 alkoxy group, S, N, O, P and Si at least one substituted or unsubstituted C5-C60 alkenyl group containing at least one hetero atom, S, N, O, P and Si At least one substituted or unsubstituted C5-C60 arylene group containing a hetero atom, S, N, O, P and Si; A substituted or unsubstituted C5-C60 aryl group containing a hetero atom of S, N, O, P and Si comprising a substituted or unsubstituted C5-C60 aryloxy group containing at least one hetero atom It may be one selected from where d is an integer of 1 to 4.

(4) R ₃ may be independently defined as different substituents when e is 1 or more, and different R ₃ may combine with each other to form a ring. R ₃ as defined above is each independently a hydrogen atom, a halogen atom, a cyano group, an alkoxy group, a thiol group, a substituted or unsubstituted C1-C50 alkyl group, a substituted or unsubstituted C1-C50 alkoxy group, C1 -C50 substituted or unsubstituted alkenyl group, C5-C60 substituted or unsubstituted arylene group, substituted or unsubstituted C5-C60 aryl group, substituted or unsubstituted C5-C60 aryloxy group, S, Substituted or unsubstituted C1-C50 alkyl group containing at least one hetero atom, N, O, P and Si, Substituted or unsubstituted containing at least one hetero atom, S, N, O, P and Si C1-C50 alkoxy group, S, N, O, P and Si at least one substituted or unsubstituted C5-C60 alkenyl group containing at least one hetero atom, S, N, O, P and Si At least one substituted or unsubstituted C5-C60 arylene group containing a hetero atom, S, N, O, P and Si; A substituted or unsubstituted C5-C60 aryl group containing a hetero atom of S, N, O, P and Si comprising a substituted or unsubstituted C5-C60 aryloxy group containing at least one hetero atom It may be one selected from, wherein e is an integer of 1 to 4.

(5) In Formula 1, when c, d, and e are each 1 or more, R ₁ and R ₂ , and R ₁ and R ₃ may combine with each other to form a ring.

(6) R ₄ through R ₅ are each independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group, a substituted or unsubstituted C _{1 -50,} Substituted or unsubstituted C _{1 -50} alkoxy group, a substituted or unsubstituted aryl thiol groups, substituted or unsubstituted of C _1-50 alkyl, a thiol group, a substituted or unsubstituted C _{6 -50} ring of ring unsubstituted C _2-50 representation of a alkenyl group, a substituted or unsubstituted aryl group of C _{6 -50} aryl group, a substituted or unsubstituted C _{4 -60} of, -N (R _{6) 2} or -N (R ₆₎ ring (R ₇₎ Substituted or unsubstituted amino group

A C _{4 -60} aryl group, C _1-50 substituted or unsubstituted alkyl group comprising at least one hetero atom of S, N, O, P and Si, at least one of S, N, O, P and Si or more with a heteroatom substituted or unsubstituted of C _{3 -50} ring alkenyl group, S, N, O, optionally substituted C _{6 -50} of including at least one or more hetero atoms of P and Si or unsubstituted arylene group, It may be one selected from the group consisting of C _{4 -60} substituted or unsubstituted aryl group containing at least one hetero atom of S, N, O, P and Si, wherein R ₆ to R ₇ is substituted or unsubstituted of a C _{1 -50} alkyl, substituted or unsubstituted C _{2 -50} of the Alkenyl group, a substituted or unsubstituted C _{6 -50} aryl group, a substituted or unsubstituted C _{4 -60} aryl group, a substituted containing at least one or more heteroatoms of S, N, O, P and Si or unsubstituted hwandoen C _{1 -50} of the alkyl group, S, N, O, P and Si, at least one heteroatom _{2 -50} C a substituted or unsubstituted alkenyl group, S, N, O of, containing P and Si in substitution of C _{2 -50} containing at least one heteroatom or unsubstituted arylene group, S, N, O, optionally substituted containing P and Si, at least one or more hetero atoms in the or unsubstituted aryl of C _{4 -60} May be one selected from the group consisting of groups, wherein R ₄ And R ₅ may be bonded to each other to form a ring.

(7) Ar ₁ To Ar ₄ is a substituted or unsubstituted C _{2 -50} An alkenyl group, a substituted or unsubstituted C _6-50 arylene group, a substituted or unsubstituted C _{4 -60} aryl group, C _{2 -} containing at least one hetero atom of S, N, O, P and Si; ₅₀ substituted or unsubstituted alkenyl group, S, N, O, P and Si at least _-50 C ₆ substituted or unsubstituted arylene group, S, in containing one or more heteroatoms of N, O, P and Si Or a substituted or unsubstituted amino group represented by a substituted or unsubstituted C _{6 -60} aryl group, -N (R ₆ ) ₂ or -N (R ₆ ) (R ₇ ) It may be one selected from the group consisting of a substituted C _{4 -60} aryl group, wherein R ₆ to R ₇ are as defined above.

As a result, the compounds according to the examples provide novel aromatic amine compounds.

As a specific example of the compound according to an embodiment of the present invention, there are compounds of the formula (2) belonging to the formula (1), but the present invention is not limited thereto.

Various organic electronic devices exist in which the compounds described with reference to Chemical Formulas 1 and 2 are used as hole injection materials and hole transport materials. Examples of the organic electronic device in which the compounds described with reference to Chemical Formulas 1 and 2 may be used include, for example, an organic light emitting diode (OLED), an organic solar cell, an organic photoconductor (OPC) drum, an organic transistor (organic TFT), and a photodiode. It can be used in organic semiconductor materials such as photodiode, organic laser, laser diode.

As an example of the organic electronic device to which the compounds described with reference to Chemical Formulas 1 and 2 may be applied, organic light emitting diodes (OLEDs) will be described as follows. Can be.

Another embodiment of the present invention is an organic electronic device comprising a first electrode, a second electrode and an organic material layer disposed between the electrodes, wherein at least one of the organic material layer of the organic electric field comprising the compounds of Formulas 1 and 2 Provided is a light emitting device.

An organic light emitting display device according to another embodiment of the present invention, except that at least one layer of the organic material layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer to form the compounds of Formulas 1 and 2 It can be prepared in a structure known in the art using conventional manufacturing methods and materials in the art. The structure of the organic light emitting display device according to the present invention is illustrated in FIGS. 1 to 5, but is not limited thereto. In this case, reference numeral 101 denotes a substrate, 102 an anode, 103 a hole injection layer, 104 a hole transport layer, 105 a light emitting layer, 106 an electron injection layer, and 107 a cathode.

Compounds described with reference to Formulas 1 and 2 may be included in one or more of a hole injection layer and a hole transport layer. Specifically, the compounds described with reference to Chemical Formulas 1 and 2 may be used in place of one or more of the hole injection materials and hole transport materials described below, or may be used in conjunction with them to form a layer. Of course, it is not only used in one layer of the organic material layer but may be used in two or more layers.

An organic light emitting display device according to another embodiment of the present invention is a metal oxide having a metal or conductivity on a substrate by using a physical vapor deposition (PVD) method, such as sputtering or e-beam evaporation By depositing these alloys to form an anode, it can be prepared by forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting 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 electronic 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 multilayer structure including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer, but is not limited thereto and may have a single layer structure. In addition, the organic material layer may be formed using a variety of polymer materials by a solvent process such as a spin coating process, a dip coating process, a doctor blading process, a screen printing process, an inkjet printing process or a thermal transfer process, Layer.

The organic light emitting device according to another embodiment of the present invention may form an organic material layer, for example, a light emitting layer, by the soluble process of the compounds described above.

The substrate is a support of the organic light emitting device, and a silicon wafer, quartz or glass plate, metal plate, plastic film or sheet, or the like can be used.

An anode is positioned over the substrate. This anode injects holes into the hole injection layer located thereon. As the anode material, a material having a large work function is usually preferred to facilitate hole injection into the organic material layer. Specific examples of the positive electrode 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), 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 hole injection layer is located on the anode. The conditions required for the material of the hole injection layer are high hole injection efficiency from the anode, it should be able to transport the injected holes efficiently. This requires a small ionization potential, high transparency to visible light, and excellent hole stability.

As the hole injecting material, it is preferable that the highest occupied molecular orbital (HOMO) of the hole injecting material be between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of hole injection materials include metal porphyrine, oligothiophene, arylamine-based organics, hexanitrile hexaazatriphenylene, quinacridone-based organics, perylene-based organics, Anthraquinone, polyaniline and polythiophene-based conductive polymers, but are not limited thereto.

The hole transport layer is positioned on the hole injection layer. The hole transport layer receives holes from the hole injection layer and transports the holes to the organic light emitting layer located thereon, and serves to prevent high hole mobility, hole stability, and electrons. In addition to these general requirements, when applied for vehicle body display, heat resistance to the device is required, and a material having a glass transition temperature (Tg) of 70 ° C. or higher is preferable. Materials satisfying these conditions include NPD (or NPB), spiro-arylamine compounds, perylene-arylamine compounds, azacycloheptatriene compounds, bis (diphenylvinylphenyl) anthracene and silicon germanium oxide. Compounds, silicone arylamine compounds and the like.

The organic light emitting layer is positioned on the hole transport layer. The organic light emitting layer is a layer for emitting light by recombination of holes and electrons injected from the anode and the cathode, respectively, and is made of a material having high quantum efficiency. The light emitting material is a material capable of emitting light in the visible region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency with respect to fluorescence or phosphorescence is preferable.

Substances or compounds that satisfy these conditions include Alq3 for green, Balq (8-hydroxyquinoline beryllium salt) for blue, DPVBi (4,4'-bis (2,2-diphenylethenyl) -1,1'- biphenyl) series, Spiro material, Spiro-DPVBi (Spiro-4,4'-bis (2,2-diphenylethenyl) -1,1'-biphenyl), LiPBO (2- (2-benzoxazoyl) -phenol lithium salt), bis (diphenylvinylphenylvinyl) benzene, aluminum-quinoline metal complex, metal complexes of imidazole, thiazole and oxazole, and the like, perylene, and BczVBi (3,3 ') to increase blue light emission efficiency. [(1,1'-biphenyl) -4,4'-diyldi-2,1-ethenediyl] bis (9-ethyl) -9H-carbazole; DSA (distrylamine) can be used by doping in small amounts. In the case of red, DCJTB ([2- (1,1-dimethylethyl) -6- [2- (2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H, 5H A small amount of doping such as -benzo (ij) quinolizin-9-yl) ethenyl] -4H-pyran-4-ylidene] -propanedinitrile) is used. When forming a light emitting layer using a process such as inkjet printing, roll coating, or spin coating, a polymer of polyphenylene vinylene (PPV) -based polymer or poly fluorene may be used for the organic light emitting layer. .

As described above, the compounds described with reference to Chemical Formulas 1 and 2 may form the corresponding layer instead of the hole injection layer and the hole transport layer or together with existing materials.

The electron transport layer is positioned on the organic light emitting layer. The electron transport layer needs a material having high electron injection efficiency from the cathode positioned thereon and capable of efficiently transporting the injected electrons. To this end, it must be made of a material having high electron affinity and electron transfer speed and excellent stability to electrons. Examples of the electron transport material that satisfies such conditions include Al complexes of 8-hydroxyquinoline; Complexes including Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited thereto.

The cathode is positioned on the electron transport layer. This cathode serves to inject electrons into the electron transport layer. As the material used as the cathode, it is possible to use the material used for the anode, and a metal having a low work function is more preferable for efficient electron injection. In particular, a suitable metal such as tin, magnesium, indium, calcium, sodium, lithium, aluminum, silver, or a suitable alloy thereof can be used. In addition, an electrode having a two-layer structure such as lithium fluoride and aluminum, lithium oxide and aluminum, strontium oxide and aluminum having a thickness of 100 μm or less may also be used.

The organic light emitting device according to the present invention may be a top emission type, a bottom emission type or a double-sided emission type according to the material used.

Meanwhile, the present invention includes a display device including the organic electronic device described above, and a terminal including a control unit for driving the display device. This terminal means a current or future wired or wireless communication terminal. The terminal according to the present invention described above may be a mobile communication terminal such as a mobile phone, and includes all terminals such as a PDA, an electronic dictionary, a PMP, a remote control, a navigation device, a game machine, various TVs, various computers, and the like.

Example

Hereinafter, the present invention will be described in more detail with reference to Preparation Examples and Experimental Examples. However, the following Production Examples and Experimental Examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

Manufacturing example

Hereinafter, the preparation or synthesis examples of the compounds belonging to the formula (2). However, since the number of compounds belonging to Formula 2 is large, one or more of the compounds belonging to Formula 2 will be exemplarily described. Those skilled in the art, that is, those skilled in the art can prepare the compounds belonging to the present invention not illustrated through the preparation examples described below.

Preparation Example 1 Preparation of the Following Compound 1 belonging to the Group of Formula 2

1. Synthesis of Intermediate 1-1 [3,5-dichloro-N, N-diphenylaniline]

(Scheme 1a)

1,3-dichloro-5-iodobenzene (50.0 mmol, 13.6 g), diphenylamine (47.5 mmol, 8.04 g), Pd ₂ (dba) ₃ (1.0 mmol, 0.9 g) in a 250 mL two-neck round bottom flask ), t- BuONa (100.0 mmol, 9.6 g) was added and charged with nitrogen. 150 mL of toluene was added thereto as a solvent, and P ( t- Bu) ₃ (1.0 mmol, 0.2g) was added thereto, followed by stirring at 80 ° C. for 2 hours. The reaction solution was cooled to room temperature and extracted with dichloromethane. The extract was dried over MgSO ₄ and dried under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography using ethyl acetate and normal hexane to give the intermediate 1-1 as a white solid. 13.2 g was obtained. (Yield 84%)

2. Compound 1

(Scheme 1b)

Intermediate 1-1 (25 mmol, 6.28 g), N , N -diphenyl-4- (4,4,5,5-tetramethyl-1,3,2-dioxabo in 250 mL two-necked round bottom flask Rrolen-2-yl) aniline (52.5 mmol, 19.5 g), Pd (PPh ₃ ) ₄ (0.75 mmol, 0.86 g), K ₂ CO ₃ (50 mmol, 6.93g) was added, 75 mL of tetrahydrofuran and 25 mL of water were added, charged with nitrogen, and stirred at 100 ° C. for 12 hours. After the reaction is completed, the temperature of the reaction solution is cooled to room temperature, extracted with dichloromethane, the organic solvent layer is dried using MgSO ₄ and dried under reduced pressure to remove the solvent. The obtained reaction product was separated and purified by silica gel column chromatography using ethyl acetate and normal hexane, and recrystallized with alcohol to obtain 12.8 g of compound 1 as a yellow solid. (Yield: 70%)

¹ H-NMR (CDCl ₃ , 400 MHz) δ7.62 (d, 4H), 7.36 (t, 4H), 7.28 (t, 8H), 7.12 (s, 1H), 6.95-6.83 (m, 8H), 6.71 -6.54 (m, 16 H).

Preparation Example 2 Preparation of the Following Compound 5 belonging to the Group of Formula 2

1.Synthesis of Intermediate 5-1 [N- (biphenyl-4-yl) -N- (3-bromo-5-chlorophenyl) biphenyl-4-amine]

(Scheme 2a)

In a 250 mL two-neck round bottom flask, 1,3-dibromo-5-chlorobenzene (50.0 mmol, 13.5 g), dibiphenylamine (47.5 mmol, 15.3 g), Pd ₂ (dba) ₃ (1.0 mmol, 0.9 g), t- BuONa (100.0 mmol, 9.6 g) was added and charged with nitrogen. 150 mL of toluene was added thereto as a solvent, and P ( t- Bu) ₃ (1.0 mmol, 0.2g) was added thereto, followed by stirring at 80 ° C. for 2 hours. The reaction solution was cooled to room temperature and extracted with dichloromethane. The resulting extract was dried under reduced pressure after dried over MgSO ₄ to obtain a crude product (crude product), the intermediate 5-1 was purified by separation by silica gel column chromatography using ethyl acetate and n-hexane as a yellow solid 19.9 g was obtained. (Yield: 78%)

2. Synthesis of Intermediate 5-3 [ N ³ , N ³ , N ^{4 '} , N ^4' -tetra (biphenyl-4-yl) -5-chlorobiphenyl-3,4'-diamine]

(Scheme 2b)

In a 250 mL two necked round bottom flask, Intermediate 5-1 (25 mmol, 12.8g), Intermediate 5-2 (25 mmol, 13.1g), Pd (PPh ₃ ) ₄ (0.75 mmol, 0.86g), K ₂ CO ₃ (50 mmol, 6.93g) was added, 75 mL of tetrahydrofuran and 25 mL of water were added, charged with nitrogen, and stirred at 80 ° C. for 6 hours. After the reaction is completed, the temperature of the reaction solution is cooled to room temperature, extracted with dichloromethane, the organic solvent layer is dried using MgSO ₄ and dried under reduced pressure to remove the solvent. The obtained reaction product was separated and purified by silica gel column chromatography using ethyl acetate and dichloromethane to obtain 21.0 g of an intermediate 5-3 as a yellow solid. (Yield 81%)

3. Compound 5

(Scheme 2c)

In a 250 mL two necked round bottom flask, intermediate 5-3 (25 mmol, 20.7 g), intermediate 5-4 (27.5 mmol, 10.2 g), Pd (PPh ₃ ) ₄ (0.75 mmol, 0.86 g), K ₂ CO ₃ (50 mmol, 6.93g) was added, 75 mL of tetrahydrofuran and 25 mL of water were added, charged with nitrogen, and stirred at 100 ° C. for 12 hours. After the reaction is completed, the temperature of the reaction solution is cooled to room temperature, extracted with dichloromethane, the organic solvent layer is dried using MgSO ₄ and dried under reduced pressure to remove the solvent. The obtained reaction product was separated and purified by silica gel column chromatography using ethyl acetate and dichloromethane, and recrystallized with alcohol and normal hexane to obtain 19.9 g of compound 5 as a yellow solid. (Yield 77%)

¹ H-NMR (CDCl ₃ , 400 MHz) δ 7.69-7.51 (m, 28H), 7.42-7.33 (m, 4H), 7.25 (t, 4H), 7.03 (s, 1H), 6.88 (td, 2H) , 6.79 (s, 2 H), 6.68-6.54 (m, 16 H).

Preparation Example 3 Preparation of the Following Compound 10 belonging to the Group of Formula 2

1. Intermediate 10-1: Synthesis of [N - N, 9-diphenyl -9 H -carbazol-3-amine - (3-bromo-5-chlorophenyl)]

(Scheme 3a)

1,3-dibromo-5-chlorobenzene (50.0 mmol, 13.5 g), N , 9-diphenyl-9 H -carbazol-3-amine (47.5 mmol, 15.9 g) in a 250 mL two-neck round bottom flask ), Pd ₂ (dba) ₃ (1.0 mmol, 0.9g), t- BuONa (100.0 mmol, 9.6g) was added and filled with nitrogen. 150 mL of toluene was added thereto as a solvent, and P ( t- Bu) ₃ (1.0 mmol, 0.2g) was added thereto, followed by stirring at 90 ° C. for 3 hours. The reaction solution was cooled to room temperature and extracted with dichloromethane. The extract was dried over MgSO ₄ and dried under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography using ethyl acetate and normal hexane to give intermediate 10-1 as a yellow solid. 10.8 g was obtained. (Yield 83%)

2. Synthesis of Intermediate 10-2 [ N- (4-bromophenyl) -N , 9-diphenyl-9 H -carbazol-3-amine]

(Scheme 3b)

1-bromo-4-iodobenzene (50.0 mmol, 14.1 g), N , 9-diphenyl-9 H -carbazol-3-amine (47.5 mmol, 15.9 g), in a 250 mL two-neck round bottom flask Pd ₂ (dba) ₃ (1.0 mmol, 0.9g) and t- BuONa (100.0 mmol, 9.6g) were added and charged with nitrogen. 150 mL of toluene was added thereto as a solvent, and P ( t- Bu) ₃ (1.0 mmol, 0.2g) was added thereto, followed by stirring at 80 ° C. for 2 hours. The reaction solution was cooled to room temperature and extracted with dichloromethane. The extract was dried over MgSO ₄ and dried under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography using ethyl acetate and normal hexane to give intermediate 10-2 as a yellow solid. 20.5 g was obtained. (Yield 88%)

3. Intermediate 10-3 [N, 9-diphenyl- N - (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -9 H -carbazol-3 -amine] Synthesis

(Scheme 3c)

In a 250 mL two-neck round bottom flask, intermediate 10-2 (50.0 mmol, 24.5 g), bispinacolatodiborone (52.5 mmol, 13.3 g), PdCl ₂ (dppf) (1.0 mmol, 0.73 g), potassium acetate (100.0 mmol, 9.81 g) was dissolved in 150 mL of DMF and charged with nitrogen. The reaction mixture was stirred at 130 ° C. for 5 hours. After the reaction is completed, the reaction mixture is further added to diethyl ether and distilled water at room temperature, and then stirred at room temperature for another 30 minutes. After the stirring was stopped, the organic layer and the water layer were separated, and each was extracted with dichloromethane. The extract thus obtained was dried with MgSO ₄ and dried under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography using ethyl acetate and normal hexane to give intermediate 10-3 as a yellow solid. 20.1 g were obtained. (Yield 75%)

4. Intermediate 10-4 [5-chloro- N ³ , N ^{4 '} -diphenyl- N ³ , N ^4' -bis (9-phenyl-9 H -carbazol-3-yl) biphenyl-3,4'-diamine Synthesis

(Scheme 3d)

In a 250 mL two-necked round bottom flask, Intermediate 10-1 (25 mmol, 13.1 g), Intermediate 10-3 (23.5 mmol, 12.7 g), Pd (PPh ₃ ) ₄ (0.75 mmol, 0.86 g), K ₂ CO ₃ (50 mmol, 6.93 g) was added, 75 mL of tetrahydrofuran and 25 mL of water were added, charged with nitrogen, and stirred at 80 ° C. for 12 hours. After the reaction is completed, the temperature of the reaction solution is cooled to room temperature, extracted with dichloromethane, the organic solvent layer is dried using MgSO ₄ and dried under reduced pressure to remove the solvent. The obtained reaction product was separated and purified by silica gel column chromatography using ethyl acetate and normal hexane, and recrystallized with alcohol to obtain 14.2 g of intermediate 10-4 as a yellow solid. (Yield 71%)

5. Compound 10

(Scheme 3e)

In a 250 mL two-necked round bottom flask, intermediate 10-4 (25 mmol, 21.3 g), intermediate 5-4 (27.5 mmol, 10.2 g), Pd (PPh ₃ ) ₄ (0.75 mmol, 0.86 g), K ₂ CO ₃ (50 mmol, 6.93g) was added, 75 mL of tetrahydrofuran and 25 mL of water were added, charged with nitrogen, and stirred at 100 ° C. for 12 hours. After the reaction is completed, the temperature of the reaction solution is cooled to room temperature, extracted with dichloromethane, the organic solvent layer is dried using MgSO ₄ and dried under reduced pressure to remove the solvent. The obtained reaction product was purified by silica gel column chromatography using ethyl acetate and normal hexane, and then recrystallized with alcohol to obtain 19.1 g of compound 10 as a yellow solid. (Yield 72%)

¹ H-NMR (CDCl ₃ , 400 MHz) δ 8.48 (d, 1H), 8.43 (d, 1H), 7.97 (d, 1H), 7.92 (d, 1H), 7.67-7.51 (m, 28H), 7.11 (s, 1 H), 6.82-6.67 (m, 22 H).

Preparation Example 4 Preparation of the Following Compound 13 belonging to the Group of Formula 2

1.Synthesis of Intermediate 13-1 [ N- (3-bromo-5-chlorophenyl) -N , 9-diphenyl-9 H -carbazol-3-amine]

(Scheme 4a)

1,3-dibromo-5-chlorobenzene (50.0 mmol, 13.5 g), N , 9-diphenyl-9 H -carbazol-3-amine (47.5 mmol, 15.9 g) in a 250 mL two-neck round bottom flask ), Pd ₂ (dba) ₃ (1.0 mmol, 0.9g), t- BuONa (100.0 mmol, 9.6g) was added and filled with nitrogen. 150 mL of toluene was added thereto as a solvent, and P ( t- Bu) ₃ (1.0 mmol, 0.2g) was added thereto, followed by stirring at 90 ° C. for 3 hours. The reaction solution was cooled to room temperature and extracted with dichloromethane. The obtained extract was dried over MgSO ₄ and dried under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography using ethyl acetate and normal hexane to give intermediate 13-1 as a yellow solid. 21.7 g were obtained. (Yield 83%)

2. Synthesis of Intermediate 13-2 [ N ¹ , N ¹ , N ⁴ -triphenylbenzene-1,4-diamine]

(Scheme 4b)

In a 250 mL two-neck round bottom flask, 4-bromo- N , N -diphenylamine (50.0 mmol, 16.2 g), aniline (50.0 mmol, 4.66 g), Pd ₂ (dba) ₃ (1.0 mmol, 0.9 g) , t- BuONa (100.0 mmol, 9.6 g) was added and charged with nitrogen. 150 mL of toluene was added thereto as a solvent, and P ( t- Bu) ₃ (1.0 mmol, 0.2g) was added thereto, followed by stirring at 80 ° C. for 2 hours. The reaction solution was cooled to room temperature and extracted with dichloromethane. The extract was dried over MgSO ₄ and dried under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography using ethyl acetate and normal hexane to give the intermediate 13 -2 as a yellow solid. 15.3 g was obtained. (Yield 91%)

3. Synthesis of Intermediate 13-3 [ N ^1- (4-bromophenyl) -N ¹ , N ⁴ , N ⁴ -triphenylbenzene-1,4-diamine]

(Scheme 4c)

In a 250 mL two-neck round bottom flask, Intermediate 13-2 (50.0 mmol, 16.8 g), 1-bromo-4-iodobenzene (50.0 mmol, 14.1 g), Pd ₂ (dba) ₃ (1.0 mmol, 0.9 g ), t- BuONa (100.0 mmol, 9.6 g) was added and charged with nitrogen. 150 mL of toluene was added thereto as a solvent, and P ( t- Bu) ₃ (1.0 mmol, 0.2g) was added thereto, followed by stirring at 80 ° C. for 3 hours. The reaction solution was cooled to room temperature and extracted with dichloromethane. The obtained extract was dried over MgSO ₄ and dried under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography using ethyl acetate and normal hexane to give intermediate 13-3 as a yellow solid. 12.6g was obtained. (Yield 88%)

4. Intermediate ^{13-4 [N 1, N 1,} N 4 -triphenyl- N 4 - (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) benzene -1,4-diamine]

(Scheme 4d)

In a 250 mL two-necked round bottom flask, intermediate 13-3 (50.0 mmol, 24.6 g), bispinacolatodiborone (52.5 mmol, 13.3 g), PdCl ₂ (dppf) (1.0 mmol, 0.73 g), potassium acetate (100.0 mmol, 9.81 g) was dissolved in 150 mL of DMF and charged with nitrogen. The reaction mixture was stirred at 130 ° C. for 2 hours. After the reaction is completed, the reaction mixture is further added to diethyl ether and distilled water at room temperature, and then stirred at room temperature for another 30 minutes. After the stirring was stopped, the organic layer and the water layer were separated, and each was extracted with dichloromethane. The extract thus obtained was dried over MgSO ₄ and dried under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography using ethyl acetate and normal hexane to give intermediate 13 -4 as a yellow solid. 21.0 g were obtained. (Yield: 78%)

5. Intermediate 13-5 [5-chloro- N ^{4 '} -(4- (diphenylamino) phenyl) -N ³ , N ^4' -diphenyl- N ^3- (9-phenyl-9 H -carbazol-3-yl) synthesis of biphenyl-3,4'-diamine]

(Scheme 4e)

In a 250 mL two necked round bottom flask, Intermediate 13-1 (25 mmol, 13.1 g), Intermediate 13-4 (27.5 mmol, 14.8 g), Pd (PPh ₃ ) ₄ (0.75 mmol, 0.86 g), K ₂ CO ₃ (50 mmol, 6.93g) was added, 75 mL of tetrahydrofuran and 25 mL of water were added, charged with nitrogen, and stirred at 100 ° C. for 12 hours. After the reaction is completed, the temperature of the reaction solution is cooled to room temperature, extracted with dichloromethane, the organic solvent layer is dried using MgSO ₄ and dried under reduced pressure to remove the solvent. The obtained reaction product was purified by silica gel column chromatography using ethyl acetate and normal hexane, and recrystallized with alcohol to obtain 13.9 g of intermediate 13-5 as a yellow solid. (Yield 65%)

6. Compound 13

(Scheme 4f)

In a 250 mL two neck round bottom flask, Intermediate 13-5 (25 mmol, 21.4 g), Intermediate 5-4 (27.5 mmol, 10.2 g), Pd (PPh ₃ ) ₄ (0.75 mmol, 0.86 g), K ₂ CO ₃ (50 mmol, 6.93g) was added, 75 mL of tetrahydrofuran and 25 mL of water were added, charged with nitrogen, and stirred at 100 ° C. for 12 hours. After the reaction is completed, the temperature of the reaction solution is cooled to room temperature, extracted with dichloromethane, the organic solvent layer is dried using MgSO ₄ and dried under reduced pressure to remove the solvent. The obtained reaction product was purified by silica gel column chromatography using ethyl acetate and normal hexane, and then recrystallized with alcohol to obtain 18.4 g of compound 13 as a yellow solid. (Yield 69%)

¹ H-NMR (CDCl ₃ , 400 MHz) δ 8.48 (d, 1H), 7,94 (d, 1H), 7.81-7.54 (m, 24H), 7.04 (s, 1H), 6.88-6.67 (m, 26H), 6.35 (d, 2H), 6.29 (d, 2H).

Preparation Example 5 Preparation of the Following Compound No. 14 Belonging to the Group of Formula 2

1. Synthesis of Intermediate 1-1 [3,5-dichloro- N , N -diphenylaniline]

(Scheme 5a)

In a 250 mL two-neck round bottom flask, 1,3-dichloro-5-iodobenzene (50.0 mmol, 13.6 g), diphenylamine (47.5 mmol, 8.04 g), Pd ₂ (dba) ₃ (1.0 mmol, 0.9 g ), t- BuONa (100.0 mmol, 9.6 g) was added and charged with nitrogen. 150 mL of toluene was added thereto as a solvent, and P ( t- Bu) ₃ (1.0 mmol, 0.2g) was added thereto, followed by stirring at 80 ° C. for 2 hours. The reaction solution was cooled to room temperature and extracted with dichloromethane. The extract was dried over MgSO ₄ and dried under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography using ethyl acetate and normal hexane to give the intermediate 1-1 as a white solid. 13.2 g was obtained. (Yield 84%)

2. Synthesis of Intermediate 14-1 [5-chloro- N ³ , N ³ , N ^{4 '} , N ^4' -tetraphenylbiphenyl-3,4'-diamine]

(Scheme 5b)

In a 500 mL two-necked round-bottom flask, Intermediate1-1 (50 mmol, 15.7g), Intermediate 5-4 (47.5 mmol, 17.6g), Pd (PPh ₃ ) ₄ (1.00 mmol, 1.15g), K ₂ CO ₃ (100 mmol, 13.9g) was added, 150 mL of tetrahydrofuran and 50 mL of water were added, charged with nitrogen, and stirred at 100 ° C. for 12 hours. After the reaction is completed, the temperature of the reaction solution is cooled to room temperature, extracted with dichloromethane, the organic solvent layer is dried using MgSO ₄ and dried under reduced pressure to remove the solvent. Recrystallization of the obtained reaction product with an alcohol after separation and purification by silica jelgwan chromatography using ethyl acetate and n-hexane to give 14.7g of intermediate 14-1 as a yellow solid. (Yield 59%)

3. Synthesis of Intermediate 10-2 [ N- (4-bromophenyl) -N , 9-diphenyl-9 H -carbazol-3-amine]

(Scheme 5c)

1-bromo-4-iodobenzene (50.0 mmol, 14.1 g), N , 9-diphenyl-9 H -carbazol-3-amine (47.5 mmol, 15.9 g), in a 250 mL two-neck round bottom flask Pd ₂ (dba) ₃ (1.0 mmol, 0.9g) and t- BuONa (100.0 mmol, 9.6g) were added and charged with nitrogen. 150 mL of toluene was added thereto as a solvent, and P ( t- Bu) ₃ (1.0 mmol, 0.2g) was added thereto, followed by stirring at 80 ° C. for 2 hours. The reaction solution was cooled to room temperature and extracted with dichloromethane. The extract was dried over MgSO ₄ and dried under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography using ethyl acetate and normal hexane to give intermediate 10-2 as a yellow solid. 20.5 g was obtained. (Yield 88%)

4. Intermediate 10-3 [N, 9-diphenyl- N - (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -9 H -carbazol-3 -amine] Synthesis

(Scheme 5d)

In a 250 mL two-neck round bottom flask, intermediate 10-2 (50.0 mmol, 24.5 g), bispinacolatodiborone (52.5 mmol, 13.3 g), PdCl ₂ (dppf) (1.0 mmol, 0.73 g), potassium acetate (100.0 mmol, 9.81 g) was dissolved in 150 mL of DMF and charged with nitrogen. The reaction mixture was stirred at 130 ° C. for 5 hours. After the reaction is completed, the reaction mixture is further added to diethyl ether and distilled water at room temperature, and then stirred at room temperature for another 30 minutes. After the stirring was stopped, the organic layer and the water layer were separated, and each was extracted with dichloromethane. The extract thus obtained was dried with MgSO ₄ and dried under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography using ethyl acetate and normal hexane to give intermediate 10-3 as a yellow solid. 20.1 g were obtained. (Yield 75%)

5. Compound 14

(Scheme 5e)

In a 250 mL two necked round bottom flask, Intermediate 14-1 (25 mmol, 13.1 g), Intermediate 10-3 (27.5 mmol, 14.8 g), Pd (PPh ₃ ) ₄ (0.75 mmol, 0.86 g), K ₂ CO ₃ (50 mmol, 6.93g) was added, 75 mL of tetrahydrofuran and 25 mL of water were added, charged with nitrogen, and stirred at 100 ° C. for 12 hours. After the reaction is completed, the temperature of the reaction solution is cooled to room temperature, extracted with dichloromethane, the organic solvent layer is dried using MgSO ₄ and dried under reduced pressure to remove the solvent. The obtained reaction product was purified by silica gel column chromatography using ethyl acetate and normal hexane, and recrystallized with alcohol to obtain 16.8 g of compound 14 as a yellow solid. (Yield 75%)

¹ H-NMR (CDCl ₃ , 400 MHz) δ 8.17 (d, 1H), 7.69-7.43 (m, 13H), 7.31 (t, 1H), 7.27-7.16 (m, 10H), 7.04 (s, 1H) , 6.89-6.78 (m, 7H), 6.61-6.49 (m, 14H), 6.15 (d, 1H).

Preparation Example 6 Preparation of the Following Compound 41 belonging to the Group of Formula 2

1.Synthesis of Intermediate 41-1 [9- (3,5-dichlorophenyl) -9 H -carbazole]

(Scheme 6a)

In a 250 mL two-neck round bottom flask, 9 H -carbazole (47.5 mmol, 7.94 g), 1,3-dichloro-5-iodobenzene (50.0 mmol, 13.6 g), Pd ₂ (dba) ₃ (1.0 mmol, 0.9 g), t- BuONa (100.0 mmol, 9.6 g) was added and charged with nitrogen. 150 mL of toluene was added thereto as a solvent, and P ( t -Bu) ₃ (1.0 mmol, 0.2g) was added thereto, followed by stirring at 80 ° C. for 6 hours. The reaction solution was cooled to room temperature and extracted with dichloromethane. The resulting extract was dried under reduced pressure after dried over MgSO ₄ to obtain a crude product (crude product), the intermediate 41-1 to the separated and purified by silica gel column chromatography using ethyl acetate and n-hexane as a yellow solid 10.1 g was obtained. (Yield 68%)

2. Synthesis of Intermediate 41-2 [9- (4-bromophenyl) -9 H -carbazole]

(Scheme 6b)

9 H -carbazole (47.5 mmol, 7.94 g), 1-bromo-4-iodobenzene (50.0 mmol, 14.1 g), Pd ₂ (dba) ₃ (1.0 mmol, 0.9) in a 250 mL two-neck round bottom flask g), t- BuONa (100.0 mmol, 9.6 g) was added and charged with nitrogen. 150 mL of toluene was added thereto as a solvent, and P ( t- Bu) ₃ (1.0 mmol, 0.2g) was added thereto, followed by stirring at 80 ° C. for 3 hours. The reaction solution was cooled to room temperature and extracted with dichloromethane. The extract was dried over MgSO ₄ and dried under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography using ethyl acetate and normal hexane to give the intermediate 41-2 as a yellow solid. 13.6 g were obtained. (Yield 89%)

3. Synthesis of Intermediate 41-3 [9- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -9 H -carbazole]

(Scheme 6c)

In a 250 mL two-neck round bottom flask, intermediate 41-2 (50.0 mmol, 16.1 g), Bis (pinacolato) diboron (52.5 mmol, 13.3 g), PdCl ₂ (dppf) (1.0 mmol, 0.73 g), potassium acetate (100.0 mmol, 9.81 g) was dissolved in 150 mL of DMF and charged with nitrogen. The reaction mixture was stirred at 80 ° C. for 3 hours. After the reaction is completed, the reaction mixture is further added to diethyl ether and distilled water at room temperature, and then stirred at room temperature for another 30 minutes. After the stirring was stopped, the organic layer and the water layer were separated, and each was extracted with dichloromethane. The extract thus obtained was dried over MgSO ₄ and dried under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography using ethyl acetate and normal hexane to give an intermediate 41-3 as a yellow solid. 14.4 g was obtained. (Yield: 78%)

4. Synthesis of Intermediate 41-4 [9,9 '-(5-chlorobiphenyl-3,4'-diyl) bis (9 H -carbazole)]

(Scheme 6d)

In a 250 mL two-neck round bottom flask, intermediate 41-1 (25 mmol, 7.80 g), intermediate 41-3 (23.7 mmol, 8.75 g), Pd (PPh ₃ ) ₄ (0.75 mmol, 0.86 g), K ₂ CO ₃ (50 mmol, 6.93g) was added, 75 mL of tetrahydrofuran and 25 mL of water were added, charged with nitrogen, and stirred at 80 ° C. for 6 hours. After the reaction is completed, the temperature of the reaction solution is cooled to room temperature, extracted with dichloromethane, the organic solvent layer is dried using MgSO ₄ and dried under reduced pressure to remove the solvent. The obtained reaction product was purified by silica gel column chromatography using ethyl acetate and normal hexane to give 6.77 g of an intermediate 41-4 as a yellow solid. (Yield 55%)

5. Compound 41

(Scheme 6e)

In a 250 mL two-necked round bottom flask, intermediate 41-4 (25 mmol, 13.0 g), intermediate 5-4 (27.5 mmol, 10.2 g), Pd (PPh ₃ ) ₄ (0.75 mmol, 0.86 g), K ₂ CO ₃ (50 mmol, 6.93g) was added, 75 mL of tetrahydrofuran and 25 mL of water were added, charged with nitrogen, and stirred at 100 ° C. for 12 hours. After the reaction is completed, the temperature of the reaction solution is cooled to room temperature, extracted with dichloromethane, the organic solvent layer is dried using MgSO ₄ and dried under reduced pressure to remove the solvent. The obtained reaction product was separated and purified by silica gel column chromatography using ethyl acetate and normal hexane, and recrystallized with alcohol to obtain 13.6 g of compound 41 as a yellow solid. (Yield 75%)

¹ H-NMR (CDCl ₃ , 400 MHz) δ 8.53 (d, 1H), 8.44 (d, 1H), 8.21 (d, 1H), 8.14 (d, 1H), 8.05 (s, 2H), 7.91 (d , 1H), 7.86 (d, 1H), 7.81 (s, 1H), 7.75 (d, 2H), 7.65-7.59 (m, 4H), 7.50-6.44 (m, 4H), 7.31-7.13 (m, 10H ), 6.91 (t, 2H), 6.69 (dt, 4H), 6.61 (d, 2H).

Experimental Example

- Hole injection layer Comparative example  And Example  -

For comparison with the compounds 10, 13, and 14 of the present invention, the physical properties of organic light emitting diodes using “2-TNATA” as the hole injection layer were measured and compared.

Comparative example  Measurement of physical properties of 1 device

An organic light emitting display device was fabricated according to a conventional method using 4,4'4 "Tris [2-naphthyl (phenyl) amino] -triphenylamine (2-TNATA) as a hole injection layer material. 600 Å hole injection layer ( hole injection layer material: 2- TNATA ), 300 Å hole hole transport layer (hole transport layer material: NPB), 450 Å thick BD-052X (Idemitsu) on ITO layer (anode) 7% doped light emitting layer (where BD-052X is a blue fluorescent dopant and 9,10-di (naphthalen-2-yl) anthracene (ADN) was used as a light emitting host material), an electron transport layer having a thickness of 250 kHz ( Electron transport layer material: Tris (8-quinolinolato) aluminum (Alq ₃ )), 10 Å thick electron injection layer (electron injection layer material: LiF) and 1500 Å thick aluminum cathode are sequentially deposited Was produced.

When the characteristics such as color coordinates, luminance, luminous efficiency, etc. of the organic light emitting diode were examined, the current density was 14.31 mA / cm ² , the color coordinates were (0.150, 0.151) and the luminous efficiency was 6.34 cd / A at 6.95 V DC.

Experimental Example 1 (Measurement of Physical Properties of Organic Electroluminescent Device Using Compound 10 of the Present Invention as Hole Injection Layer)

Using organic compound 10 as a hole injection layer, an organic light emitting display device was manufactured according to a conventional method.

First, a 600 Å hole injection layer ( hole injection layer material: compound 10 ), a 300 Å hole transport layer (hole transport layer material: NPB), and 450 Å thickness BD-052X on the ITO layer (anode) formed on the glass substrate. (Idemitsu Co., Ltd.) 7% doped light emitting layer (where BD-052X is a blue fluorescent dopant, and 9,10-di (naphthalen-2-yl) anthracene (ADN) was used as a light emitting host material), 250 Hz A thick electron transport layer (electron transport layer material: tris (8-quinolinolato) aluminum (Alq ₃ )), a 10, thick electron injection layer (electron injection layer material: LiF), and a 1500Å thick aluminum cathode were sequentially deposited. To produce an organic light emitting device.

When the characteristics such as color coordinates, luminance, luminous efficiency, etc. of the organic light emitting diode were examined, the current density was 14.53 mA / cm ² , the color coordinates were (0.150, 0.149) and the luminous efficiency was 8.26 cd / A at 5.18 V DC.

Experimental Example 2 (Measurement of Physical Properties of Organic Electroluminescent Device Using Compound 13 of the Present Invention as Hole Injection Layer)

Using organic compound 13 as a hole injection layer, an organic light emitting display device was manufactured according to a conventional method.

First, a 600 Å hole injection layer ( hole injection layer material: compound 13 ), a 300 Å hole transport layer (hole transport layer material: NPB), and 450 Å thickness BD-052X on the ITO layer (anode) formed on the glass substrate. (Idemitsu Co., Ltd.) 7% doped light emitting layer (where BD-052X is a blue fluorescent dopant, and 9,10-di (naphthalen-2-yl) anthracene (ADN) was used as a light emitting host material), 250 Hz A thick electron transport layer (electron transport layer material: tris (8-quinolinolato) aluminum (Alq ₃ )), a 10, thick electron injection layer (electron injection layer material: LiF), and a 1500Å thick aluminum cathode were sequentially deposited. To produce an organic light emitting device.

When the characteristics such as color coordinates, luminance, luminous efficiency, etc. of the organic light emitting device were examined, the current density was 14.47 mA / cm ² , the color coordinates were (0.151, 0.149), and the luminous efficiency was 8.04 cd / A at 5.43 V DC.

Experimental Example 3 (Measurement of Physical Properties of Organic Electroluminescent Device Using Compound 14 of the Present Invention as Hole Injection Layer)

Using organic compound 14 as the hole injection layer, an organic light emitting display device was manufactured according to a conventional method.

First, a 600 Å hole injection layer ( hole injection layer material: Compound 14 ), a 300 Å hole transport layer (hole transport layer material: NPB), and 450 Å thickness BD-052X on the ITO layer (anode) formed on the glass substrate. (Idemitsu Co., Ltd.) 7% doped light emitting layer (where BD-052X is a blue fluorescent dopant, and 9,10-di (naphthalen-2-yl) anthracene (ADN) was used as a light emitting host material), 250 Hz A thick electron transport layer (electron transport layer material: tris (8-quinolinolato) aluminum (Alq ₃ )), a 10, thick electron injection layer (electron injection layer material: LiF), and a 1500Å thick aluminum cathode were sequentially deposited. To produce an organic light emitting device.

When the characteristics such as color coordinates, luminance, luminous efficiency, etc. of the organic light emitting diode were examined, the current density was 14.41 mA / cm ² , the color coordinates were (0.150, 0.150) and the luminous efficiency was 7.83 cd / A at 5.87 V DC.

The physical properties of the organic electroluminescent device of Comparative Example 1 and the organic electroluminescent devices of Experimental Examples 1 to 3 using 2-TNATA as the hole injection layer material are summarized in Table 1 below.

Hole injection layer
matter Voltage
(V) Currentdensity
(mA / cm ² ) Efficiency
(㏅ / A) CIE
(x, y) Comparative Example 1 2-TNATA 6.95 14.31 6.34 (0.150, 0.151) Experimental Example 1 Compound 10 5.18 14.53 8.26 (0.150, 0.149) Experimental Example 2 Compound 13 5.43 14.47 8.04 (0.151, 0.149) Experimental Example 3 Compound 14 5.87 14.41 7.83 (0.150, 0.150)

As can be seen from Table 1, the organic electroluminescent devices of Experimental Examples 1 to 3 exhibit substantially the same color coordinates as the organic electroluminescent device using 2-TNATA as the hole injection layer material, while driving voltage and current density, It can be seen that the luminous efficiency is improved with a critical significance.

- Hole transport layer Comparative example  And Example  -

For comparison with the compounds 1, 5, and 41 of the present invention, the physical properties of the organic light emitting diode using “NPB” as the hole transport layer were measured and compared.

Comparative Example 2  Measurement of Physical Properties of Devices

An organic light emitting display device was manufactured according to a conventional method using N, N'-Di-1-naphthyl-N, N'-diphenylbenzidine (NPB) as a hole transport material. First, a 600 층 hole injection layer (hole injection layer material: 2-TNATA), a 300 Å hole transport layer ( hole transport layer material: NPB ), and 450 Å thickness BD- on an ITO layer (anode) formed on a glass substrate. Luminescent layer doped with 052X (Idemitsu) 7% (where BD-052X is a blue fluorescent dopant and 9,10-di (naphthalen-2-yl) anthracene (ADN) was used as a light emitting host material), 250 전자 thick electron transport layer (electron transport layer material: tris (8-quinolinolato) aluminum (Alq ₃ )), 10 Å thick electron injection layer (electron injection layer material: LiF) and 1500 Å thick aluminum cathode The deposition produced an organic light emitting display device.

When the characteristics such as color coordinates, luminance, luminous efficiency, etc. of the organic light emitting diode were examined, the current density was 14.31 mA / cm ² , the color coordinates were (0.150, 0.151) and the luminous efficiency was 6.34 cd / A at a direct current voltage of 6.95 V.

Experimental Example 4 (Measurement of Physical Properties of Organic Electroluminescent Device Using Compound 1 of the Present Invention as Hole Transport Layer)

Using organic compound 1 as a hole transport layer, an organic light emitting display device was manufactured according to a conventional method.

First, a 600 Å hole injection layer (hole injection layer material: 2-TNATA), a 300 Å hole transport layer ( hole transport layer material: Compound 1 ), and a 450 Å BD on the ITO layer (anode) formed on the glass substrate. A light emitting layer doped with -052X (Idemitsu Co., Ltd.) 7% (where BD-052X is a blue fluorescent dopant, and 9,10-di (naphthalen-2-yl) anthracene (ADN) was used as a light emitting host material), An electron transport layer of 250 Å thickness (electron transport layer material: tris (8-quinolinolato) aluminum (Alq ₃ )), an electron injection layer of 10 Å thickness (electron injection layer material: LiF), and an aluminum cathode of 1500 Å thickness By sequentially depositing, an organic light emitting display device was manufactured.

When the characteristics such as color coordinates, luminance, luminous efficiency, etc. of the organic light emitting diode were examined, the current density was 14.34 mA / cm ² , the color coordinates were (0.151, 0.149) and the luminous efficiency was 8.17 cd / A at 5.59 V DC.

Experimental Example 5 (Measurement of Physical Properties of Organic Electroluminescent Device Using Compound 5 of the Present Invention)

Using organic compound 5 as the hole transport layer, an organic light emitting display device was manufactured according to a conventional method.

First, a 600 Å hole injection layer (hole injection layer material: 2-TNATA), a 300 Å hole transport layer ( hole transport layer material: compound 5 ), 450 Å thickness BD on the ITO layer (anode) formed on the glass substrate A light emitting layer doped with -052X (Idemitsu Co., Ltd.) 7% (where BD-052X is a blue fluorescent dopant, and 9,10-di (naphthalen-2-yl) anthracene (ADN) was used as a light emitting host material), An electron transport layer of 250 Å thickness (electron transport layer material: tris (8-quinolinolato) aluminum (Alq ₃ )), an electron injection layer of 10 Å thickness (electron injection layer material: LiF), and an aluminum cathode of 1500 Å thickness By sequentially depositing, an organic light emitting display device was manufactured.

When the characteristics such as color coordinates, luminance, luminous efficiency, etc. of the organic light emitting diode were examined, the current density was 14.28 mA / cm ² , the color coordinates were (0.150, 0.151) and the luminous efficiency was 8.34 cd / A at 5.21 V DC.

Experimental Example 6 (Measurement of Physical Properties of Organic Electroluminescent Device Using Compound 41 of the Present Invention)

Using organic compound 41 as a hole transport layer, an organic light emitting display device was manufactured according to a conventional method.

First, a 600 Å hole injection layer (hole injection layer material: 2-TNATA), a 300 Å hole transport layer ( hole transport layer material: Compound 41 ), and a 450 Å BD on the ITO layer (anode) formed on the glass substrate. A light emitting layer doped with -052X (Idemitsu Co., Ltd.) 7% (where BD-052X is a blue fluorescent dopant, and 9,10-di (naphthalen-2-yl) anthracene (ADN) was used as a light emitting host material), An electron transport layer of 250 Å thickness (electron transport layer material: tris (8-quinolinolato) aluminum (Alq ₃ )), an electron injection layer of 10 Å thickness (electron injection layer material: LiF), and an aluminum cathode of 1500 Å thickness By sequentially depositing, an organic light emitting display device was manufactured.

When the characteristics such as color coordinates, luminance, luminous efficiency, etc. of the organic light emitting diode were examined, the current density was 14.45 mA / cm ² , the color coordinates were (0.149, 0.149) and the luminous efficiency was 7.82 cd / A at 5.74 V DC.

The physical properties of the organic electroluminescent device of Comparative Example 2 and the organic electroluminescent devices of Experimental Examples 4 to 6 using NPB as the hole transport layer material are summarized in Table 2 below.

Hole transport layer
matter Voltage
(V) Currentdensity
(mA / cm ² ) E fficiency
(㏅ / A) CIE
(x, y) Comparative Example 2 NPB 6.95 14.31 6.34 (0.150, 0.151) Experimental Example 4 Compound 1 5.59 14.34 8.17 (0.151, 0.149) Experimental Example 5 Compound 5 5.21 14.28 8.34 (0.150, 0.150) Experimental Example 6 Compound 41 5.74 14.45 7.82 (0.149, 0.149)

As can be seen from Table 2, the organic electroluminescent devices of Experimental Examples 4 to 6 exhibit substantially the same color coordinates as the organic electroluminescent devices using NPB as the hole transport layer material, and have the driving voltage, current density, and luminous efficiency. It can be seen that it improved with critical significance.

Based on the above results, the compounds of the present invention have excellent electrical and light emission characteristics, and thus, when used in organic light emitting diodes as hole injection materials and hole transport materials, high-efficiency, Low voltage, high brightness and long life can be expected. On the other hand, even if the compounds of the present invention are used in other organic material layer of the organic light emitting device it is obvious that the same effect can be obtained.

The above description is merely illustrative of the present invention, and those skilled in the art to which the present invention pertains may various modifications without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed herein are not intended to limit the present invention but to describe the present invention, and the spirit and scope of the present invention are not limited by these embodiments. The protection scope of the present invention should be interpreted by the following claims, and all the technologies within the equivalent scope should be interpreted as being included in the scope of the present invention.

Claims (9)

A compound represented by the following formula;

(1) wherein L ₁ to L ₂ independently represent a single bond, a substituted or unsubstituted alkyl group of C1-C50, a substituted or unsubstituted alkenyl group of C1-C50, a substituted or unsubstituted C5-C60 Arylene group, C5-C60 substituted or unsubstituted aryl group, S, N, O, P and Si substituted or unsubstituted C1-C50 alkyl group containing at least one hetero atom, S, N, O Substituted or unsubstituted C5-C60 alkenyl groups containing at least one hetero atom, P and Si, substituted, unsubstituted C5- containing at least one hetero atom, S, N, O, P and Si; C60 arylene group, S, N, O, P and Si is one selected from the group consisting of a substituted or unsubstituted C5-C60 aryl group containing at least one hetero atom, wherein a or b is 0 to 3 Is an integer.
(2) The R ₁ may be independently defined as different substituents when c is 1 or more, and different R ₁ may be bonded to each other to form a ring. R ₁ as defined above is each independently a hydrogen atom, a halogen atom, a cyano group, an alkoxy group, a thiol group, a substituted or unsubstituted C1-C50 alkyl group, a substituted or unsubstituted C1-C50 alkoxy group, C1 -C50 substituted or unsubstituted alkenyl group, C5-C60 substituted or unsubstituted arylene group, substituted or unsubstituted C5-C60 aryl group, substituted or unsubstituted C5-C60 aryloxy group, S, Substituted or unsubstituted C1-C50 alkyl group containing at least one hetero atom, N, O, P and Si, Substituted or unsubstituted containing at least one hetero atom, S, N, O, P and Si At least one C1-C50 alkoxy group, S, N, O, P and Si
A substituted or unsubstituted C5-C60 alkenyl group containing at least one hetero atom, S, N, O, P, and Si a substituted or unsubstituted C5-C60 arylene group containing at least one hetero atom, S, Substituted or unsubstituted C5-C60 aryl group containing at least one hetero atom, N, O, P and Si, Substituted or unsubstituted containing at least one hetero atom, S, N, O, P and Si It may be one selected from the group consisting of C5-C60 aryloxy group, wherein c is an integer of 1 to 3.
(3) R ₂ may be independently defined as different substituents when d is 1 or more, and different R ₂ may be bonded to each other to form a ring. R ₂ as defined above is each independently a hydrogen atom, a halogen atom, a cyano group, an alkoxy group, a thiol group, a substituted or unsubstituted C1-C50 alkyl group, a substituted or unsubstituted C1-C50 alkoxy group, C1 -C50 substituted or unsubstituted alkenyl group, C5-C60 substituted or unsubstituted arylene group, substituted or unsubstituted C5-C60 aryl group, substituted or unsubstituted C5-C60 aryloxy group, S, Substituted or unsubstituted C1-C50 alkyl group containing at least one hetero atom, N, O, P and Si, Substituted or unsubstituted containing at least one hetero atom, S, N, O, P and Si C1-C50 alkoxy group, S, N, O, P and Si at least one substituted or unsubstituted C5-C60 alkenyl group containing at least one hetero atom, S, N, O, P and Si At least one substituted or unsubstituted C5-C60 arylene group containing a hetero atom, S, N, O, P and Si; A substituted or unsubstituted C5-C60 aryl group containing a hetero atom of S, N, O, P and Si comprising a substituted or unsubstituted C5-C60 aryloxy group containing at least one hetero atom It may be one selected from wherein d is an integer of 1 to 4.
(4) R ₃ may be independently defined as different substituents when e is 1 or more, and different R ₃ may combine with each other to form a ring. R ₃ as defined above is each independently a hydrogen atom, a halogen atom, a cyano group, an alkoxy group, a thiol group, a substituted or unsubstituted C1-C50 alkyl group, a substituted or unsubstituted C1-C50 alkoxy group, C1 -C50 substituted or unsubstituted alkenyl group, C5-C60 substituted or unsubstituted arylene group, substituted or unsubstituted C5-C60 aryl group, substituted or unsubstituted C5-C60 aryloxy group, S, Substituted or unsubstituted C1-C50 alkyl group containing at least one hetero atom, N, O, P and Si, Substituted or unsubstituted containing at least one hetero atom, S, N, O, P and Si At least one C1-C50 alkoxy group, S, N, O, P and Si
A substituted or unsubstituted C5-C60 alkenyl group containing at least one hetero atom, S, N, O, P, and Si a substituted or unsubstituted C5-C60 arylene group containing at least one hetero atom, S, Substituted or unsubstituted C5-C60 aryl group containing at least one hetero atom, N, O, P and Si, Substituted or unsubstituted containing at least one hetero atom, S, N, O, P and Si And one selected from the group consisting of C5-C60 aryloxy groups, wherein e is an integer of 1 to 4.
5, the R ₄ and the R ₅ each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group, a substituted or unsubstituted C _{1 -50,} Substituted or unsubstituted C _{1 -50} alkoxy group, a substituted or unsubstituted C _{1 -50} alkyl thiol group, a substituted or unsubstituted aryl thiol group, a substituted C _{6 -50} or unsubstituted C _{2 -50} representation of a alkenyl group, a substituted or unsubstituted aryl group of C _{6 -50} aryl group, a substituted or unsubstituted C _{4 -60} of, -N (R _{6) 2} or -N (R ₆₎ ring (R ₇₎ substituted or unsubstituted amino group is a substituted or unsubstituted of C _{1 -50} ring containing substituted C _{4 -60} of the aryl group, S, N, O, P, and Si of at least one or more heteroatom ring group, S, N, O, C ₆ containing P and Si in one or more heteroatoms at least one heteroatom of _-50 C ₃ substituted or unsubstituted alkenyl group, S, N, O, P and Si, including the _{- A} group consisting of a substituted or unsubstituted arylene group of ₅₀ , a C _4-60 substituted or unsubstituted aryl group including at least one hetero atom of S, N, O, P, and Si From may be one selected, in which the said R ₆ to R ₇ is a substituted or unsubstituted C _{1 -50} alkyl, substituted or unsubstituted C _{2 -50} of the ring Alkenyl group, a substituted or unsubstituted C _{6 -50} aryl group, a substituted or unsubstituted C _{4 -60} aryl group, a substituted containing at least one or more heteroatoms of S, N, O, P and Si or unsubstituted hwandoen C _{1 -50} of the alkyl group, S, N, O, P and Si, at least one heteroatom _{2 -50} C a substituted or unsubstituted alkenyl group, S, N, O of, containing P and Si in substitution of C _{2 -50} containing at least one heteroatom or unsubstituted arylene group, S, N, O, optionally substituted containing P and Si, at least one or more hetero atoms in the or unsubstituted aryl of C _{4 -60} It may be one selected from the group consisting of groups, wherein R ₄ And R ₅ may be bonded to each other to form a ring.
(6) the Ar ₁ To the Ar ₄ is a substituted or unsubstituted C _{2 -50 -} alkenyl, C ₂ comprising a substituted or unsubstituted C _{6 -50} aryl group, a substituted or unsubstituted C for _4-60 aryl group, or more S, N, O, at least one of P and Si heteroatoms ₅₀ substituted or unsubstituted alkenyl group, S, N, O, P and Si at least _-50 C ₆ substituted or unsubstituted arylene group, S, in containing one or more heteroatoms of N, O, P and Si Or a substituted or unsubstituted amino group represented by a substituted or unsubstituted C _{6 -60} aryl group, -N (R ₆ ) ₂ or -N (R ₆ ) (R ₇ ) It may be one selected from the group consisting of a substituted C _{4 -60} aryl group, wherein R ₆ to R ₇ are as defined above. The method of claim 1,
When c, d, and e are each one or more, R ₁ and R ₂ , and R ₁ and R ₃ combine with each other to form a ring. The method of claim 1,
Said compound being used in a soluble process. An organic electronic device comprising at least one organic material layer comprising a compound of claim 1. The method of claim 4, wherein
The organic electronic device is an organic electroluminescent device comprising a first electrode, the at least one organic material layer and the second electrode in a stacked form sequentially. The method of claim 5,
The organic material layer includes a hole injection layer, a hole transport layer, a light emitting layer and an electron injection layer, wherein the compound of claim 1 is included in one or more of the hole injection layer and the hole transport layer. The method of claim 6,
The compound is an organic electronic device, characterized in that used as a fluorescent host material containing blue, green, red, white in the light emitting layer. The method of claim 6,
An organic electronic device comprising the compound of claim 1 to form the light emitting layer by a solution process (soluble process). A display device comprising the organic electronic device of claim 5;
And a control unit for driving the display device.

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