KR102118875B1 - Compound for organic light emitting diode, organic light emitting diode having the same, and display apparatus having organic light emitting diode - Google Patents

Abstract

The present description relates to a compound for an organic electronic device represented by Formula 1, an organic electronic device including the same, and a display device including the organic electronic device, and specific details of Formula 1 are as defined in the specification.

Description

Compound for organic electronic device, organic electronic device including same, and display device including organic electronic device {COMPOUND FOR ORGANIC LIGHT EMITTING DIODE, ORGANIC LIGHT EMITTING DIODE HAVING THE SAME, AND DISPLAY APPARATUS HAVING ORGANIC LIGHT EMITTING DIODE}

The present disclosure relates to a compound for an organic electronic device, an organic electronic device including the same, and a display device including the organic electronic device.

In general, organic light emitting diodes (OLEDs) are composed of a cathode, an anode, and an organic material layer interposed between the cathode and the anode. The overall structure of the device is transparent ITO anode, hole injection layer (HIL), hole transport layer (HTL), light emitting layer (EL), hole blocking layer (HBL), electron transport layer (ETL), electron injection layer (EIL), It is formed of a cathode such as LiAl, and, if necessary, one or two of the organic material layers may be omitted. When an electric field is applied between the configured electrodes, electrons are injected from the cathode side and holes are injected from the anode side.

Further, this electron recombines with holes in the light emitting layer to generate an excited state, and when the excited state returns to the ground state, energy is emitted as light. These luminescent materials are largely divided into fluorescence and phosphorescence, and the method of forming the luminescent layer is a method of doping phosphorescence (organic metal) to a fluorescent host (pure organic substance) and a method of doping a fluorescent dopant (organic substance containing nitrogen, etc.) to the fluorescent host. And a method for realizing a long wavelength using a dopant (DCM, Rubrene, DCJTB, etc.) in the light emitter. Through such doping, it is trying to improve the emission wavelength, efficiency, driving voltage, and lifetime. In general, materials for forming a light emitting layer include benzene, naphthalene, florene, spiroflorene, anthracene, pyrene, and carbazole, and ligands such as phenyl, biphenyl, naphthalene, and heterocycle, and ortho, meta, and para. Bonding sites and substituted structures of amine, cyanide, fluorine, methyl, trimethyl, and the like.

Currently, as the screen of the display progresses in the direction of enlargement, high-performance light emitting materials are required. In addition, in addition to the color coordinates of the emission wavelength, there is a need to improve characteristics of a high glass transition temperature, which is high luminous efficiency and chemical structural thermal stability of a material at a low driving voltage of a device.

The present disclosure is intended to provide a compound for an organic electronic device capable of providing an improved organic light-emitting performance having an asymmetric structure having excellent performance, an organic electronic device including the same, and a display device including the organic electronic device.

In addition, the technical problems to be solved by the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned are clearly understood by those skilled in the art from the following description. Will be understandable.

Compound for an organic electronic device according to an embodiment of the present invention is represented by the following formula (1).

[Formula 1]

Q ₁ is a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 30 carbon atoms or a substituted or unsubstituted aromatic hetero ring having 5 to 30 carbon atoms;

R ₁ is hydrogen, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted carbon number 5 To 30 cycloalkenyl groups, substituted or unsubstituted alkoxy groups having 1 to 30 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted alkylthioxy groups having 1 to 30 carbon atoms, substituted or Unsubstituted arylthiooxy group having 5 to 30 carbon atoms, substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, substituted or unsubstituted 5 to 50 carbon atoms An aryl group, a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, or a combination thereof,

Ar ₁ is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylthioxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon number 2 To 30 heterocycloalkyl groups, substituted or unsubstituted heteroaryl groups having 2 to 50 carbon atoms, substituted or unsubstituted aryl groups having 6 to 50 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or An unsubstituted arylthiooxy group having 6 to 30 carbon atoms, a substituted or unsubstituted arylamine group having 6 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, or a combination thereof,

Ar ₂ is hydrogen, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted carbon number 5 To 30 cycloalkenyl groups, substituted or unsubstituted alkoxy groups having 1 to 30 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted alkylthioxy groups having 1 to 30 carbon atoms, substituted or Unsubstituted arylthiooxy group having 5 to 30 carbon atoms, substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, substituted or unsubstituted 5 to 50 carbon atoms Aryl group, substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, substituted or unsubstituted silyl group, substituted or unsubstituted germanium group, substituted or unsubstituted boron group, substituted or unsubstituted aluminum group, carbonyl group , Phosphoryl group, amino group, nitrile group, hydroxy group, nitro group, halogen group, selenium group, tellurium group, amide group and ester group, or combinations thereof.

The organic electronic device according to another embodiment of the present invention includes a first electrode, a second electrode, and at least one organic material layer interposed between the first electrode and the second electrode, and at least one of the organic material layers is the aforementioned organic And compounds for electronic devices.

The display device according to another embodiment of the present invention includes the above-described organic electronic device.

According to the present description, it is possible to provide a compound for an organic electronic device having excellent performance by providing a structure of an asymmetric structure, an organic electronic device including the same, and a display device including the organic electronic device.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, in describing the present description, descriptions of already known functions or configurations will be omitted to clarify the subject matter of the present description.

"Substituted" in this specification, unless otherwise defined, at least one hydrogen in the substituent or compound is deuterium, halogen group, hydroxy group, amino group, substituted or unsubstituted amine group, nitro group, substituted or unsubstituted silyl group , An alkyl group having 1 to 30 carbon atoms, an alkylsilyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a fluoro group, a trifluoromethyl group, etc. It means that it is substituted with a trifluoroalkyl group having 1 to 10 carbon atoms or a cyano group.

Also, the substituted halogen group, hydroxy group, amino group, substituted or unsubstituted amine group, nitro group, substituted or unsubstituted silyl group, alkyl group having 1 to 30 carbon atoms, alkylsilyl group having 1 to 10 carbon atoms, 3 to 30 carbon atoms Two adjacent substituents among 1 to 10 carbon atoms, such as a cycloalkyl group, an aryl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a fluoro group, a trifluoromethyl group, or a cyano group are fused It may form a ring.

As used herein, "hetero" means that one or three heteroatoms selected from the group consisting of N, O, S, and P are contained in one functional group, and the rest are carbon, unless otherwise defined.

"Combination of these" in the present specification means that two or more substituents are bonded to a linking group, or two or more substituents are condensed to bond, unless otherwise defined.

"Alkyl (alkyl) group" as used herein means an aliphatic hydrocarbon group, unless otherwise defined. The alkyl group may be a "saturated alkyl group" that does not contain any double or triple bonds.

The alkyl group may be an alkyl group having 1 to 20 carbon atoms. More specifically, the alkyl group may be an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 6 carbon atoms. For example, an alkyl group having 1 to 4 carbon atoms means that the alkyl chain contains 1 to 4 carbon atoms, and methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and t- It is selected from the group consisting of butyl.

The alkyl group is, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl It means practical skill.

"Aryl (aryl) group" means a substituent in which all elements of a cyclic substituent have p-orbitals, and these p-orbitals form a conjugate, and monocyclic or fused ring polycyclic ( That is, it contains a ring) functional group that divides adjacent pairs of carbon atoms.

"Heteroaryl (heteroaryl) group" means that the aryl group contains 1 to 3 hetero atoms selected from the group consisting of N, O, S and P, and the rest is carbon. When the heteroaryl group is a fused ring, each ring may include 1 to 3 heteroatoms.

In the present specification, the hole property means a property that has conductivity characteristics along the HOMO level and facilitates injection of holes formed at the anode into the light emitting layer and movement in the light emitting layer. More specifically, it may be similar to the property of repelling electrons.

In addition, the electronic property means a property that has conductivity characteristics along the LUMO level to facilitate injection of electrons formed at the cathode into the light emitting layer and movement in the light emitting layer. More specifically, it may be similar to the characteristic of pulling electrons.

According to one embodiment of the present invention, a compound for an organic electronic device represented by the following Chemical Formula 1 is provided.

[Formula 1]

Q ₁ is a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 30 carbon atoms or a substituted or unsubstituted aromatic hetero ring having 5 to 30 carbon atoms;

R ₁ is hydrogen, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted carbon number 5 To 30 cycloalkenyl groups, substituted or unsubstituted alkoxy groups having 1 to 30 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted alkylthioxy groups having 1 to 30 carbon atoms, substituted or Unsubstituted arylthiooxy group having 5 to 30 carbon atoms, substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, substituted or unsubstituted 5 to 50 carbon atoms An aryl group, a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, or a combination thereof,

Ar ₁ is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylthioxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon number 2 To 30 heterocycloalkyl groups, substituted or unsubstituted heteroaryl groups having 2 to 50 carbon atoms, substituted or unsubstituted aryl groups having 6 to 50 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or An unsubstituted arylthiooxy group having 6 to 30 carbon atoms, a substituted or unsubstituted arylamine group having 6 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, or a combination thereof,

Ar ₂ is hydrogen, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted carbon number 5 To 30 cycloalkenyl groups, substituted or unsubstituted alkoxy groups having 1 to 30 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted alkylthioxy groups having 1 to 30 carbon atoms, substituted or Unsubstituted arylthiooxy group having 5 to 30 carbon atoms, substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, substituted or unsubstituted 5 to 50 carbon atoms Aryl group, substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, substituted or unsubstituted silyl group, substituted or unsubstituted germanium group, substituted or unsubstituted boron group, substituted or unsubstituted aluminum group, carbonyl group , Phosphoryl group, amino group, nitrile group, hydroxy group, nitro group, halogen group, selenium group, tellurium group, amide group and ester group, or combinations thereof.

For example, in Formula 1, Ar ₂ is a substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, a substituted or unsubstituted aryl having 5 to 50 carbon atoms. Group, a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, or a combination thereof.

The Chemical Formula 1 may be represented by any one of the following Chemical Formulas 2-1 to 2-15.

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

[Formula 2-6]

[Formula 2-7]

[Formula 2-8]

[Formula 2-9]

[Formula 2-10]

[Formula 2-11]

[Formula 2-12]

[Formula 2-13]

[Formula 2-14]

[Formula 2-15]

In Chemical Formulas 2-1 to 2-15,

Ar ₁ is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylthioxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon number 2 To 30 heterocycloalkyl groups, substituted or unsubstituted heteroaryl groups having 2 to 50 carbon atoms, substituted or unsubstituted aryl groups having 6 to 50 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or An unsubstituted arylthiooxy group having 6 to 30 carbon atoms, a substituted or unsubstituted arylamine group having 6 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, or a combination thereof,

Ar ₂ is hydrogen, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted carbon number 5 To 30 cycloalkenyl groups, substituted or unsubstituted alkoxy groups having 1 to 30 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted alkylthioxy groups having 1 to 30 carbon atoms, substituted or Unsubstituted arylthiooxy group having 5 to 30 carbon atoms, substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, substituted or unsubstituted 5 to 50 carbon atoms Aryl group, substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, substituted or unsubstituted silyl group, substituted or unsubstituted germanium group, substituted or unsubstituted boron group, substituted or unsubstituted aluminum group, carbonyl group , Phosphoryl group, amino group, nitrile group, hydroxy group, nitro group, halogen group, selenium group, tellurium group, amide group and ester group, or combinations thereof,

X are each independently CR ₅ or nitrogen (N),

Y is oxygen (O) or sulfur (S),

R ₁ to R ₅ are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, Substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, substituted or unsubstituted carbon number 1 to 30 Alkyl thioxy group, substituted or unsubstituted arylthioxy group having 5 to 30 carbon atoms, substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, substituted or unsubstituted A substituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, or a combination thereof,

Z ₁ is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylthioxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon number 2 To 30 heterocycloalkyl groups, substituted or unsubstituted heteroaryl groups having 2 to 50 carbon atoms, substituted or unsubstituted aryl groups having 6 to 50 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or Unsubstituted arylthiooxy group having 6 to 30 carbon atoms, substituted or unsubstituted arylamine group having 6 to 30 carbon atoms, substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, or a combination thereof.

The compound for an organic electronic device according to Formula 1 may be represented by any one of the following formulas.

According to another embodiment of the present invention, an organic electronic device including a first electrode, a second electrode, and at least one organic material layer interposed between the first electrode and the second electrode, wherein at least one of the organic material layers is described above. An organic electronic device comprising the compound for an organic electronic device of Formula 1 is provided.

The compound for an organic electronic device may be included in the organic material layer in the form of a single material or a mixture of different materials.

In the present specification, "organic layer" is a term referring to all layers interposed between the first electrode and the second electrode in the organic electronic device. The organic material layer may be a layer having hole characteristics and a layer having electronic characteristics. For example, the organic material layer is a hole injection layer, a hole transport layer, a function layer having a hole injection function and a hole transport function simultaneously, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and an electron transport function and an electron injection It may include one or more of the functional layer having a function at the same time.

At least one of the hole injection layer, the hole transport layer, and the functional layer having the hole injection function and the hole transport function at the same time, in addition to a conventional hole injection material, a hole transport material and a material simultaneously performing the hole injection and transport function, charge- It may further include a product.

For example, the organic material layer includes a light emitting layer, and the light emitting layer may include at least one of a phosphorescent host, a fluorescent host, a phosphorescent dopant, and a fluorescent dopant. Here, the compound for the organic electronic device is included in the light emitting layer, i) the fluorescent host is the compound for the organic electronic device, ii) the fluorescent dopant is the compound for the organic electronic device, or iii) the fluorescent host And each of the fluorescent dopant may be a compound for the organic electronic device.

The emission layer may be a red, green or blue emission layer. For example, the light emitting layer may be a blue light emitting layer. At this time, the compound for an organic electronic device may be used as a blue host and/or a blue dopant, to provide an organic electronic device having high efficiency, high brightness, high color purity, and long life.

Further, the organic material layer includes an electron transport layer, and the compound for the organic electronic device may be included in the electron transport layer. Here, the electron transport layer may further include a metal-containing compound in addition to the compound for an organic electronic device.

The organic material layer includes both a light emitting layer and an electron transport layer, and each of the light emitting layer and the electron transport layer includes the compound for an organic electronic device (the compound for the organic electronic device included in the light emitting layer and the electron transport layer may be the same or different from each other). It may be.

The organic electronic device may be manufactured by a conventional method and material for manufacturing an organic electronic device, except for using the compound for an organic electronic device of Formula 1.

The organic electronic device may be any one of an organic photoelectric device, an organic light emitting device (OLED), an organic solar cell (OSC), an electronic paper (e-Paper), an organic photoreceptor (OPC), an organic transistor (OTFT), and an organic memory device. Can be.

For example, the organic light emitting device deposits a metal or conductive metal oxide or alloys thereof on a substrate using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation. It can be prepared by forming an anode, forming 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 depositing a material that can be used as a cathode thereon. In addition to this method, an organic light emitting device may be formed by sequentially depositing a cathode material, an organic material layer, and a cathode 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. In addition, the organic material layer uses a variety of polymer materials to reduce the number of layers by a solvent process (e.g., spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer), not a deposition method. Can be produced.

The organic light emitting device according to the embodiment may be a front emission type, a back emission type, or a double-sided emission type depending on the material used. The compound for an organic electronic device according to an embodiment may also act on a principle similar to that applied to an organic light emitting device in organic electronic devices including organic solar cells, lighting OLEDs, flexible OLEDs, organic photoconductors, and organic transistors.

Hereinafter, preferred embodiments are provided to help understanding of the present invention. However, the following examples are only provided to more easily understand the present invention, and the contents of the present invention are not limited thereby.

In addition, it is understood that in each embodiment of the present invention, a compound in which the manufacturing method is not specifically disclosed is prepared by a conventional method in the art or by referring to a manufacturing method described in another example.

<Production of intermediates>

* Preparation of intermediate 3-chloro-4-nitro-N,N-diphenylaniline (A-1)

Diphenylamine 31.6g (187 mmol), 4-bromo-2-chloro-1-nitrobenzene 43.2 g (183 mmol), Pd(C2H3O2 )2 0.4 g (1.83 mmol), Pt-Bu3 (0.37 g, 1.83 mmol) and NaOt-Bu 22.8 g (238 mmol) dissolved in 1000 ml of toluene and stirred at 80 °C for 4 hours. After the reaction solution was cooled to room temperature, it was extracted three times with 300 mL of water and 300 mL of diethyl ether. The collected organic layer was dried with magnesium sulfate, and the residue obtained by evaporating the solvent was separated and purified through silica gel column chromatography to obtain 47.5 g (yield 80%) of Intermediate A-1. The obtained compound was confirmed by LC-MS.

Mass spectrum m/z: 324.76 (calculated value 324.07)

* Preparation of intermediates A-2 to A-7

A compound of the following [Table 1] was obtained by the method for preparing the intermediate A-1.

* Preparation of intermediate 3-chloro-4-nitro-1,1'-biphenyl (B-1)

(4-bromophenyl)broonic acid ((4-bromophenyl)boronic acid) 36.7 g (183 mmol), 4-bromo-2-chloro-1-nitrobenzene (4-bromo-2-chloro-1-nitrobenzene ) 43.3g (183mmol), Pd(PPh3)4 2.1 g (1.83 mmol) and K2CO3 75.7 g (549 mmol) were dissolved in 60 ml of THF/H2O (2/1) mixed solution and stirred at 70°C for 5 hours. . After the reaction solution was cooled to room temperature, 40 mL of water was added and extracted three times with 50 mL of ethyl ether. The collected organic layer was dried over magnesium sulfate, and the residue obtained by evaporating the solvent was separated and purified through silica gel tube chromatography to obtain 29.9 g of B-1 (70% yield). The obtained compound was confirmed by LC-MS.

Mass spectrum m/z: 233.65 (calculated 233.02)

* Preparation of intermediate 2-chloro-3-nitro-6-phenylpyridine (B-2)

(4-bromophenyl)broonic acid (36.7 g (183 mmol), 6-bromo-2-chloro-3-nitropyridine (6-bromo-2-chloro-3- After dissolving nitropyridine) 43.5g (183mmol), Pd(PPh3)4 2.1g (1.83 mmol) and K2CO3 75.7 g (549 mmol) in 500 ml of THF/H2O (2/1) mixed solution, stir at 70°C for 5 hours. Did. After the reaction solution was cooled to room temperature, 40 mL of water was added and extracted three times with 50 mL of ethyl ether. The collected organic layer was dried over magnesium sulfate, and the residue obtained by evaporating the solvent was separated and purified through silica gel column chromatography to obtain 27.9 g (yield 65%) of B-2. The obtained compound was confirmed by LC-MS.

Mass spectrum m/z: 234.64 (calculated 234.02)

* Preparation of intermediate (4-((3-cyanophenyl)(phenyl)amino)phenyl)boronic acid (C-1)

14.8 g of 3-((4-bromophenyl)(phenyl)amino)benzonitrile (3-((4-bromophenyl)(phenyl)amino)benzonitrile) and 200 mL of tetrahydrofuran were dissolved in a reactor and dissolved at -76°C. After cooling, 21 mL of 2.5M n-butyllithium was slowly added dropwise and stirred for 30 minutes. After adding 14 g of triisopropyl borate and stirring at room temperature for 18 hours, 300 mL of 1N aqueous hydrochloric acid solution was added and stirred for 1 hour, and the reaction was terminated. After extraction with 500 mL of ethyl acetate and 500 mL of brine, the organic layer was dehydrated with 20 g of anhydrous magnesium sulfate and concentrated under reduced pressure. The solid was filtered and washed with a mixed solvent of toluene hexane to obtain 10.6 g of C-1 (80% yield).

Mass spectrum m/z: 314.15 (calculated value 314.12)

* Preparation of intermediates C-2 to C-37

The compound of the following [Table 2] was obtained by the method for preparing the intermediate C-1:

* Preparation of intermediates D-1 to D-30

A compound of the following [Table 3] was obtained as a method for preparing the intermediate B-1.

* Preparation of intermediates E-1 to E-43

A compound of the following [Table 4] was obtained as a method for preparing the intermediate A-1.

* Preparation of intermediates F-1 to F-34

A compound of the following [Table 5] was obtained as a method for preparing the intermediate B-1.

* Preparation of intermediate (4-((3-cyanophenyl)(phenyl)amino)phenyl)boronic acid (G-1)

In the reactor, 4.9 g (10.0 mmol) of 7-(2-nitrophenyl)-N,N-diphenylpyren-2-amine and 5.77 g (22 mmol) of PPh3 were dissolved in 1,2-dichlorobenzene (30 ml), and then at 170°C. Stirred for 12 hours. After the reaction was cooled, the solvent was removed under vacuum, and distilled water and dichloromethane solution (50 mL: 50 mL) were extracted three times.. The collected organic layer was dried with magnesium sulfate, and the residue obtained by evaporating the solvent was silica gel tube. Separated by chromatography to give 3.3 g of G-1 (72% yield).

Mass spectrum m/z: 458.55 (calculated value: 458.18)

* Preparation of intermediates H-2 to H-83

The compound of the following [Table 6] was obtained by the method for preparing the intermediate H-1:

Preparation of Examples

* Preparation of Examples H-1 to H-90

The compound of the following [Table 7] was obtained by the production method of A-1:

<Experimental Example>

A glass substrate coated with a thin film coated with ITO at a thickness of 1500 에 was placed in secondary distilled water in which Fischer's detergent was dissolved and washed with ultrasonic waves for 30 minutes. After washing the ITO for 30 minutes, ultrasonic washing was repeated for 2 minutes with distilled water twice. After washing with distilled water was completed, ultrasonic cleaning with a solvent of isopropyl alcohol, acetone, and methanol was performed, followed by drying, and then transferred to a plasma cleaner, followed by washing the substrate for 5 minutes using oxygen plasma and then transferred to a vacuum evaporator.

After the 500 Å vacuum deposition of 2-TNATA (4,4',4"-Tris[2-naphthyl(phenyl)amino]triphenylamine) as a hole injection layer on the prepared ITO transparent electrode, a-NPD (N, N'-Di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine) 300Å after vacuum deposition, AND (9,10-Di(2-naphthyl )anthracene) and dopant DPAP-DPPA (6-(4-(diphenylamino)phenyl)-N,N-diphenylpyren-1-amine) or vacuum with a thickness of 300 하여 by doping 5% of the material of the example as shown in Table 3 It was deposited and vacuum-deposited a TPBi (1,3,5-tris(N-phenylbenzimidizol-2-yl)benzene) material as a hole blocking layer and a hole transport layer to a thickness of 400Å, and sequentially LiF 5Å and Al (aluminum) A cathode was formed by deposition at 2000 Pa. In the above process, the deposition rate of the organic material was maintained at 1 Pa/sec, LiF was 0.2 Pa/sec, and aluminum was maintained at a deposition rate of 3-7 Pa/sec.

The electroluminescence properties of the organic light-emitting device manufactured above are shown in Table 8 below.

Current density
(mA/cm ² ) color efficiency
(cd/A) life span
(hrs) Comparative Experimental Example
(DPAP-DPPA) 20 blue 4.6 3,100 H-1 20 blue 6.7 6,600 H-2 20 blue 6.5 7,400 H-3 20 blue 6.8 7,500 H-6 20 blue 6.6 6,500 H-7 20 blue 7.6 7,200 H-27 20 blue 6.9 6,400 H-28 20 blue 7.4 7,300 H-29 20 blue 6.7 6,100 H-32 20 blue 6.5 6,600 H-33 20 blue 6.8 5,500 H-40 20 blue 7.0 5,300 H-41 20 blue 6.7 5,400 H-53 20 blue 7.2 7,100

From the results of Table 8, it was confirmed that the compound for an organic electronic device according to the present invention has improved luminous efficiency and lifetime characteristics in the role of blue.

As described above, according to the present disclosure, it is possible to provide a compound for an organic electronic device having excellent performance by providing a structure of an asymmetric structure, an organic electronic device including the same, and a display device including the organic electronic device.

In the foregoing, although specific embodiments of the present invention have been described and illustrated, the present invention is not limited to the described embodiments, and it is common knowledge in the field of this technology that various modifications and modifications can be made without departing from the spirit and scope of the present invention. It is obvious to those who have it. Therefore, such modifications or variations should not be individually understood from the technical spirit or viewpoint of the present invention, and the modified embodiments should belong to the claims of the present invention.

Claims (8)

Compound for an organic electronic device represented by the following formula 1:
[Formula 1]

Q ₁ is a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 30 carbon atoms or a substituted or unsubstituted aromatic hetero ring having 5 to 30 carbon atoms;
R ₁ is hydrogen, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted carbon number 5 To 30 cycloalkenyl groups, substituted or unsubstituted alkoxy groups having 1 to 30 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted alkylthioxy groups having 1 to 30 carbon atoms, substituted or Unsubstituted arylthiooxy group having 5 to 30 carbon atoms, substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, substituted or unsubstituted 5 to 50 carbon atoms An aryl group, a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, or a combination thereof,
Ar ₁ is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylthioxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon number 2 To 30 heterocycloalkyl groups, substituted or unsubstituted heteroaryl groups having 2 to 50 carbon atoms, substituted or unsubstituted aryl groups having 6 to 50 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or An unsubstituted arylthiooxy group having 6 to 30 carbon atoms, a substituted or unsubstituted arylamine group having 6 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, or a combination thereof,
Ar ₂ is a substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, or a substituted or unsubstituted arylamine group having 5 to 30 carbon atoms. delete According to claim 1,
Chemical Formula 1 is represented by any one of the following Chemical Formulas 2-1 to 2-15, an organic electronic device compound:
[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

[Formula 2-6]

[Formula 2-7]

[Formula 2-8]

[Formula 2-9]

[Formula 2-10]

[Formula 2-11]

[Formula 2-12]

[Formula 2-13]

[Formula 2-14]

[Formula 2-15]

R ₁ to R ₄ are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, Substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, substituted or unsubstituted carbon number 1 to 30 Alkyl thioxy group, a substituted or unsubstituted arylthioxy group having 5 to 30 carbon atoms, a substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, substituted or unsubstituted A substituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, or a combination thereof,
X is C,
X ₁ and X ₂ are each C or N,
Y is O or S,
Z ₁ is hydrogen, an alkyl group having 1 to 30 carbon atoms, or an unsubstituted aryl group having 5 to 50 carbon atoms,
Ar ₁ is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylthioxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon number 2 To 30 heterocycloalkyl groups, substituted or unsubstituted heteroaryl groups having 2 to 50 carbon atoms, substituted or unsubstituted aryl groups having 6 to 50 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or An unsubstituted arylthiooxy group having 6 to 30 carbon atoms, a substituted or unsubstituted arylamine group having 6 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, or a combination thereof,
Ar ₂ is a substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, or a substituted or unsubstituted arylamine group having 5 to 30 carbon atoms. According to claim 1,
The compound for an organic electronic device is represented by any one of the following formulas, a compound for an organic electronic device:

. In the organic electronic device including a first electrode, a second electrode and at least one organic material layer interposed between the first electrode and the second electrode,
At least one of the organic layer comprises the compound for an organic electronic device according to any one of claims 1, 3, and 4, an organic electronic device. The method of claim 5,
The organic material layer is any one selected from the group consisting of a light emitting layer, a hole transport layer, a hole injection layer, an electron transport layer, an electron injection layer, a hole blocking layer, and combinations thereof. The method of claim 5,
The organic electronic device,
An organic electronic device, which is any one selected from the group consisting of an organic photoelectric device, an organic light emitting device, an organic solar cell, an organic transistor, an organic photoreceptor, an electronic paper and an organic memory device. A display device comprising the organic electronic device according to claim 5.