KR101472057B1 - An asymmetric anthracene derivatives, a method of making the same, and organic electroluminescent device using the same - Google Patents

Abstract

상기 식에서,
Ar₁과 Ar₂는 각각 독립적으로 동일 또는 상이하며, 비치환 또는 C₁~C₂₀ 알킬기 또는 C₆~C₄₀ 아릴기로 치환 가능한 페닐; 바이페닐; 나프틸; 안트라세닐; 펜안트라세닐; 파이레닐; 피리디닐; 바이피리디닐; 피라지닐 및 트리아지닐로 이루어진 군으로부터 선택된 치환기이고,
Ar₃은 비치환 또는 C₁~C₂₀ 알킬기 또는 C₆~C₄₀ 아릴기로 치환 가능한 C₆~C₄₀ 아릴기 또는 C₅~C₄₀ 헤테로아릴기이다.The present invention relates to an asymmetric anthracene derivative represented by the following formula (1), a process for producing the same, and an organic light emitting device comprising the asymmetric anthracene derivative:
Formula 1

In this formula,
Ar ₁ and Ar ₂ are independently the same or different and are phenyl which is unsubstituted or substituted with a C ₁ to C ₂₀ alkyl group or a C ₆ to C ₄₀ aryl group; Biphenyl; Naphthyl; Anthracenyl; Phenanthracenyl; Pyrenyl; Pyridinyl; Bipyridinyl; Lt; / RTI > is a substituent selected from the group consisting of < RTI ID = 0.0 >
Ar ₃ is a C ₆ to C ₄₀ aryl group or a C ₅ to C ₄₀ heteroaryl group which is unsubstituted or substituted with a C ₁ to C ₂₀ alkyl group or a C ₆ to C ₄₀ aryl group.

Description

TECHNICAL FIELD [0001] The present invention relates to an asymmetric anthracene derivative, a process for producing the same, and an organic electronic device comprising the same. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a novel asymmetric anthracene derivative which can be used as a light source for display or illumination for mobile phones, navigation and televisions, a process for producing the same, and an organic electronic device including the derivative.

&Quot; Organic electronic device " means a device requiring charge exchange between an electrode and an organic material using holes and / or electrons. The organic electronic device can be roughly classified into two types according to the operating principle as described below. First, electrons and holes are separated from each other by excitons formed in the organic layer by photons flowing from the external light source to the device, and electrons and holes are transferred to different electrodes to be used as a current source (voltage source) Device. The second type is an electric device that injects holes and / or electrons into an organic semiconductor, which forms an interface with an electrode by applying a voltage or current to two or more electrodes, and operates by injected electrons and holes.

Examples of the organic electronic device include an organic light emitting diode (OLED), an organic solar cell (OSC), an illumination OLED, a flexible OLED, an organic photoconductor (OPC), and an organic transistor (OTFT) All of these require hole injecting or transporting materials, electron injecting or transporting materials, or light emitting materials for driving the devices.

Hereinafter, the organic light emitting device will be described in detail. However, in the organic electronic devices, hole injecting or transporting materials, electron injecting or transporting materials, or light emitting materials act on a similar principle.

Generally, an organic light emitting device is composed of an organic material layer between a cathode and an anode. The overall structure of the organic light emitting device is a transparent ITO anode, a hole injection layer (HIL), a hole transport layer (HTL), a light emitting layer (EL), a hole blocking layer (HBL) ), An electron transport layer (ETL), an electron injection layer (EIL), a LiAl cathode, and the like, and one or two layers may be omitted from the organic layer if necessary. When an electric field is applied between the electrodes, electrons are injected from the cathode side and holes are injected from the anode side. Further, electrons supplied from the cathode recombine with holes in the light emitting layer to generate an excited state, and emit energy as light when the excited state returns to the ground state.

Such a luminescent material is largely divided into fluorescence and phosphorescence. The method of forming a luminescent layer includes a method of doping a fluorescent host (pure organic material) with phosphorescence (organic metal), a method of doping a fluorescent dopant (organic material including nitrogen etc.) And a method of implementing a long wavelength using a dopant (for example, DCM, Rubrene, DCJTB, etc.) on a light emitting body. Such doping is intended to improve the emission wavelength, efficiency, driving voltage, and the like.

The luminescent material is generally a center body such as benzene, naphthalene, fluorene, spiropro lrene, anthracene, pyrene, carbazole and the like; Ligands such as phenyl, biphenyl, naphthalene and heterocycle; Bonding positions of ortho, meta, para, etc .; And substituents such as amine, cyan, fluorine, methyl, trimethyl and the like.

The luminescent material currently used in the art is a material capable of emitting light in the visible light region by transporting and combining holes and electrons from the hole transporting layer and the electron transporting layer, and specific examples thereof include blue-based AND, MADN, DPVBi, BAlq ; Green series Alq3; And other compounds represented by anthracene, pyrene, fluorene, spiro, fluorene, carbazole, benzoxazole, benzthiazole and benzimidazole series, and high molecular weight poly (p-phenylenevinylene) , Polypyrene, polyfluorene, and the like.

The following compounds are symmetric / asymmetric anthracene derivatives used as a host and dopant emitter in OLED devices:

In recent years, OLEDs are required to have luminescent materials capable of displaying more delicate and brighter colors as the display screen progresses in the direction of enlargement. Among them, the problem to be solved and the luminescent material to be solved is a blue luminescent material according to a large surface area, and a high performance luminescent material is required in the current blue sky (Blue) and deep blue (Deep Blue) directions. In addition to the chromaticity coordinates of the emission wavelength, high luminous efficiency at a low driving voltage of the device and high glass transition temperature, which is a chemical structural thermal stability of the material, are required.

As a result of studies for meeting these demands, Japanese Patent Application Laid-Open No. 2008-239988 discloses a compound for an organic light emitting device having the following formula:

Japanese Laid-Open Patent Publication No. 2006-199629 discloses an anthracene derivative used in an organic light-emitting device having the following formula:

KR 10-2004-0105853 discloses a blue light emitting organic compound having the formula:

KR 10-2009-0126978 discloses compounds for organic light emitting devices having the following formula:

However, the compounds disclosed in the above-mentioned prior art have problems in that they are easily crystallized at a high temperature due to the symmetrical structure thereof, shortening the lifetime or unsatisfying color purity and efficiency.

1. JP 2008-239988 2. JP 2006-199629 A 3. KR 10-2004-0105853 A 4. KR 10-2009-126978 A

In order to solve the above problems, the present invention provides asymmetric anthracene derivatives having high glass transition temperature, high thermal stability, and satisfactory color purity and efficiency, which are used in organic light emitting devices.

In addition, the present invention provides a method for producing the anthracene derivative.

Also, the present invention provides an organic electronic device including the anthracene derivative.

According to one aspect of the present invention, there is provided an asymmetric anthracene derivative represented by the following general formula (1): < EMI ID =

In this formula,

Ar ₁ and Ar ₂ are independently the same or different and are phenyl which is unsubstituted or substituted with a C ₁ to C ₂₀ alkyl group or a C ₆ to C ₄₀ aryl group; Biphenyl; Naphthyl; Anthracenyl; Phenanthracenyl; Pyrenyl; Pyridinyl; Bipyridinyl; Lt; / RTI > is a substituent selected from the group consisting of < RTI ID = 0.0 >

Ar ₃ is a C ₆ to C ₄₀ aryl group or a C ₅ to C ₄₀ heteroaryl group which is unsubstituted or substituted with a C ₁ to C ₂₀ alkyl group or a C ₆ to C ₄₀ aryl group.

The asymmetric anthracene derivative represented by Formula 1 may be represented by Formula 2:

In this formula,

Ar ₁ and Ar ₂ are independently the same or different and are phenyl which is unsubstituted or substituted with a C ₁ to C ₂₀ alkyl group or a C ₆ to C ₄₀ aryl group; Biphenyl; Naphthyl; Anthracenyl; Phenanthracenyl; Pyrenyl; Pyridinyl; Bipyridinyl; Lt; / RTI > is a substituent selected from the group consisting of < RTI ID = 0.0 >

Ar ₄ is a C ₆ to C ₄₀ aryl group or a C ₅ to C ₄₀ heteroaryl group which is unsubstituted or substituted with a C ₁ to C ₂₀ alkyl group or a C ₆ to C ₄₀ aryl group.

According to another aspect of the present invention, there is provided an asymmetric anthracene derivative, wherein each of Ar ₁ and Ar ₂ is independently selected from the following substituents:

According to another aspect of the present invention there is provided a compound characterized in that the Ar ₃ is selected from the group consisting of the following substituents:

According to another aspect of the present invention there is provided a compound characterized in that the asymmetric anthracene derivative is selected from the group consisting of:

According to another aspect of the present invention there is provided a process for preparing an asymmetric anthracene derivative, characterized by comprising the steps of:

- amination reaction of phenylboronic acid bromide with an aryl substituted secondary amine compound to give a tertiary amine compound;

- synthesizing an anthracene derivative by subjecting the obtained tertiary amine compound and 1,5-dibromoanthracene to a first Suzuki coupling reaction; And

- subjecting the resultant anthracene derivative and the aryl-substituted boronic acid compound to a second Suzuki coupling reaction to obtain an asymmetric anthracene derivative.

According to another aspect of the present invention, there is provided another method of producing an asymmetric anthracene derivative, which comprises the steps of:

- 1,5-dibromoanthracene to obtain an anthracene 1,5-diboronic acid;

- subjecting the resultant anthracene 1,5-diboronic acid and 1,4-dibromobenzene to a first Suzuki coupling reaction to obtain an anthracene derivative;

- an amination reaction and a second Suzuki coupling reaction of the obtained anthracene derivative

Step of obtaining an asymmetric anthracene derivative

According to another aspect of the present invention, there is provided an organic electronic device characterized in that the asymmetric anthracene derivative is contained in an organic material layer.

According to another aspect of the present invention, there is provided an organic electronic device, wherein the organic material layer is a hole injection layer, a hole transporting layer, a light emitting layer, a hole blocking layer, or an electron transporting layer.

According to another aspect of the present invention, there is provided an organic electronic device, wherein the organic electronic device is an organic light emitting device, an organic solar cell, an electronic paper, an organophotoreceptor, or an organic transistor.

An anthracene derivative having a symmetrical structure has a disadvantage in that it crystallizes easily at high temperature preservation and high temperature driving. However, the asymmetric 1,5-anthracene derivative according to the present invention improves the problem of crystallization in an organic light emitting device, The efficiency and life span were also greatly improved.

1 is a schematic diagram schematically illustrating the structure of one embodiment of an OLED.
2 is a schematic diagram schematically illustrating the structure of one embodiment of an OLED.
3 is a schematic view schematically showing a structure which does not have a hole blocking layer as an embodiment of an OLED.

Hereinafter, the present invention will be described in detail with reference to the drawings. The terms and words used in the present specification and claims should not be construed in an ordinary or dictionary sense and the inventor can define the concept of a term appropriately to explain its invention in the best way And should be construed in accordance with the principles and meanings and concepts consistent with the technical idea of the present invention.

In addition, the embodiments described in the present specification and the configurations shown in the drawings are merely the most preferred embodiments of the present invention and do not represent all the technical ideas of the present invention. Therefore, various equivalents It should be understood that water and variations may be present.

According to an aspect of the present invention, there is provided an asymmetric anthracene derivative represented by the following Formula 1:

Formula 1

In this formula,

Ar ₁ and Ar ₂ are independently the same or different and are phenyl which is unsubstituted or substituted with a C ₁ to C ₂₀ alkyl group or a C ₆ to C ₄₀ aryl group; Biphenyl; Naphthyl; Anthracenyl; Phenanthracenyl; Pyrenyl; Pyridinyl; Bipyridinyl; Lt; / RTI > is a substituent selected from the group consisting of < RTI ID = 0.0 >

Ar ₃ is a C ₆ to C ₄₀ aryl group or a C ₅ to C ₄₀ heteroaryl group which is unsubstituted or substituted with a C ₁ to C ₂₀ alkyl group or a C ₆ to C ₄₀ aryl group.

The asymmetric anthracene derivative of Formula 1 may be represented by Formula 2:

(2)

In this formula,

Ar ₁ and Ar ₂ are independently the same or different and are phenyl which is unsubstituted or substituted with a C ₁ to C ₂₀ alkyl group or a C ₆ to C ₄₀ aryl group; Biphenyl; Naphthyl; Anthracenyl; Phenanthracenyl; Pyrenyl; Pyridinyl; Bipyridinyl; Lt; / RTI > is a substituent selected from the group consisting of < RTI ID = 0.0 >

Ar ₄ is a C ₆ to C ₄₀ aryl group or a C ₅ to C ₄₀ heteroaryl group which is unsubstituted or substituted with a C ₁ to C ₂₀ alkyl group or a C ₆ to C ₄₀ aryl group.

Preferably, Ar ₁ and Ar ₂ may each independently be selected from the following substituents:

Preferably, Ar ₃ and Ar ₄ each independently may be selected from the following substituents, and EMS 1 to EMS 60 are used as reference symbols for identifying substituents of Ar ₃ and Ar _{4 in} the following description:

More preferably, the asymmetric anthracene derivative according to the present invention may be a compound selected from the following group, and L-1 to L-12 are used as reference symbols for identifying an asymmetric anthracene derivative in the following description.

Among the substituents used in the present invention, the alkyl group is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, more preferably a linear or branched alkyl group having 1 to 12 carbon atoms, and a straight-chain Or branched alkyl groups are most preferred. Examples of such unsubstituted alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, pentyl, isoamyl and hexyl. At least one hydrogen atom contained in the alkyl group may be substituted with at least one substituent selected from the group consisting of a halogen atom, a hydroxy group, -SH, a nitro group, a cyano group, a substituted or unsubstituted amino group (-NH ₂ , -NH (R) ''), R 'and R "are independently alkyl group having 1 to 10 carbon atoms with each other Im), an amidino group, hydrazine, hydrazone or jongi carboxyl group, an alkyl group of a sulfonic acid group, phosphoric acid _{group, C 1 -C 20, C 1} -C _A C ₁ -C ₂₀ alkenyl group, a C ₁ -C ₂₀ alkynyl group, a C ₁ -C ₂₀ heteroalkyl group, a C ₆ -C ₂₀ aryl group, a C ₆ -C ₂₀ arylalkyl group , A C ₆ -C ₂₀ heteroaryl group, or a C ₆ -C ₂₀ heteroarylalkyl group.

Among the substituent groups used in the present invention, the aryl group is used alone or in combination to mean a carbocyclic aromatic system having 6 to 40 carbon atoms including at least one ring, which rings may be attached or fused together by a pendant method. The term aryl includes aromatic radicals such as phenyl, naphthyl, tetrahydronaphthyl, indan, and biphenyl. More preferably phenyl. At least one hydrogen atom in the aryl group may be substituted with the same substituent as in the case of the alkyl group.

Among the substituent groups used in the present invention, the heteroaryl group is a monovalent monocyclic group having 5 to 40 ring atoms having 1, 2 or 3 hetero atoms selected from N, O or S and the remaining ring atoms being C Or an acyclic aromatic radical. The term also refers to monovalent monocyclic or bicyclic aromatic radicals in which the heteroatoms in the ring are oxidized or tanned to form, for example, N-oxides or quaternary salts. Representative examples include thienyl, benzothienyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, quinolinyl, quinoxalinyl, imidazolyl, furanyl, benzofuranyl, thiazolyl, isoxazoline, Benzimidazolyl, benzimidazolyl, benzimidazolyl, triazolyl, pyrazolyl, pyrrolyl, indolyl, 2-pyridonyl, N-alkyl-2-pyridonyl, pyridazinonyl, pyridazinonyl, , Oxazolonyl, and the corresponding N-oxides (e.g., pyridyl N-oxide, quinolinyl N-oxide), quaternary salts thereof, and the like. At least one hydrogen atom in the heteroaryl group may be substituted with the same substituent as the alkyl group.

The asymmetric anthracene derivative according to the present invention can emit light by receiving energy generated by recombination of electrons and electrons.

According to one aspect of the present invention, an asymmetric anthracene derivative can be prepared by a method comprising the steps of:

- amidating an aryl-substituted boronic acid derivative with an aryl-substituted secondary amine compound (Formula A) to obtain a tertiary amine compound (Formula B);

- a first Suzuki coupling reaction of the obtained tertiary amine compound (Formula B) with 1,5-dibromoanthracene (Formula C) to obtain an anthracene derivative (Formula D); And

- a second Suzuki coupling reaction of the obtained anthracene derivative (Formula D) with an aryl-substituted boronic acid (Formula E) to obtain an asymmetric anthracene derivative.

The process can be illustrated by the following scheme:

Scheme 1

The asymmetric anthracene derivatives according to the present invention can be prepared by other methods including the following steps:

- 1,5-dibromoanthracene to obtain an anthracene 1,5-diboronic acid;

- subjecting the resultant anthracene 1,5-diboronic acid and 1,4-dibromobenzene to a first Suzuki coupling reaction to obtain an anthracene derivative; And

- an amination reaction and a second Suzuki coupling reaction of the obtained anthracene derivative To obtain an asymmetric anthracene derivative.

Concretely, the amination reaction using the obtained anthracene derivative and the second Suzuki coupling reaction can be classified by the following two methods.

First, when the amination reaction first proceeds, and thereafter the second Suzuki coupling reaction proceeds, the asymmetric anthracene derivative according to the present invention can be prepared by a process comprising the following steps:

- 1,5-dibromoanthracene (Formula C) to obtain an anthracene 1,5-diboronic acid (Formula F);

A first Suzuki coupling reaction of the obtained anthracene 1,5-diboronic acid (Formula F) with 1,4-dibromobenzene (Formula G) to obtain an anthracene derivative (Formula H);

- obtaining an anthracene derivative (formula (I)) by subjecting the obtained anthracene derivative (Formula H) to an amination reaction with an aryl-substituted secondary amine compound (Formula A); And

- a second Suzuki coupling reaction of the obtained anthracene derivative (I) with an aryl-substituted boronic acid derivative (E) to obtain an asymmetric anthracene derivative.

The process can be illustrated by the following scheme:

Scheme 2

Secondly, when the second Suzuki coupling reaction proceeds first and then the amination reaction proceeds, the asymmetric anthracene derivative according to the present invention can be prepared by other methods including the following steps:

- 1,5-dibromoanthracene derivative (Formula C) to obtain an anthracene 1,5-diboronic acid (Formula F);

A first Suzuki coupling reaction of the obtained anthracene 1,5-diboronic acid (Formula F) with 1,4-dibromobenzene (Formula G) to obtain an anthracene derivative (Formula H);

A second Suzuki coupling reaction of the obtained anthracene derivative (Formula H) with an aryl-substituted boronic acid compound (Formula E) to obtain an anthracene derivative (Formula J); And

- An amination reaction of the obtained anthracene derivative (Formula J) with an aryl-substituted secondary amine compound (Formula A) to obtain an asymmetric anthracene derivative.

The process can be illustrated by the following scheme 3:

Scheme 3

The organic light emitting device of the present invention includes a first electrode, a second electrode, and one or more organic layers disposed between the electrodes, wherein at least one layer of the organic layer includes an asymmetric anthracene derivative according to the present invention .

The organic layer in the organic light emitting device of the present invention may have a single-layer structure of one layer, and one embodiment of such a structure is shown in FIG. 1, a structure in which a cathode 02 is stacked on a substrate 01, a light emitting layer 06 containing an asymmetric anthracene derivative according to the present invention is stacked thereon, and a cathode 03 is stacked thereon .

The organic layer in the organic light emitting device of the present invention may have a multilayer structure of two or more layers, and an exemplary embodiment of such a structure is shown in FIGS. As shown in FIG. 2, the multilayer structure includes a substrate 01, an anode 02, a hole injection layer 04, a hole transport layer 05, an electroluminescence layer 06, (Hole Blocking Layer) 07, an electron transport layer 08, and a cathode 03 may be sequentially stacked in a downward direction, but this is for illustrative purposes only, But is not limited thereto. Alternatively, as shown in FIG. 3, the organic material layer may have no hole blocking layer and may be composed of the hole injecting layer 04, the hole transporting layer 05, the light emitting layer 06, and the electron transporting layer 08. In such a multilayer structure, the asymmetric anthracene derivative according to the present invention can be used for a hole injecting layer, a hole transporting layer, and a light emitting layer. More preferably, the asymmetric anthracene derivative according to the present invention is used in the light emitting layer.

The organic light emitting device of the present invention can be manufactured by a conventional method and material for manufacturing an organic light emitting device, except that the organic light emitting device includes an asymmetric anthracene derivative of the present invention in one or more organic material layers.

The organic material layer may be formed into a smaller number of layers by a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer instead of vapor deposition using various polymer materials can do.

The anode material used in the organic light emitting device of the present invention is preferably a material having a large work function so that injection of holes into the organic material layer can be smoothly performed. Specific examples thereof include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), titanium oxide (TiO), and indium zinc oxide (IZO); ZnO: Al or SnO _2: a combination of a metal and an oxide such as Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline.

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

The hole injecting material used in the organic light emitting device of the present invention is a material capable of injecting holes from the anode well at a low voltage. The highest occupied molecular orbital (HOMO) of the hole injecting material is a function of the work function of the anode material, HOMO. It is also preferable to use a material having a surface adhesion with the anode and a planarizing ability capable of alleviating the surface roughness of the anode. And a material having HOMO and LUMO values larger than the bandgap of the light emitting layer is preferable. Materials having high chemical stability and thermal stability are also desirable. Specific examples thereof include metal porphyrine, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene-based organic materials, quinacridone-based organic materials, perylene-based organic materials, Quinone, polyaniline and polythiophene-based conductive polymers, but are not limited thereto.

The hole transporting material used in the organic light emitting device of the present invention is a material capable of transporting holes from the anode or the hole injection layer to the light emitting layer, and is preferably a material having high hole mobility. A material having HOMO and LUMO values larger than the bandgap of the light emitting layer is suitable. Materials with high chemical stability and thermal stability are also suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion together, but are not limited thereto.

As the hole blocking layer material used in the organic light emitting device of the present invention, a material larger than the HOMO value of luminescence is suitable. Materials with high chemical stability and thermal stability are also suitable. Specifically, TPBi and BCP are mainly used, and CBP, PBD, PTCBI, BPhen, and the like can be used, but not limited thereto.

The electron transporting material used in the organic light emitting device of the present invention is a material capable of transferring electrons from the cathode well into the light emitting layer, and is preferably a material having high mobility to electrons. Materials with high chemical stability and thermal stability are also suitable. Specific examples include an Al complex of 8-hydroxyquinoline; Complexes containing Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited thereto.

The organic light emitting device according to the present invention may be formed by depositing a metal or a conductive metal oxide on the substrate or a metal oxide having conductivity by using physical vapor deposition (PVD) such as sputtering or e-beam evaporation An anode is formed by depositing an alloy on the anode, and an organic material layer including a hole injecting layer, a hole transporting layer, a light emitting layer, a hole blocking layer and an electron transporting layer is formed thereon, and then a substance usable as a cathode is deposited thereon . In addition to such a 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 light emitting device according to the present invention may be a front emission type, a back emission type, or a both-sided emission type, depending on the material used.

The asymmetric anthracene derivative compound according to the present invention may be used in an organic electronic device such as an organic solar cell (OSC), an illumination OLED, a flexible OLED, an organic photoconductor (OPC) or an organic transistor (OTFT) And can act on a principle similar to that of an organic light emitting device.

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

<Preparation of Anthracene Derivative>

Example  1-1: N- (4- (5- ( Biphenyl 4 Yl) anthracene-1-yl) Phenyl ) -N- Phenylbiphenyl -4-amine (L-1)

(1) Step 1: Substitution reaction

30 mL (75 mmol) of n-butyl lithium ethyl ether was added to a solution of 1,5-dibromoanthracene (Formula C, 29.94 mmol) in anhydrous ether (100 mL) at -78 ° C. The resulting mixture was stirred at ambient temperature for 3 hours, cooled to -78 &lt; 0 &gt; C and triethyl borate (144 mmol) was added. After stirring for 8 hours, 2N aqueous HCl solution was added to the mixture. After stirring for 1 hour, the solid was filtered, washed several times with ether, and recrystallized from ethyl acetate to obtain anthracene-1,5-diboronic acid (Formula F). (Yield: 31%) MS (EI) (C 14 H 12 B 2 O 4 calculated 265.86, found 266)

(2) Second step: First Suzuki coupling reaction

(F) (10 mmol), 1,4-dibromobenzene (G, 25 mmol) and Pd (PPh ₃ ) ₄ (0.5 mmol) obtained in the first step, After 20 mL of toluene was dissolved, 20 mL of ₂ M K ₂ CO ₃ aqueous solution was added, and the mixture was refluxed for 10 hours. Extraction with dichloromethane followed by removal of the solvent followed by column purification yielded 1,5-bis (4-bromophenyl) anthracene. (Yield: 68%), MS (EI) (C ₂₆ H ₁₆ Br ₂ calculated: 488.21, found 488)

(3) Third step: Second Suzuki coupling reaction

Pd (PPh ₃ ) ₄ (0.5 mmol), phenylboronic acid (12 mmol), and 1,5-bis (4-bromophenyl) anthracene (Formula H, 10 mmol) obtained in the second step were dissolved in 50 mL of toluene , And 50 mL of 2M K ₂ CO ₃ aqueous solution was added thereto and refluxed for 10 hours. Extraction with dichloromethane followed by removal of the solvent followed by column purification yielded 1- (biphenyl-4-yl) -5- (4-bromophenyl) anthracene (Formula J). (Yield: 63%), MS (EI ) (C 32 H 21 Br Calculated: 485.41, Found: 485)

(4) Step 4: Amination reaction

(10 mmol) of 1- (biphenyl-4-yl) -5- (4-bromophenyl) anthracene (Formula J, 10 mmol) and N-phenylbiphenyl- ), Pd₂(dba)₃(0.4 g), P- (t-Bu)₃(0.13 g), NaOBu^t (3.3 g) was dissolved in toluene (50 mL) under nitrogen atmosphere, followed by stirring under reflux for 24 hours. Extraction with dichloromethane and removal of the solvent followed by column purification gave the title compound. (Yield: 71%), MS (EI) (C₅₀H₃₅N calculated: 649.82, found: 650), and of compound L-1^OneH-NMR was 8.33 to 8.29, 7.92 to 7.86, 7.65 to 7.37, 7.26 to 7.16, 6.85 to 6.78, and 6.73 to 6.60.

Example  1-2: N- (4- (5- ( Biphenyl Yl) anthracene-1-yl) Phenyl ) -N- (naphthalen-1-yl) naphthalene-1 -amine (L-2)

(1) Step 1: Substitution reaction

Anthracene-1,5-diboronic acid (Formula F) was obtained according to the first step of Example 1.

(2) Second step: First Suzuki coupling reaction

(Formula G, 25 mmol) and Pd (PPh ₃ ) ₄ (0.5 mmol) obtained in the first step were dissolved in 20 mL of toluene , 20 mL of ₂ M K ₂ CO ₃ aqueous solution was added, and the mixture was refluxed for 10 hours. Extraction with dichloromethane, removal of the solvent, and column purification yielded 1,5-bis (3-bromophenyl) anthracene (Formula H). (Yield: 49%), MS (EI) (C ₂₆ H ₁₆ Br ₂ calculated: 488.21, found 488)

(3) Third step: Second Suzuki coupling reaction

(Formula H, 10 mmol), phenylboronic acid (E, 12 mmol) and Pd (PPh ₃ ) ₄ (0.5 mmol) obtained in the second step were dissolved in 50 mL of toluene , 50 mL of ₂ M K ₂ CO ₃ aqueous solution was added, and the mixture was refluxed for 10 hours. After extraction with dichloromethane and removal of the solvent, column purification was performed to give 1- (biphenyl-3-yl) -5- (3-bromophenyl) anthracene (Formula J). (Yield: 42%), MS (EI ) (C 32 H 21 Br Calculated: 485.41, Found: 485).

(4) Step 4: Amination reaction

(Formula J, 10 mmol) and dynaphthalen-1-ylamine (formula (A), 12 mmol) obtained in the third step were added to a solution of 1- (biphenyl- , Pd ₂ (dba) ₃ (0.4 g), P- (t-Bu) ₃ (0.13 g) and NaOBu ^t (3.3 g) were dissolved in 50 mL of toluene under nitrogen atmosphere and stirred under reflux for 24 hours. Extraction with dichloromethane and removal of the solvent followed by column purification gave the title compound. ¹ H-NMR of Compound L-2 was 8.35 to 8.29, 8.11 to 7.99, 7.91 to 7.86, 7.65 to 7.65, and 1.35 g (yield: 62%). MS (EI) (C ₅₂ H ₃₅ N calculated 673.84, 7.34, 7.27 to 7.22, 7.01 to 6.96, and 6.72 to 6.66.

Example  1-3: N- (4- (5- ( Biphenyl Yl) anthracene-1-yl) Phenyl ) -N- (naphthalen-2-yl) naphthalen-1 -amine <L-3>

(4-bromophenyl) anthracene (Formula J, 10 mmol) and dynaphthalen-2-ylamine (compound of Formula A, 12 mmol), Pd ₂ (dba) ₃ (0.4 g), P- (t-Bu) ₃ (0.13 g), NaOBu ^t (3.3 g) was dissolved in toluene (50 mL), and the mixture was refluxed with stirring for 24 hours. Extraction with dichloromethane and removal of the solvent followed by column purification gave the title compound. (Yield: 48%), MS (EI ) (C 52 H 35 N calculated: 673.84, found: 674), ¹ H-NMR of Compound L-3 is 8.35 ~ 8.29, 8.10 ~ 7.99, 7.90 ~ 7.74, 7.65 ~ 7.32, 7.28 to 7.23, 7.01 to 6.96, and 6.73 to 6.68.

Example  1-4: 3- (5- ( Biphenyl Yl) anthracene-1-yl) -N, N- die -m- Tolylaniline  &Lt; L-4 >

(1) Preparation of 3- (5- (3-bromophenyl) anthracen-1-yl) -N, N-di-m-tolylaniline

Bis (3-bromophenyl) anthracene (Formula H, 10 mmol) and 3,3'-dimethyldiphenylamine (12 mmol) prepared in accordance with steps 1-2 of Example 1-2, , Pd ₂ (dba) ₃ (0.4 g), P- (t-Bu) ₃ (0.13 g), NaOBu ^t (3.3 g) was dissolved in 100 mL of toluene under a nitrogen atmosphere, followed by stirring under reflux for 24 hours. Extraction with dichloromethane followed by removal of the solvent followed by column purification gave 3- (5- (3-bromophenyl) anthracen-1-yl) -N, N-di-m- tolylaniline . (Yield: 58%), MS (EI) (C ₄₀ H ₃₀ BrN calculated: 604.58, found: 605).

(2) Preparation of 3- (5-biphenyl-3-yl) anthracene-1-yl) -N, N-di-m-tolylaniline

(I) (10 mmol) and phenylboronic acid (E, 12 mmol) were added to a solution of 3- (5- (3-bromophenyl) anthracen- ) And Pd (PPh ₃ ) ₄ (0.5 mmol) were dissolved in 60 mL of toluene, 60 mL of ₂ M K ₂ CO ₃ aqueous solution was added, and the mixture was refluxed for 10 hours. Extraction with dichloromethane and removal of the solvent followed by column purification gave the title compound. (Yield: 64%), MS (EI) (calculated for C ₄₆ H ₃₅ N: 601.78, found 602).

Example  1-5: 3- methyl -N- (3- (5- (3- (naphthalen-2-yl) Phenyl ) Anthracene-1-yl) Phenyl ) -N-m- Toll Preparation of Reilaniline < L-5 >

N, N-di-m-tolylaniline (formula I, 10 mmol) prepared in the same manner as in Example 1-4 and naphthalene 2-yl boronic acid (formula E, 12 mmol), Pd ( PPh 3) after the dissolved in toluene _{60mL 4 (0.5 mmol), 2M} K 2 CO 3 60 mL of an aqueous solution was added and the mixture was refluxed for 10 hours. Extraction with dichloromethane and removal of the solvent followed by column purification gave the title compound. (Yield: 41%), MS (EI ) (C 50 H 37 N calculated: 651.84, found: 652).

Example  1-6: 3- methyl -N- (3- (5- (3- (naphthalen-1-yl) Phenyl ) Anthracene-1-yl) Phenyl ) -N-m- Tolylaniline  &Lt; L-6 >

N, N-di-m-tolylaniline (formula I, 10 mmol) prepared in the same manner as in Example 1-4 and naphthalene -1-ylboronic acid (Formula E, 12 mmol) and Pd (PPh ₃ ) ₄ (0.5 mmol) were dissolved in 60 mL of toluene, 60 mL of ₂ M K ₂ CO ₃ aqueous solution was added and the mixture was refluxed for 10 hours. Extraction with dichloromethane and removal of the solvent followed by column purification gave the title compound. (Yield: 47%), MS (EI ) (C 50 H 37 N calculated: 651.84, found: 652).

Example  1-7: N- (3- (5- ( Biphenyl Yl) anthracene-1-yl) Phenyl ) -N-p- Tolyl Biphenyl -4-amine < L-7 >

(Biphenyl-3-yl) -5- (3-bromophenyl) anthracene (Formula J, 10 mmol) and Np-tolylbiphenyl- -Amine (formula A, 12 mmol), Pd ₂ (dba) ₃ (0.4 g), P- (t-Bu) ₃ (0.13 g), NaOBu ^t (3.3 g) were dissolved in 50 mL of toluene, and the mixture was refluxed and stirred for 24 hours. Extraction with dichloromethane and removal of the solvent followed by column purification gave the title compound. (Yield: 38%), MS (EI) (calculated for C ₅₁ H ₃₇ N, 663.85, found 664).

Example  1-8: N- (3- (5- ( Biphenyl Yl) anthracene-1-yl) Phenyl ) -N- Phenyl naphthalene -1-amine < L-8 >

(Biphenyl-3-yl) -5- (3-bromophenyl) anthracene (Formula J, 10 mmol) prepared in accordance with Steps 1-3 of Example 1-2 and N-phenylnaphthalene 1-amine (formula _{A, 12mmol), Pd 2 (} dba) 3 (0.4g), P- (t-Bu) 3 (0.13g), NaOBu t (3.3 g) were dissolved in 50 mL of toluene, and the mixture was refluxed and stirred for 24 hours. Extraction with dichloromethane and removal of the solvent followed by column purification gave the title compound. (Yield: 49%), MS (EI) (C ₄₈ H ₃₃ N calculated: 623.78, found 624).

Example  1-9: N- (3- (5- ( Biphenyl Yl) anthracene-1-yl) Phenyl ) -N- (naphthalen-1-yl) naphthalen-1 -amine <L-9>

(B) was prepared by reacting 1- (biphenyl-3-yl) -5- (3-bromophenyl) anthracene (Formula J, 10 mmol) and dinaphthalene- (12 mmol), Pd ₂ (dba) ₃ (0.4 g), P- (t-Bu) ₃ (0.13 g), NaOBu ^t (3.3 g) were dissolved in 50 mL of toluene, and the mixture was refluxed and stirred for 24 hours. Extraction with dichloromethane and removal of the solvent followed by column purification gave the title compound. (Yield: 42%), MS (EI) (C ₅₂ H ₃₅ N calculated: 673.84, found 674).

Example  1-10: 4- (5- (Naphthalen-1-yl) anthracen-1-yl) -N, N- Diphenyl aniline  Production of <L-10>

As described in Scheme 1, 1,5-dibromo-anthracene (Formula C, 10mmol) and 4- (diphenylamino) phenylboronic acid (Formula B, 12mmol), Pd (PPh 3) 4 (0.5mmol) in toluene 60 mL of 2M K ₂ CO ₃ aqueous solution was added, and the mixture was refluxed for 10 hours. Extraction with dichloromethane, removal of the solvent, and column purification. Thus obtained 4- (5-bromo-anthracene-1-yl) -N, N- diphenyl-aniline (formula D, 10mmol) and naphthalene-1-Daily acid (Formula E, 12mmol), Pd (PPh 3) 4 ( 0.5 mmol) were dissolved in 60 mL of toluene, 60 mL of ₂ M K ₂ CO ₃ aqueous solution was added, and the mixture was refluxed for 10 hours. Extraction with dichloromethane and removal of the solvent followed by column purification gave the title compound. (Yield: 53%), MS (EI) (C ₄₂ H ₂₉ N calculated: 547.69, found 548).

Example  1-11: 4- (5- (Naphthalen-2-yl) anthracene-1-yl) -N, N- Diphenyl aniline  Production of <L-11>

(Formula D, 10 mmol) and naphthalene-2-ylboronic acid (Formula E, 10 mmol) prepared in the same manner as in Example 1-10 and 4- (5-bromoanthracen- And Pd (PPh ₃ ) ₄ (0.5 mmol) were dissolved in 60 mL of toluene, 60 mL of ₂ M K ₂ CO ₃ aqueous solution was added, and the mixture was refluxed for 10 hours. Extraction with dichloromethane and removal of the solvent followed by column purification gave the title compound. (Yield: 38%), MS (EI) (C ₄₂ H ₂₉ N calculated: 547.69, found 548).

Example  1-12: 4- (5- ( Phenanthrene -9-yl) anthracene-1-yl) -N, N- Of diphenyl aniline < L-12 >  Produce

(D, 10mmol) and phenanthrene-9-ylboronic acid (E in the formula (E)) prepared in the same manner as in Example 1-10 and 4- (5-bromoanthracen- , 12 mmol) and Pd (PPh ₃ ) ₄ (0.5 mmol) were dissolved in 60 mL of toluene, 60 mL of ₂ M K ₂ CO ₃ aqueous solution was added, and the mixture was refluxed for 10 hours. Extraction with dichloromethane and removal of the solvent followed by column purification gave the title compound. (Yield: 40%), MS (EI) (calculated for C ₄₆ H ₃₁ N: 597.75, found 598).

Comparative Example  1-1: 4- (10- (3 ', 5'- Diphenyl biphenyl Yl) anthracene-9-yl) -N, N-diphenyl aniline ( TATa )

Suzuki coupling and amination reactions were carried out according to the method described in Organic Electronics 10 (2009) 822-833 (10-2009-0126978), and pure 4- (10- (3 ', 5'-diphenylbiphenyl-4-yl) anthracene-9-yl) -N, N-diphenyl aniline (TATa).

Comparative Example  1-2: 2- methyl -9,10- die  (2- Naphthyl ) Anthracene ( MADN )

2-methyl-9,10-di (2-naphthyl) anthracene (MADN), a compound commonly used in the art for organic electronic devices, is commercially available from Luminescence Technology Co., Ltd. of Taiwan. (Lumtect).

&Lt; Production of organic light emitting device >

Using the compounds provided in Examples 1-1 to 1-3 and Comparative Examples 1-1 and 1-2 according to the present invention, an organic light emitting device was prepared as follows.

Example  2-1: ITO  / 2- TNATA  / NPB  / Example  1-1 compound / Alq ₃  / LiF  / Al

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

On this ITO transparent electrode, 2-TNATA (4,4 ', 4 "-tris (N- (2-naphthyl) -N-phenylamino) -triphenylamine as a hole injection layer, 50 nm After vacuum deposition, NPB (N, N'-di-1-naphthyl-N, N'-diphenylbenzidine, 30 nm in the following formula) was deposited as a hole transporting layer, The prepared compound was vacuum deposited to a thickness of 30 nm, and an Alq ₃ compound (tris (8-hydroxyquinolinato) aluminum, see the following chemical formula) was vacuum deposited as an electron transfer layer to a thickness of 30 nm. And Al 200 nm were deposited to form a cathode.

In this process, the deposition rate of the organic material was maintained at 1 Å / sec, the deposition rate of lithium fluoride was 0.2 Å / sec, and the deposition rate of aluminum was 2 to 3 Å / sec. Table 1 shows the electroluminescence characteristics of the organic light-emitting device prepared above.

Example  2-2: ITO  / 2- TNATA  / NPB  / Example  1-2 compound / Alq ₃  / LiF  / Al

The organic luminescent device was fabricated in the same manner as in Example 2-1 except that the compound of Example 1-2 was used as the luminescent layer, and the electric luminescent properties thereof were shown in Table 1.

Example  2-3: ITO  / 2- TNATA  / NPB  / Example  1-3 compounds / Alq ₃  / LiF  / Al

The organic luminescent device was fabricated in the same manner as in Example 2-1 except that the compound of Example 1-3 was used as the luminescent layer, and the electric luminescent properties thereof were shown in Table 1. [

Comparative Example  2-1: ITO  / 2- TNATA  / NPB  / TATa  / Alq ₃  / LiF  / Al

An organic light emitting device was fabricated in the same manner as in Example 2-1 except that the MADN compound of Comparative Example 1-1 was used as the light emitting layer.

Comparative Example  2-2: ITO  / 2- TNATA  / NPB  / MADN  / Alq ₃  / LiF  / Al

An organic light emitting device was fabricated in the same manner as in Example 2-1, except that the TATa compound of Comparative Example 1-2 was used as the light emitting layer, and the electrical luminescent characteristics thereof were shown in Table 1.

Current density
(mA / cm ² ) Color coordinates
(x, y) efficiency
(cd / A) life span
(hrs) Example 2-1 10 (0.156, 0.088) 5.40 392 Example 2-1 10 (0.144, 0.030) 6.72 532 Example 2-3 10 (0.149, 0.177) 5.75 510 Comparative Example 2-1 10 (0.148, 0.175) 5.32 386 Comparative Example 2-2 10 (0.172, 0.139) 2.53 322 The current density was calculated in terms of mA / cm ² , the color coordinate system was CIE 1931 (x, y), the efficiency was calculated using luminance and current density, the unit was cd / A, the lifetime was 10,00nit and the unit was hrs.

As can be seen from the results of Table 1, the OLED device manufactured using the compound of Formula 1 or 2 according to the present invention for the light emitting layer emits light in the deep blue and blue regions, and the color coordinates, luminous efficiency, I could confirm. In particular, in Examples 2-1 to 2-3 using the asymmetric anthracene compound according to the present invention, the region of the emission wavelength showed a darker blue color than the anthracene derivatives of Comparative Examples 2-1 and 2-2, And improved lifetime characteristics.

The OLED device using the asymmetric anthracene derivative of the present invention has a high luminous efficiency and a long life, and blue light emission is obtained. Therefore, it is highly industrially useful as an OLED having high practicality. The OLED of the present invention can be suitably used for a light source such as a flat panel display, a planar light emitting body, a light emitting body of a surface emitting OLED for illumination, a flexible light emitting body, a copying machine, a printer, an LCD backlight or a meter, a display plate,

Claims (10)

delete delete delete delete An asymmetric anthracene derivative, characterized in that it is selected from the group consisting of:

delete A process for producing an asymmetric anthracene derivative according to claim 5, comprising the steps of:
- 1,5-dibromoanthracene to obtain an anthracene 1,5-diboronic acid;
- subjecting the resultant anthracene 1,5-diboronic acid and 1,4-dibromobenzene to a first Suzuki coupling reaction to obtain an anthracene derivative; And
- subjecting the obtained anthracene derivative to an amination reaction and a second Suzuki coupling reaction to obtain an asymmetric anthracene derivative. An organic electronic device characterized by comprising an asymmetric anthracene derivative according to claim 5 in an organic material layer. 9. The method of claim 8,
Wherein the organic material layer is a hole injection layer, a hole transporting layer, a light emitting layer, a hole blocking layer or an electron transporting layer. 10. The method of claim 9,
Wherein the organic electronic device is an organic light emitting device, an organic solar cell, an electronic paper, an organophotoreceptor, or an organic transistor.

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