KR20100137983A - New anthracene derivatives, preparation method thereof and organic electronic device using the same - Google Patents

Abstract

PURPOSE: An anthracene derivative is provided to act as hole injection, hole transport, electron injection, electron transport, or a luminescent material, especially a luminous host alone, preferably a green host, and to ensure excellent efficiency, driving voltage and stability. CONSTITUTION: An anthracene derivative is represented by chemical formula 1. In chemical formula 1, Q is C6~C20 arylene group, R1, R2 and X are independently substituted or unsubstituted C6~C20 aryl group substituted with one or more selected from the group consisting of halogen, CN, NO2, C1~C20 alkyl group, C1~C20 alkoxy group, C1~C20 alkylamine group, C6~C20 arylamine group, C1~C20 alkyl thiophene group, C6~C20 aryl thiophene group, C2~C20 alkenyl group, C2~C20 alkynyl group, C3~C20 cycloalkyl group, C6~C20 aryl group, -BRR', -SiRR'R", -GeRR'R"; and C5~C20 heterocyclic group.

Description

Novel anthracene derivative, preparation method thereof, and organic electronic device using the same {NEW ANTHRACENE DERIVATIVES, PREPARATION METHOD THEREOF AND ORGANIC ELECTRONIC DEVICE USING THE SAME}

The present invention relates to a novel anthracene derivative, a preparation method thereof and an organic electronic device using the same.

The organic electronic device refers to a device that requires charge exchange between an electrode and an organic material using holes and / or electrons. The organic electronic device can be divided into two types according to the operation principle. First, an exciton is formed in the organic layer by photons introduced into the device from an external light source, and the exciton is separated into electrons and holes, and these electrons and holes are transferred to different electrodes to be used as current sources (voltage sources). It is an electronic device of the form. The second type is an electronic device in which holes and electrons are injected into an organic semiconductor forming an interface with the electrodes by applying voltage or current to two or more electrodes, and operated by the injected electrons and holes.

Examples of the organic electronic device include an organic light emitting device, an organic solar cell, an organic photoconductor (OPC), an organic transistor, etc., all of which are used to inject or transport holes, inject or transport materials, or emit light for driving the device. It needs a substance.

Hereinafter, the organic light emitting device will be described in detail. However, in the organic electronic devices, a hole injection or transport material, an electron injection or transport material, or a light emitting material functions on a similar principle.

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 light emitting device using an organic light emitting phenomenon usually has a structure including an anode, a cathode and an organic material layer therebetween. The organic material layer is often made of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light emitting 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. When the voltage is applied between the two electrodes in the structure of the organic light emitting diode, holes are injected into the organic material layer at the anode and electrons are injected into the organic material layer, and excitons are formed when the injected holes and electrons meet. When it falls back to the ground, it glows. Such organic light emitting diodes are known to have characteristics such as self-luminous, high brightness, high efficiency, low driving voltage, wide viewing angle, high contrast, and high speed response.

Materials used as the organic material layer in the organic light emitting 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 according to molecular weight, and may be classified into a fluorescent material derived from a singlet excited state of electrons and a phosphorescent material derived from a triplet excited state of electrons according to a light emitting mechanism. . In addition, the light emitting materials include blue, green, and red light emitting materials, and yellow and orange light emitting materials required to realize better natural colors, depending on the color of light emitted.

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 the 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 shifts to the wavelength of the dopant, light having a desired wavelength can be obtained according to the type of dopant to be used.

In order for the organic light emitting device to fully exhibit the above-mentioned excellent features, it is supported that 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 it should be preceded, the development of a stable and efficient organic material layer for an organic light emitting device has not been made yet. Therefore, the development of new materials continues to be demanded, and the necessity of such material development is the same in other organic electronic devices described above.

The present invention is to solve the problems of the prior art as described above, an object of the present invention is to provide a novel anthracene derivative, a preparation method thereof and an organic electronic device using the same.

One aspect of the present invention for achieving the above object provides an anthracene derivative represented by the following formula (1).

[Formula 1]

In Chemical Formula 1,

Q is an arylene group of C ₆ ~ C ₂₀ ,

R1, R2 and X are each, independently, a halogen, CN, NO _2, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkyl amine group, C ₆ ~ C ₂₀ of the Arylamine group, C ₁ to C ₂₀ alkyl thiophene group, C ₆ to C ₂₀ aryl thiophene group, C ₂ to C ₂₀ alkenyl group, C ₂ to C ₂₀ alkynyl group, C ₃ to C ₂₀ A cycloalkyl group, a C ₆ -C ₂₀ aryl group, -BRR ', -SiRR'R ", -GeRR'R" and a substituted or unsubstituted C ₅ -C ₂₀ heterocyclic group substituted with one or more groups selected from the group Or unsubstituted C ₆ -C ₂₀ aryl group; or

Halogen, CN, NO ₂ , C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkylamine group, C ₆ ~ C ₂₀ arylamine group, C ₁ ~ C ₂₀ alkylthio group, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C ₂₀ alkynyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ aryl group, -BRR ', -SiRR'R "of, and -GeRR'R "and substituted or unsubstituted C ₅ ~ C ₂₀ heterocyclic group of the or unsubstituted C ₅ ~ C ₂₀ substituted with one or more groups selected from the group consisting of a heterocyclic ring,

Wherein, R, R 'and R "are each independently, hydrogen, C ₁ ~ C ₂₀ alkyl group, C cycloalkyl group of ₃ ~ C _20, C aryl group of ₆ ~ C ₂₀ or C ₅ ~ heterocycle of the C ₂₀ Qi.

The second aspect of the present invention for achieving the above object provides a method for producing an anthracene derivative represented by the formula (1).

A third aspect of the present invention for achieving the above object is an organic electronic device comprising a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode, one of the organic material layer Layer or more provides an organic electronic device, characterized in that it comprises an anthracene derivative represented by the formula (1).

The anthracene derivative according to the present invention may play a role of hole injection, hole transport, electron injection, electron transport, or light emitting material in organic electronic devices including organic light emitting devices, and in particular, serves as a light emitting host, preferably a green host. can do. The organic electronic device according to the present invention exhibits excellent characteristics in terms of efficiency, driving voltage, and stability.

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

One aspect of the present invention relates to an anthracene derivative represented by Chemical Formula 1.

Hereinafter, the substituent of the formula (1) will be described in more detail.

Preferably, in the anthracene derivative represented by Formula 1, Q may be phenylene, naphthylene or biphenylene.

R 1 and R 2 are each independently phenyl; 1-naphthyl; 2-naphthyl; Biphenyl; Triphenyl; 1-tetralinyl; 2-tetralinyl; Stilbenyl; Fluorenyl; Or anthracenyl substituted with diphenyl, biphenyl, 1-naphthyl, 2-naphthyl, anthracenyl, phenyl or naphthyl; Preference is given to phenyl substituted with a group selected from the group consisting of phenylthiophenyl, carbazolyl and diphenylamine.

In addition, X is preferably a C ₆ ~ C ₂₀ aryl group containing 1-naphthyl, 2-naphthyl, biphenyl, a substituted or unsubstituted C ₅ ~ C ₂₀ heterocyclic group.

In addition, X is preferably selected from the group consisting of the following structural formulas.

In the above structural formula, Ar ₁ to Ar ₅ are the same as or different from each other, and each independently phenyl; 1-naphthyl; 2-naphthyl; Biphenyl; Triphenyl; 1-tetralinyl; 2-tetralinyl; Stilbenyl; Fluorenyl; Or anthracenyl substituted with diphenyl, biphenyl, 1-naphthyl, 2-naphthyl, anthracenyl, phenyl or naphthyl; It is preferably a phenyl group substituted with a group selected from the group consisting of phenylthiophenyl, carbazolyl and diphenylamine.

In addition, in the anthracene derivative, X is preferably represented by the following formula (2).

[Formula 2]

In Formula 2, n, p, q and r are 0 or an integer of 1 to 10, p + q ≥ 1,

L ₁ is directly connected; Halogen, CN, NO ₂ , C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkylamine group, C ₆ ~ C ₂₀ arylamine group, C ₁ ~ C ₂₀ alkylthiophene group, C ₆ ~ aryl T of C ₂₀ thiophene group, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ aryl of C ₂₀ alkynyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ of the group, -BRR ', -SiRR'R ", -GeRR'R " and a substituted or unsubstituted C ₅ ~ C ₂₀ by at least one group selected from the group consisting of heterocyclic ring groups is substituted or unsubstituted C ₅ ~ C ₂₀ of Arylene group; Or halogen, CN, NO ₂ , C ₁ -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy group, C ₁ -C ₂₀ alkylamine group, C ₆ -C ₂₀ arylamine group, C ₁ -C ₂₀ the coming of the alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C ₂₀ of the alkynyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ aryl group, -BRR ', -SiRR'R " , -GeRR'R "and a substituted or unsubstituted C ₅ ~ C ₂₀ heterocyclic group unsubstituted or substituted with one or more groups selected from the group consisting of C ₅ ~ C ₂₀ is a heterocyclic group,

L ₂ is an aryl group of C ₅ to C ₂₀ ,

Wherein, R, R 'and R "are each independently, hydrogen, C ₁ ~ C ₂₀ alkyl group, C cycloalkyl group of ₃ ~ C _20, C aryl group of ₆ ~ C ₂₀ or C ₅ ~ heterocycle of the C ₂₀ Gigi,

R ₇ and R ₈ are the same as or different from each other, and each independently hydrogen; halogen; Hydroxyl; Mercapto; Cyano; Nitro; Carbonyl; Carboxyl; Formyl; Substituted or unsubstituted C ₁ -C ₂₀ alkyl; Substituted or unsubstituted C ₂ -C ₁₀ alkenyl; Substituted or unsubstituted C ₂ -C ₇ alkynyl; Substituted or unsubstituted C ₆ -C ₂₀ aryl; Substituted or unsubstituted C ₄ -C ₂₀ heteroaryl; Substituted or unsubstituted C ₃ -C ₇ cycloalkyl, wherein the carbon atoms in the ring may be optionally substituted by oxygen, nitrogen or sulfur atoms; C ₄ -C ₇ cycloalkenyl, wherein the carbon atoms in the ring may be optionally substituted by oxygen, nitrogen or sulfur atoms; Substituted or unsubstituted C ₁ -C ₂₀ alkoxy; Substituted or unsubstituted C ₂ -C ₁₀ alkenyloxy; Substituted or unsubstituted C ₂ -C ₇ alkynyloxy; Substituted or unsubstituted C ₆ -C ₂₀ aryloxy; Substituted or unsubstituted C ₁ -C ₂₀ alkylamine; Substituted or unsubstituted C ₂ -C ₁₀ alkenylamine; Substituted or unsubstituted C ₂ -C ₇ alkynylamine; Substituted or unsubstituted C ₆ -C ₂₀ arylamine; Substituted or unsubstituted C ₇ -C ₂₀ alkylarylamine; Substituted or unsubstituted C ₁ -C ₂₀ alkylsilyl; Substituted or unsubstituted C ₂ -C ₁₀ alkenylsilyl; Substituted or unsubstituted C ₂ -C ₇ alkynylsilyl; Substituted or unsubstituted C ₆ -C ₂₀ arylsilyl; Substituted or unsubstituted C ₇ -C ₂₀ alkylarylsilyl; Substituted or unsubstituted C ₁ -C ₂₀ alkylboranyl; Substituted or unsubstituted C ₂ -C ₁₀ alkenylboranyl; Substituted or unsubstituted C ₂ -C ₇ alkynylboranyl; Substituted or unsubstituted C ₆ -C ₂₀ arylboranyl; Substituted or unsubstituted C ₇ -C ₂₀ alkylarylboranyl; Substituted or unsubstituted C ₁ -C ₂₀ alkylthio; Substituted or unsubstituted C ₂ -C ₁₀ alkenylthio; Substituted or unsubstituted C ₂ -C ₇ alkynylthio; And a substituted or unsubstituted C ₆ -C ₂₀ arylthio group.

Preferably, in Formula 2, R ₇ and R ₈ are the same as or different from each other, and each independently, hydrogen, cyano, nitro, substituted or unsubstituted C ₁ -C ₂₀ alkyl, substituted or unsubstituted C ₂ -C ₁₀ alkenyl, substituted or unsubstituted C ₃ -C ₇ cycloalkyl, substituted or unsubstituted C ₄ -C ₇ cycloalkenyl, substituted or unsubstituted C ₆ -C ₂₀ aryl, substituted or unsubstituted C ₄ -C ₂₀ hetero Aryl, substituted or unsubstituted C ₁ -C ₂₀ alkoxy, substituted or unsubstituted C ₆ -C ₂₀ aryloxy, substituted or unsubstituted C ₁ -C ₂₀ Alkylamines, substituted or unsubstituted C ₆ -C ₂₀ arylamines, substituted or unsubstituted C ₇ -C ₂₀ alkylarylamines, substituted or unsubstituted C ₁ -C ₂₀ alkylsilyl; Substituted or unsubstituted C ₁ -C ₂₀ alkylboranyl, substituted or unsubstituted C ₆ -C ₂₀ arylboranyl, substituted or unsubstituted C ₇ -C ₂₀ alkylarylboranyl, substituted or unsubstituted C ₁ -C ₂₀ alkyl Thio, and substituted or unsubstituted C ₆ -C ₂₀ arylthio groups.

In the present specification, the term "substituted or unsubstituted", unless otherwise specified, halogen, alkyl, alkenyl, alkoxy, aryl, arylalkyl, arylalkenyl, heterocyclic, carbazolyl, flu It is meant to be substituted or unsubstituted with one or more substituents selected from the group consisting of an orenyl group, a nitrile group and an acetylene group, but is not limited thereto.

Specific examples of the compound represented by Formula 1 according to the present invention are shown below, but are not limited thereto.

The second aspect of the present invention relates to a method for preparing an anthracene derivative represented by the formula (1).

Method for producing the anthracene derivative,

1) reacting 1-chloroanthraquinone with boronic acid compound (XQB (OH) ₂ ) to prepare compound (II),

2) reacting compound (II) with a bromo compound (R1-Br or R2-Br) to produce a dialcohol compound (III), and

3) preferably reacting the dialcohol compound (III) with potassium iodide and sodium hypophosphite to produce compound (I).

Scheme 1

In Scheme 1, Q, R1, R2, and X are as defined in Chemical Formula 1.

More specific method for producing an anthracene derivative according to the present invention is described in the Examples, and a person skilled in the art to prepare an anthracene derivative represented by the formula (1) of the present invention only by different starting materials based on the description herein It can be manufactured easily.

The third aspect of the present invention relates to an organic electronic device using the compound of Formula 1.

The organic electronic device of the present invention may be manufactured by a conventional method and material for manufacturing an organic electronic device, except that one or more organic material layers are formed using the above-described compounds.

Hereinafter, an organic light emitting diode will be described.

The compounds of the present invention described above may serve as hole injection, hole transport, electron injection, electron transport, or light emitting materials in the organic light emitting device, and in particular, may not only serve as light emitting materials alone, but also suitable light emitting dopants. Together with a light emitting host, or a suitable light emitting host.

In one exemplary embodiment of the present invention, the organic light emitting diode may have a structure including a first electrode, a second electrode, and an organic material layer disposed therebetween, and the anthracene derivative represented by Chemical Formula 1 according to the present invention described above. It may be prepared using a conventional method and material for manufacturing an organic light emitting device, except that is used in at least one layer of the organic material layer of the organic light emitting device. The structure of the organic light emitting device according to the present invention is illustrated in FIG.

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

The organic material layer may have a 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 by using a variety of polymer materials, and by using a method such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer method, rather than a deposition method. It can be prepared in layers.

As the cathode 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.

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

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

As the hole transport material, a material capable of transporting holes from the anode or the hole injection layer to be transferred to the light emitting layer is suitable. Specific examples thereof include an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together, but are not limited thereto.

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. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole series compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compound; Benzoxazole, benzthiazole and benzimidazole series compounds; Poly (p-phenylenevinylene) (PPV) -based polymers; Spiro compounds; Polyfluorene, rubrene and the like, but are not limited thereto.

As the electron transport material, a material capable of injecting electrons well from the cathode and transferring the electrons to the light emitting layer is suitable. Specific examples 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 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.

The compound according to the present invention may act on a principle similar to that applied to organic light emitting devices in organic electronic devices including organic solar cells, organic photoconductors, organic transistors, and the like.

Hereinafter, preferred examples will be described to aid in understanding the present invention. The following examples are merely to illustrate the invention, but are not intended to limit the scope of the invention.

<Examples>

Example  One Preparation of Compound 1

1. Preparation of Compound 1-1

Dissolve 1-chloroanthraquinone (41.2 mmol, 10.0 g) in 200 mL of THF, and add 4,4,5,5-tetramethyl-2- (4- (10-phenylanthrace-9-yl) phenyl ) -1,3,2-dioxaborane (45.3 mmol, 20.6 g), 50 mL of potassium carbonate 2 M solution, tetrakis (triphenylphosphine) palladium (0)] (1.24) mmol, 1.43 g) was added thereto, and the mixture was refluxed for 19 hours. After the reaction was cooled to room temperature, filtered and washed with water and ethanol several times to give compound 1-1 (21 g, 96%). MS [M] = 536

2. Preparation of Compound 1-2

Bromophenyl (19.1 mmol, 3.0 g) was added to 100 mL of dried THF to dissolve completely, and n -butyllithium (6.2 ml, 2.5 M solution in hexane) was added very slowly under -78 ° C. After 1 hour, Compound 1-1 (9.3 mmol, 5 g) prepared in 1 was added to the reaction. After 30 minutes, the cooling vessel was removed and reacted at room temperature for 3 hours. After the reaction was added NH ₄ Cl aqueous solution and extracted with ethyl ether. The extracted reaction was dried over anhydrous magnesium sulfate and concentrated. A small amount of ethyl ether was added thereto and stirred, followed by stirring with ethanol. Subsequently, the reaction was filtered and dried to give the dialcohol compound 1-2 (4.74 g, 95%). MS [M] = 518 (-H ₂ O form)

3. Preparation of Compound 1

Compound 1-2 (3.6 g, 6.77 mmol), potassium iodide (1.12 g, 6.77 mmol) and sodium hypophosphite (7.18 g, 67.7 mmol) were refluxed in 100 mL of acetic acid for 3 hours. The reaction was cooled to room temperature, filtered, washed with water and ethanol several times and dried to obtain Compound 1 (2.90 g, 65%). MS [M] = 658

Example  2 Preparation of Compound 4

1. Preparation of Compound 2-1

Dissolve 1-chloroanthraquinone (41.2 mmol, 10.0 g) in 200 mL THF, where 4,4,5,5-tetramethyl-2- (4- (10- (2-naphthyl) anthracene- 9-Nyl) phenyl) -1,3,2-dioxaborane (45.3 mmol, 22.9 g), 50 mL of potassium carbonate 2 M solution, tetrakis (triphenylphosphine) palladium (0) 0)] (1.24 mmol, 1.43 g) and refluxed for 19 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered and washed with water and ethanol several times to obtain compound 2-1 (23 g, 96%). MS [M] = 586

2. Preparation of Compound 2-2

Bromophenyl (19.1 mmol, 3.0 g) was added to 100 mL of dried THF to dissolve completely, and n -butyllithium (6.2 ml, 2.5 M solution in hexane) was added very slowly under -78 ° C. After 1 hour, Compound 2-1 (9.3 mmol, 5.4 g) prepared in 1 was added to the reaction. After 30 minutes, the cooling vessel was removed and reacted at room temperature for 3 hours. After the reaction was added NH ₄ Cl aqueous solution and extracted with ethyl ether. The extracted reaction was dried over anhydrous magnesium sulfate and concentrated. A small amount of ethyl ether was added thereto and stirred, followed by stirring with ethanol. Subsequently, the reaction was filtered and dried to give the dialcohol compound 1-2 (6.56 g, 95%). MS [M] = 724 (-H ₂ O form)

3. Preparation of Compound 4

Compound 2-2 (5.0 g, 6.77 mmol), potassium iodide (1.12 g, 6.77 mmol) and sodium hypophosphite (7.18 g, 67.7 mmol) were refluxed in 100 mL of acetic acid for 3 hours. The reaction was cooled to room temperature, filtered, washed with water and ethanol several times and dried to obtain compound 4 (3.1 g, 65%). MS [M] = 708

Example  3 : Preparation of Compound 10

1. Preparation of Compound 3-1

Dissolve 1-chloroanthraquinone (41.2 mmol, 10.0 g) in 200 mL of THF, where 4,4,5,5-tetramethyl-2- (3- (1,8-phenyl) anthrace-9-9 Nil) phenyl) -1,3,2-dioxaborane (45.3 mmol, 21.9 g), 50 mL of potassium carbonate 2 M solution, tetrakis (triphenylphosphine) palladium (0) ] (1.24 mmol, 1.43 g) was added and refluxed for 19 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered and washed several times with water and ethanol to obtain compound 3-1 (24.2 g, 96%). MS [M] = 612

2. Preparation of Compound 3-2

Bromophenyl (19.1 mmol, 3.0 g) was added to 100 mL of dried THF to dissolve completely, and n -butyllithium (6.2 ml, 2.5 M solution in hexane) was added very slowly under -78 ° C. After 1 hour, Compound 3-1 (9.3 mmol, 5.7 g) prepared in 1 was added to the reaction. After 30 minutes, the cooling vessel was removed and reacted at room temperature for 3 hours. After the reaction was added NH ₄ Cl aqueous solution and extracted with ethyl ether. The extracted reaction was dried over anhydrous magnesium sulfate and concentrated. A small amount of ethyl ether was added thereto and stirred, followed by stirring with ethanol. Subsequently, the reaction was filtered and dried to give the dialcohol compound 3-2 (6.8 g, 95%). MS [M] = 750 (-H ₂ O form)

3. Preparation of Compound 10

The compound 3-2 (3.42 g, 6.77 mmol), potassium iodide (1.12 g, 6.77 mmol) and sodium hypophosphite (7.18 g, 67.7 mmol) were refluxed in 100 mL of acetic acid for 3 hours. The reaction was cooled to room temperature, filtered, washed with water and ethanol several times, and dried to obtain compound 10 (3.2 g, 65%). MS [M] = 734

Example  4 : Preparation of Compound 14

1. Preparation of Compound 4-1

Dissolve 1-chloroanthraquinone (41.2 mmol, 10.0 g) in 200 mL of THF, and add 4,4,5,5-tetramethyl-2- (3- (5-phenylthiophen-2-yl) phenyl ) -1,3,2-dioxaborane (45.3 mmol, 21.9 g), 50 mL of potassium carbonate 2 M solution, tetrakis (triphenylphosphine) palladium (0)] (1.24) mmol, 1.43 g) was added thereto, and the mixture was refluxed for 19 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered, and washed several times with water and ethanol to obtain compound 4-1 (16.7 g, 96%). MS [M] = 442

2. Preparation of Compound 4-2

Bromophenyl (19.1 mmol, 3.0 g) was added to 100 mL of dried THF to dissolve completely, and n -butyllithium (6.2 ml, 2.5 M solution in hexane) was added very slowly under -78 ° C. After 1 hour, Compound 4-1 (9.3 mmol, 4.1 g) prepared in 1 was added to the reaction. After 30 minutes, the cooling vessel was removed and reacted at room temperature for 3 hours. After the reaction was added NH ₄ Cl aqueous solution and extracted with ethyl ether. The extracted reaction was dried over anhydrous magnesium sulfate and concentrated. A small amount of ethyl ether was added thereto and stirred, followed by stirring with ethanol. Subsequently, the reaction was filtered and dried to give the dialcohol compound 4-2 (5.3 g, 95%). MS [M] = 580 (-H ₂ O form)

3. Preparation of Compound 14

Compound 4-2 (4.05 g, 6.77 mmol), potassium iodide (1.12 g, 6.77 mmol) and sodium hypophosphite (7.18 g, 67.7 mmol) were refluxed in 100 mL of acetic acid for 3 hours. The reaction was cooled to room temperature, filtered, washed with water and ethanol several times and dried to obtain compound 14 (2.5 g, 65%). MS [M] = 564

Experimental Example  One

A glass substrate (corning 7059 glass) coated with a thin film of ITO (Indium Tin Oxide) at a thickness of 1000 Å was placed in distilled water in which a dispersant was dissolved, and washed with ultrasonic waves. Dispersant was used Fischer Co. product, distilled water was Millipore Co. Secondly filtered distilled water was used as a filter of the product. After the ITO was washed for 30 minutes, the ultrasonic cleaning was repeated twice with distilled water for 10 minutes. After the washing of distilled water, ultrasonic cleaning was performed in the order of isopropyl alcohol, acetone, and methanol solvent, followed by drying. The substrate was then transported to a plasma cleaner, and the substrate was washed for 5 minutes using an oxygen plasma, and then transported to a vacuum evaporator.

3,6-bis-2-naphthylphenylamino-N- [4- (2-naphthylphenyl) aminophenyl] carbazole (800 Hz), 4,4'-bis [N- (1) on the ITO electrode -Naphthyl) -N-phenylamino] biphenyl (NPB) (300 Hz), each of Compounds 1, 4, 10 and 14 (300 Hz) prepared in Examples 1-4 above, and 9,10-bis 2-naphthyl-2- [4- (N-phenylbenzoimidazoyl) phenyl] anthracene (300 kV) was sequentially thermally vacuum deposited to form a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer in that order.

In the light emitting layer, the following amine compound D1 was used as a dopant material.

Comparative example  1 to 3

An organic light emitting diode was manufactured according to the same method as Experimental Example 1 except for using the following compounds A, B, and C instead of compounds 1, 4, 10, and 14 in Experimental Example 1.

The light emitting layer material and the experimental results used in the above Experimental Example and Comparative Example are summarized in Table 1 below.

TABLE 1

The compounds of Formula 1 according to the present invention have two or more fluorophores, i.e., anthracene and X are linked to each other, so that two fluorophores exist in one molecule. In particular, when the anthracene moiety and X are in the ortho or meta position rather than the para position, they are chemically bonded to each other, but do not significantly affect the conjugation with each other. The emission spectrum of can be seen. Therefore, the effect of increased efficiency can be expected by forming a molecular structure that can contain twice the carrier per molecule.

1 is a diagram illustrating a structure of an organic light emitting device according to an exemplary embodiment of the present invention.

Claims (14)

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

In Chemical Formula 1, Q is an arylene group of C ₆ ~ C ₂₀ , R1, R2 and X are each, independently, a halogen, CN, NO _2, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkyl amine group, C ₆ ~ C ₂₀ of the Arylamine group, C ₁ to C ₂₀ alkyl thiophene group, C ₆ to C ₂₀ aryl thiophene group, C ₂ to C ₂₀ alkenyl group, C ₂ to C ₂₀ alkynyl group, C ₃ to C ₂₀ A cycloalkyl group, a C ₆ -C ₂₀ aryl group, -BRR ', -SiRR'R ", -GeRR'R" and a substituted or unsubstituted C ₅ -C ₂₀ heterocyclic group substituted with one or more groups selected from the group Or unsubstituted C ₆ -C ₂₀ aryl group; or Halogen, CN, NO ₂ , C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkylamine group, C ₆ ~ C ₂₀ arylamine group, C ₁ ~ C ₂₀ alkylthio group, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C ₂₀ alkynyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ aryl group, -BRR ', -SiRR'R "of, and -GeRR'R "and substituted or unsubstituted C ₅ ~ C ₂₀ heterocyclic group of the or unsubstituted C ₅ ~ C ₂₀ substituted with one or more groups selected from the group consisting of a heterocyclic ring, Wherein, R, R 'and R "are each independently, hydrogen, C ₁ ~ C ₂₀ alkyl group, C cycloalkyl group of ₃ ~ C _20, C aryl group of ₆ ~ C ₂₀ or C ₅ ~ heterocycle of the C ₂₀ Qi. The anthracene derivative according to claim 1, wherein Q is phenylene, naphthylene or biphenylene. The compound of claim 1, wherein R 1 and R 2 are each independently phenyl; 1-naphthyl; 2-naphthyl; Biphenyl; Triphenyl; 1-tetralinyl; 2-tetralinyl; Stilbenyl; Fluorenyl; Or anthracenyl substituted with diphenyl, biphenyl, 1-naphthyl, 2-naphthyl, anthracenyl, phenyl or naphthyl; Anthracene derivative, characterized in that phenyl substituted with a group selected from the group consisting of phenylthiophenyl, carbazolyl and diphenylamine. The anthracene derivative according to claim 1, wherein X is a C ₆ -C ₂₀ aryl group including 1-naphthyl, 2-naphthyl, biphenyl, and a C ₅ -C ₂₀ heterocyclic group. The anthracene derivative according to claim 1, wherein X is selected from the group consisting of

In the above structural formula, Ar ₁ to Ar ₅ are the same as or different from each other, and each independently phenyl; 1-naphthyl; 2-naphthyl; Biphenyl; Triphenyl; 1-tetralinyl; 2-tetralinyl; Stilbenyl; Fluorenyl; Or anthracenyl substituted with diphenyl, biphenyl, 1-naphthyl, 2-naphthyl, anthracenyl, phenyl or naphthyl; Phenyl is substituted with a group selected from the group consisting of phenylthiophenyl, carbazolyl and diphenylamine. The anthracene derivative according to claim 1, wherein X is represented by the following Chemical Formula 2: [Formula 2]

In Formula 2, n, p, q and r are 0 or an integer of 1 to 10, p + q ≥ 1, L ₁ is directly connected; Halogen, CN, NO ₂ , C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkylamine group, C ₆ ~ C ₂₀ arylamine group, C ₁ ~ C ₂₀ alkylthiophene group, C ₆ ~ aryl T of C ₂₀ thiophene group, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ aryl of C ₂₀ alkynyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ of the group, -BRR ', -SiRR'R ", -GeRR'R " and a substituted or unsubstituted C ₅ ~ C ₂₀ by at least one group selected from the group consisting of heterocyclic ring groups is substituted or unsubstituted C ₅ ~ C ₂₀ of Arylene group; Or halogen, CN, NO ₂ , C ₁ -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy group, C ₁ -C ₂₀ alkylamine group, C ₆ -C ₂₀ arylamine group, C ₁ -C ₂₀ the coming of the alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C ₂₀ of the alkynyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ aryl group, -BRR ', -SiRR'R " , -GeRR'R "and a substituted or unsubstituted C ₅ ~ C ₂₀ heterocyclic group unsubstituted or substituted with one or more groups selected from the group consisting of C ₅ ~ C _{20 It} is a divalent heterocyclic group, L ₂ is an aryl group of C ₅ to C ₂₀ , Wherein, R, R 'and R "are each independently, hydrogen, C ₁ ~ C ₂₀ alkyl group, C cycloalkyl group of ₃ ~ C _20, C aryl group of ₆ ~ C ₂₀ or C ₅ ~ heterocycle of the C ₂₀ Gigi, R ₇ and R ₈ are the same as or different from each other, and each independently hydrogen; halogen; Hydroxyl; Mercapto; Cyano; Nitro; Carbonyl; Carboxyl; Formyl; Substituted or unsubstituted C ₁ -C ₂₀ alkyl; Substituted or unsubstituted C ₂ -C ₁₀ alkenyl; Substituted or unsubstituted C ₂ -C ₇ alkynyl; Substituted or unsubstituted C ₆ -C ₂₀ aryl; Substituted or unsubstituted C ₄ -C ₂₀ heteroaryl; Substituted or unsubstituted C ₃ -C ₇ cycloalkyl, wherein the carbon atoms in the ring may be optionally substituted by oxygen, nitrogen or sulfur atoms; C ₄ -C ₇ cycloalkenyl, wherein the carbon atoms in the ring may be optionally substituted by oxygen, nitrogen or sulfur atoms; Substituted or unsubstituted C ₁ -C ₂₀ alkoxy; Substituted or unsubstituted C ₂ -C ₁₀ alkenyloxy; Substituted or unsubstituted C ₂ -C ₇ alkynyloxy; Substituted or unsubstituted C ₆ -C ₂₀ aryloxy; Substituted or unsubstituted C ₁ -C ₂₀ alkylamine; Substituted or unsubstituted C ₂ -C ₁₀ alkenylamine; Substituted or unsubstituted C ₂ -C ₇ alkynylamine; Substituted or unsubstituted C ₆ -C ₂₀ arylamine; Substituted or unsubstituted C ₇ -C ₂₀ alkylarylamine; Substituted or unsubstituted C ₁ -C ₂₀ alkylsilyl; Substituted or unsubstituted C ₂ -C ₁₀ alkenylsilyl; Substituted or unsubstituted C ₂ -C ₇ alkynylsilyl; Substituted or unsubstituted C ₆ -C ₂₀ arylsilyl; Substituted or unsubstituted C ₇ -C ₂₀ alkylarylsilyl; Substituted or unsubstituted C ₁ -C ₂₀ alkylboranyl; Substituted or unsubstituted C ₂ -C ₁₀ alkenylboranyl; Substituted or unsubstituted C ₂ -C ₇ alkynylboranyl; Substituted or unsubstituted C ₆ -C ₂₀ arylboranyl; Substituted or unsubstituted C ₇ -C ₂₀ alkylarylboranyl; Substituted or unsubstituted C ₁ -C ₂₀ alkylthio; Substituted or unsubstituted C ₂ -C ₁₀ alkenylthio; Substituted or unsubstituted C ₂ -C ₇ alkynylthio; And a substituted or unsubstituted C ₆ -C ₂₀ arylthio group. The compound of claim 6, wherein R ₇ and R ₈ are the same as or different from each other, and each independently hydrogen, cyano, nitro, substituted or unsubstituted C ₁ -C ₂₀ alkyl, substituted or unsubstituted C ₂ -C ₁₀ alkenyl , Substituted or unsubstituted C ₃ -C ₇ cycloalkyl, substituted or unsubstituted C ₄ -C ₇ cycloalkenyl, substituted or unsubstituted C ₆ -C ₂₀ aryl, substituted or unsubstituted C ₄ -C ₂₀ heteroaryl, substituted Or unsubstituted C ₁ -C ₂₀ alkoxy, substituted or unsubstituted C ₆ -C ₂₀ aryloxy, substituted or unsubstituted C ₁ -C ₂₀ Alkylamines, substituted or unsubstituted C ₆ -C ₂₀ arylamines, substituted or unsubstituted C ₇ -C ₂₀ alkylarylamines, substituted or unsubstituted C ₁ -C ₂₀ alkylsilyl; Substituted or unsubstituted C ₁ -C ₂₀ alkylboranyl, substituted or unsubstituted C ₆ -C ₂₀ arylboranyl, substituted or unsubstituted C ₇ -C ₂₀ alkylarylboranyl, substituted or unsubstituted C ₁ -C ₂₀ alkyl Thio, and a substituted or unsubstituted C ₆ -C ₂₀ arylthio group, characterized in that the anthracene derivative. The anthracene derivative according to claim 1, wherein the compound of Formula 1 is selected from the group consisting of the following structural formulas:

1) reacting 1-chloroanthraquinone with boronic acid compound (XQB (OH) ₂ ) to prepare compound (II), 2) reacting compound (II) with a bromo compound (R1-Br or R2-Br) to produce a dialcohol compound (III), and 3) reacting the dialcohol compound (III) with potassium iodide and sodium hypophosphite to produce compound (I), Method for preparing an anthracene derivative represented by Scheme 1 below: Scheme 1

In Scheme 1, Q is an arylene group of C ₆ ~ C ₂₀ , R1, R2 and X are each, independently, a halogen, CN, NO _2, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkyl amine group, C ₆ ~ C ₂₀ of the Arylamine group, C ₁ to C ₂₀ alkyl thiophene group, C ₆ to C ₂₀ aryl thiophene group, C ₂ to C ₂₀ alkenyl group, C ₂ to C ₂₀ alkynyl group, C ₃ to C ₂₀ A cycloalkyl group, a C ₆ -C ₂₀ aryl group, -BRR ', -SiRR'R ", -GeRR'R" and a substituted or unsubstituted C ₅ -C ₂₀ heterocyclic group substituted with one or more groups selected from the group Or unsubstituted C ₆ -C ₂₀ aryl group; or Halogen, CN, NO ₂ , C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkylamine group, C ₆ ~ C ₂₀ arylamine group, C ₁ ~ C ₂₀ alkylthio group, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C ₂₀ alkynyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ aryl group, -BRR ', -SiRR'R "of, and -GeRR'R "and substituted or unsubstituted C ₅ ~ C ₂₀ heterocyclic group of the or unsubstituted C ₅ ~ C ₂₀ substituted with one or more groups selected from the group consisting of a heterocyclic ring, Wherein, R, R 'and R "are each independently, hydrogen, C ₁ ~ C ₂₀ alkyl group, C cycloalkyl group of ₃ ~ C _20, C aryl group of ₆ ~ C ₂₀ or C ₅ ~ heterocycle of the C ₂₀ Qi. An organic electronic device comprising a first electrode, a second electrode, and at least one organic material layer disposed between the first electrode and the second electrode, wherein at least one of the organic material layers is any one of claims 1 to 3. An organic electronic device, comprising an anthracene derivative represented by the formula (1) described. The method according to claim 10, wherein the organic material layer comprises a hole injection layer, a hole transport layer, and at least one layer of the hole injection and hole transport at the same time, one layer of the layer is an anthracene derivative represented by the formula (1) An organic electronic device, characterized in that it comprises. The organic electronic device according to claim 10, wherein the organic material layer includes a light emitting layer, and the light emitting layer includes an anthracene derivative represented by Chemical Formula 1. The organic electronic device according to claim 10, wherein the organic material layer includes an electron transport layer, and the electron transport layer includes an anthracene derivative represented by Chemical Formula 1. The organic electronic device of claim 10, wherein the organic electronic device is selected from the group consisting of an organic light emitting device, an organic solar cell, an organic photoconductor (OPC), and an organic transistor.

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