KR101408632B1 - New compounds and organic electronic device using the same - Google Patents

Abstract

The present invention relates to a novel compound and an organic electronic device using the same. The compound according to the present invention can perform hole injection, hole transport, electron injection and transport, and a light emitting material in an organic electronic device including an organic light emitting device, and the organic electronic device according to the present invention can improve efficiency, .

Description

TECHNICAL FIELD [0001] The present invention relates to a novel compound, and an organic electronic device using the same. BACKGROUND OF THE INVENTION [0002]

The present invention relates to a novel compound and an organic electronic device using the same.

In the present specification, an organic electronic device is an electronic device using an organic semiconductor material, and requires the exchange of holes and / or electrons between the electrode and the organic semiconductor material. The organic electronic device can be roughly classified into two types according to the operating principle as described below. First, an exciton is formed in an organic material layer by a photon introduced into an element from an external light source. The exciton is separated into an electron and a hole, and the electrons and holes are transferred to different electrodes to be used as a current source Is an electronic device. The second type is an electronic device that injects holes and / or electrons into an organic semiconductor material layer that interfaces with the 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 device, an organic solar cell, an organic photoconductor (OPC) drum, and an organic transistor. These devices include an electron / hole injecting material, an electron / hole extracting material, Materials or luminescent materials. Hereinafter, the organic light emitting device will be described in detail, but in the organic electronic devices, the electron / hole injecting material, the electron / hole extracting material, the electron / hole transporting material, or the light emitting material all have 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 and a cathode and an organic layer between them. Here, in order to increase the efficiency and stability of the organic light emitting device, the organic material layer may have a multi-layer structure composed of different materials and may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. When a voltage is applied between two electrodes in the structure of the organic light emitting device, holes are injected into the anode, electrons are injected into the organic layer, electrons are injected into the organic layer, excitons are formed when injected holes and electrons meet, When it falls to a state, it becomes a light. Such an organic light emitting device is known to have characteristics such as self-emission, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, and high speed response.

A material used as an organic material layer in an organic light emitting device can be classified into a light emitting material and a charge transporting material such as a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending on functions. The luminescent material has blue, green and red luminescent materials and yellow and orange luminescent materials necessary for realizing a better natural color depending on the luminescent color. Further, in order to increase the color purity and increase the luminous efficiency through energy transfer, a host / dopant system can be used as a light emitting material. The principle is that when a small amount of dopant having a smaller energy band gap and a higher luminous efficiency than a host mainly constituting the light emitting layer is mixed with the light emitting layer in a small amount, the excitons generated in the host are transported to the dopant to emit light with high efficiency. At this time, since the wavelength of the host is shifted to the wavelength band of the dopant, the desired wavelength light can be obtained depending on the type of the dopant used.

In order to sufficiently exhibit the excellent characteristics of the organic light emitting device, a material constituting the organic material layer in the device such as a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material and an electron injecting material is supported by a stable and efficient material However, the development of a stable and efficient organic material layer material for an organic light emitting device has not yet been sufficiently achieved, and therefore, the development of new materials has been continuously required.

The present inventors have found a compound having a novel structure. In addition, when the organic compound layer of the organic electronic device is formed using the novel compound, it has been found that the organic compound layer can exhibit the effects of increasing the efficiency of the device, lowering the driving voltage, and increasing the stability.

Accordingly, an object of the present invention is to provide a novel compound and an organic electronic device using the same.

The present invention provides a compound represented by the following formula (1).

In Formula 1,

Q is a condensed heteroaromatic polycyclic group in which 1 to 4 carbon atoms (C) in the condensed aromatic polycyclic group of C ₈ to C ₃₀ are replaced by nitrogen atoms (N)

CY is a pentagonal or hexagonal ring,

n is an integer of 1 to 8, m is an integer of 1 to 4,

Ar and Ar 'are the same or different from each other and each independently represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted C ₁ to C ₂₀ alkyl group, a substituted or unsubstituted C _{2 -} to C ₂₀ alkenyl group, A substituted or unsubstituted C ₃ to C ₂₀ cycloalkyl group, a substituted or unsubstituted C ₅ to C ₃₀ cycloalkenyl group, a substituted or unsubstituted C ₁ to C ₃₀ alkoxy group, a substituted or unsubstituted C ₆ to C _A substituted or unsubstituted C ₁ to C ₃₀ alkylthio group, a substituted or unsubstituted C ₅ to C ₂₀ arylthioxy group, a substituted or unsubstituted C ₁ to C ₃₀ alkylamine group , substituted or unsubstituted C ₅ ~ C ₃₀ aryl amine group, a substituted or unsubstituted C _{6 -} ~ of the C ₃₀ aryl group, a substituted or unsubstituted, and two kinds of atoms O, C ₃ ~ C ₃₀ having an N or S A substituted or unsubstituted aryl group, a substituted or unsubstituted boron group, a substituted or unsubstituted silane group, a carbonyl group, a phosphoryl group, an amino group, a nitrile group, A condensed ring of an aliphatic, aromatic, aliphatic hetero or aromatic hetero, and a spiro bond, which are selected from the group consisting of a nitro group, a hydroxy group, a halogen group, an amide group and an ester group, The two or more Ar 's may be the same as or different from each other, and when m is an integer of 2 or more, the two or more Ar' s may be the same or different,

R ₁ and R ₂ are the same or different from each other and each independently represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted C ₁ to C ₃₀ alkyl group, a substituted or unsubstituted C ₂ to C ₁₂ alkenyl group, A substituted or unsubstituted C ₃ to C ₃₀ cycloalkyl group, a substituted or unsubstituted C ₅ to C ₂₀ cycloalkenyl group, a substituted or unsubstituted C ₆ to C ₃₀ aryl group, a substituted or unsubstituted heteroatom, O, Or a C ₃ to C ₃₀ heteroaryl group having N or S.

In addition,

1) Compound A represented by the following formula 2 as an arylboronic acid or arylboronate compound is subjected to Suzuki coupling reaction with a halide aryl compound under a palladium (Pd) catalyst to obtain a compound B represented by the following formula 3 Manufacturing steps,

2) The compound B is dissolved in an anhydrous solvent, lithiated with n-, sec- or tert-BuLi, and then reacted with a substituted or unsubstituted ketone compound R ₁ COR ₂ to obtain a monoalcohol compound To produce a compound C represented by the following formula (4), and

3) coupling the rings by reacting the compound C under acidic conditions

Wherein R < 1 > and R < 2 >

Are as defined in the Ar, Ar ', Q, n and m are the Formula 1, R, R ₁ and R ₂ is as defined for R ₁ and R ₂ of formula (I).

The present invention also provides 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 represented by Formula 1 Wherein the organic compound is a compound represented by formula (I).

The novel compounds according to the present invention can be used as organic material layers of organic electronic devices including organic light emitting devices by introducing various aryl groups, heteroaryl groups, arylamino groups and the like. In addition, the organic electronic device including the organic light emitting device using the compound according to the present invention as the material of the organic material layer exhibits excellent characteristics in terms of efficiency, driving voltage, and lifetime.

1 is an example of an organic light emitting device structure in which an anode 102, a light emitting layer 105, and a cathode 107 are sequentially stacked on a substrate 101.
2 is an example of an organic light emitting device structure in which an anode 102, a hole injection / hole transporting and light emitting layer 105, an electron transporting layer 106, and a cathode 107 are sequentially stacked on a substrate 101.
3 is an example of an organic light emitting device structure in which a substrate 101, an anode 102, a hole injecting layer 103, a hole transporting and emitting layer 105, an electron transporting layer 106, and a cathode 107 are sequentially stacked .
4 is an example of an organic light emitting device structure in which a substrate 101, an anode 102, a hole injecting layer 103, a hole transporting layer 104, an electron transporting and emitting layer 105, and a cathode 107 are sequentially stacked .

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

The compound according to the present invention is characterized by being represented by the above formula (1).

In the compound according to the present invention, the substituents of the above formula (1) will be described in more detail as follows.

Q is a condensed heteroaromatic polycyclic group in which 1 to 4 carbon atoms (C) in the condensed aromatic polycyclic group of C ₈ to C ₃₀ are replaced by nitrogen atoms (N), and more specific examples include 1 to 4 N Phenanthrene derivatives, indole, benzimidazole, benzoxazole, quinoline, carbazole, acridine, and the like, but are not limited thereto.

The alkyl group may be linear or branched and the number of carbon atoms does not affect the conjugation length of the compound but only incidentally affects the application of the compound to organic electronic devices such as vacuum deposition or solution coating , And is preferably 1 to 20, although not particularly limited thereto. Specific examples include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl and heptyl.

The alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 20. Specific examples thereof include, but are not limited to, an alkenyl group having an aryl group such as a stilbenyl group or a styrenyl group.

The cycloalkyl group preferably has 3 to 20 carbon atoms and does not give steric hindrance. Specific examples thereof include, but are not limited to, a cyclopentyl group, a cyclohexyl group, and the like.

The cycloalkenyl group preferably has 5 to 30 carbon atoms, and more specifically, a cyclic compound having ethenylene in a pentagonal or hexagonal ring, but is not limited thereto.

The alkoxy group preferably has 1 to 30 carbon atoms, and more specifically, may be methoxy, ethoxy, phenyloxy, cyclohexyloxy, naphthyloxy, isopropyloxy, diphenyloxy and the like. It is not.

The arylamine group preferably has 5 to 30 carbon atoms. More specifically, the arylamine group may include a diphenylamine group, a phenylnaphthylamine group, a phenylbiphenylamine group, a naphthylbiphenylamine group, a dinaphthylamine group, a diphenylamine group, Methyl-naphthylamine group, a 2-methyl-biphenylamine group, a 9-methyl-anthracenylamine group, a ditolylamine group, a phenyltolylamine group , A triphenylaminophenylamine group, a phenylbiphenylaminophenylamine group, a naphthylphenylaminophenylbiphenylamine group, and the like, but are not limited thereto.

The aryl group may be monocyclic or polycyclic, and the number of carbon atoms is not particularly limited, but is preferably 6 to 30. Examples of the monocyclic aryl group include a phenyl group, a biphenyl group, a terphenyl group and a stilbene group. Examples of the polycyclic aryl group include a naphthyl group, an anthracenyl group, a phenanthrene group, a pyrenyl group, a perylenyl group, A decyl group, and the like, but the present invention is not limited thereto.

The heteroaryl group is a cyclic group containing hetero atoms such as O, N or S, and the number of carbon atoms is not particularly limited, but is preferably 3 to 30 carbon atoms. Examples of the heteroaryl group include carbazole groups, thiophene groups, furan groups, pyrrolyl groups, imidazole groups, thiazole groups, oxazole groups, oxadiazole groups, triazole groups, pyridyl groups, pyrazinyl groups, quinolinyl groups, isoquinoline groups , An acridyl group, and the like, but are not limited thereto.

Examples of the halogen group include, but are not limited to, fluorine, chlorine, bromine, and iodine.

Examples of the substituent which may be substituted for Ar, Ar ', R ₁ and R ₂ in the above formula (1) include deuterium, a halogen atom, a carbonyl group, an ester group, a phosphoryl group, an imide group, an amino group, a nitro group, a cyano group, An alkoxy group, an arylthioxy group, an alkylthio group, an alkylamine group, an aralkylamine group, an arylamine group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, a silane group, a boron group, a C ₆ to C ₃₀ aryl group, A C ₃ to C ₃₀ heteroaryl group, and the like, but the present invention is not limited thereto.

In the compound according to the present invention, the above-mentioned formula (1) may be represented by the following formulas (5) to (12).

Wherein R ₁ , R ₂ , Ar 'and m are the same as defined in Formula 1,

Ar ₁ to Ar ₈ each independently represent the same definition as Ar of the above formula (1)

At least one of X ₁ to X ₈ is a nitrogen atom (N) and the remainder is a carbon atom (C) or a nitrogen atom (N).

In Formula 12, R ₁ , R ₂ , Ar 'and m are the same as defined in Formula 1,

Ar ₁ to Ar ₅ are each independently the same as the definition of Ar in formula (1)

At least one of X ₁ to X ₅ is a nitrogen atom and the others are selected from the group consisting of a carbon atom (C), a nitrogen atom (N), a sulfur atom (S) and an oxygen atom (O).

Specific examples of the compound represented by the formula (1) include, but are not limited to, the following compounds.

The compound represented by Formula 1 may be prepared by a conventional method known in the art, such as alcohol production, Suzuki coupling, and the like.

More specifically, the process for preparing the compound represented by the formula (1) according to the present invention comprises the steps of 1) reacting the compound A represented by the formula (2) as an arylboric acid or arylboronate compound with a halide aryl compound And 2) dissolving the compound B in an anhydrous solvent and then lithiating it with n-, sec- or tert-BuLi, Reacting the compound C with a substituted or unsubstituted ketone compound R ₁ COR ₂ to prepare a compound C represented by the formula 4 as a monoalcohol compound; and 3) reacting the compound C with an acidic condition to form a ring .

When Q is phenanthrene containing 1 to 4 N atoms among the compounds represented by the formula (1), it can be prepared according to the following reaction scheme. In addition, the following Reaction Scheme 1 is only one example for synthesizing the compound represented by Formula 1, but it is not limited thereto.

[Reaction Scheme 1]

According to Reaction Scheme 1, when the compound represented by Formula 1 is phenanthrene wherein Q is 1 to 4 N,

1) A benzoquinolin boronic acid compound or benzoquinolin boronate compound A is reacted with 1,2-dibromobenzene or 1-bromo-2-iodobenzene compound With Suzuki coupling to prepare compound B,

2) The compound B prepared in the above step 1) is dissolved in an anhydrous solvent, lithiated with n-, sec-, tert-BuLi, and then reacted with a substituted or unsubstituted R ₁ COR ₂ ketone compound To produce a monoalcohol compound C, and

3) reacting the compound C prepared in the step 2) in an acidic condition to link the rings.

In the above Reaction Scheme 1, R ₁ , R ₂ , Ar 'and m are the same as defined in Formula 1,

Ar ₁ to Ar ₈ each independently represent the same definition as Ar of the above formula (1)

R is the same as defined for R < ₁ > and R < ₂ &

At least one of X ₁ to X ₈ is a nitrogen atom (N) and the remainder is a carbon atom (C) or a nitrogen atom (N).

The compounds represented by the formula (1) may have properties suitable for use as an organic layer used in an organic light emitting device by introducing various substituents into the core structure represented by the formula. The compound represented by the formula (1) may be used in any layer of an organic light emitting device, but may have the following characteristics.

The compounds having a substituted or unsubstituted arylamine group are suitable as a light emitting layer, a hole injecting and hole transporting layer material, and are suitable as an electron injecting, electron transporting layer and hole blocking layer material when a heterocyclic ring substituent containing N is introduced .

The conjugation length of the compound and the energy band gap are closely related. Specifically, the longer the conjugation length of the compound, the smaller the energy bandgap. As described above, since the core of the compound represented by the above formula (1) includes limited conjugation, the energy band gap has a large property from a small property.

Further, by introducing various substituents into the core structure having the above structure, it is possible to synthesize a compound having the intrinsic characteristics of the substituent introduced. For example, the hole injecting layer material and the hole transporting layer materials used in the production of the organic light emitting device have energy levels enough to transfer holes along HOMO (highest occupied molecular orbital), and the lowest unoccupied molecular orbital (LUMO) A compound capable of having an energy level enough to block the electrons passing along the electron transporting layer. Particularly, the core structure of the present compound exhibits stable characteristics in terms of electrons, which can contribute to improvement of lifetime of the device. The derivatives prepared by introducing the substituents to be used for the light emitting layer and the electron transporting layer material can be manufactured to have appropriate energy band gaps for various arylamine type dopants, aryl type dopants, metal containing dopants and the like.

In addition, by introducing various substituent groups into the core structure, it is possible to finely control the energy band gap, and to improve the interfacial characteristics between the organic materials and to diversify the use of the materials.

On the other hand, the compounds represented by Formula 1 have high glass transition temperature (Tg) and thus are excellent in thermal stability. This increase in thermal stability is an important factor in providing drive stability to the device.

Further, the organic electronic device according to the present invention 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, wherein at least one of the organic layers And a compound represented by the above formula (1).

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

The compound of Formula 1 may be formed into an organic material layer by a solution coating method as well as a vacuum evaporation method in the production of an organic electronic device. Here, the solution coating method refers to spin coating, dip coating, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited thereto.

The organic material layer of the organic electronic device of the present invention may have a single layer structure, but may have a multilayer structure in which two or more organic material layers are stacked. For example, the organic electronic device of the present invention may have a structure including a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, an electron injecting layer, and the like as an organic material layer. However, the structure of the organic electronic device is not limited to this, and may include a smaller number of organic layers.

Accordingly, in the organic electronic device of the present invention, the organic material layer may include a hole injection layer and a hole transport layer, and the hole injection layer and the hole transport layer may include the compound represented by the above formula (1).

In addition, the organic layer may include a light emitting layer, and the light emitting layer may include a compound represented by the general formula (1).

In the organic layer having such a multi-layer structure, the compound of Formula 1 may be included in a light emitting layer, a layer that simultaneously transports holes and holes, a layer that simultaneously transports holes and light, or a layer that simultaneously transports electrons and emits light.

For example, the structure of the organic light emitting device of the present invention may have a structure as shown in Figs. 1 to 4, but is not limited thereto.

FIG. 1 illustrates a structure of an organic light emitting device in which an anode 102, a light emitting layer 105, and a cathode 107 are sequentially stacked on a substrate 101. In such a structure, the compound of Formula 1 may be included in the light emitting layer 105.

2 illustrates a structure of an organic light emitting device in which an anode 102, a hole injection / hole transporting and light emitting layer 105, an electron transporting layer 106, and a cathode 107 are sequentially stacked on a substrate 101. In such a structure, the compound of Formula 1 may be included in the hole injection / hole transporting and light emitting layer 105.

3 shows a structure of an organic light emitting device in which a substrate 101, an anode 102, a hole injecting layer 103, a hole transporting and emitting layer 105, an electron transporting layer 106, and a cathode 107 are sequentially stacked. . In such a structure, the compound of Formula 1 may be included in the hole injection / hole transporting and light emitting layer 105.

4 shows a structure of an organic light emitting device in which a substrate 101, an anode 102, a hole injecting layer 103, a hole transporting layer 104, an electron transporting and emitting layer 105, and a cathode 107 are sequentially laminated. . In such a structure, the compound of Formula 1 may be included in the electron transporting and light emitting layer 105.

For example, the organic light emitting device according to the present invention may be formed by using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation to form a metal oxide or a metal oxide having conductivity on the substrate, To form an anode, an organic material layer including a hole injection layer, a hole transporting layer, a light emitting layer, and an electron transporting layer is formed on the anode, and a material which can be used 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 material layer may have a multi-layer 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. The organic material layer may be formed using a variety of polymeric materials by a method such as a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, Layer.

As the anode material, a material having a large work function is preferably used so that hole injection can be smoothly conducted into the organic material layer. Specific examples of the cathode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), 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-methyl compounds), poly [3,4- (ethylene-1,2-dioxy) compounds] (PEDT), polypyrrole and polyaniline.

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

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

As the hole transporting material, a material capable of transporting holes from the anode or the hole injecting layer to the light emitting layer and having high mobility to holes is 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.

The light emitting material is preferably a material capable of emitting light in the visible light region by transporting and receiving holes and electrons from the hole transporting layer and the electron transporting layer, respectively, and having good quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; Compounds of the benzoxazole, benzothiazole and benzimidazole series; Polymers of poly (p-phenylenevinylene) (PPV) series; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited thereto.

As the electron transporting material, a material capable of transferring electrons from the cathode well into the light emitting layer, which is suitable for electrons, is suitable. Specific examples include an Al complex of 8-hydroxyquinoline; Complexes containing Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited thereto.

The organic light emitting device according to the present invention may be a front emission type, a back emission type, or a both-sided emission type, depending on the material used.

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

Accordingly, the organic electronic device may be selected from the group consisting of an organic light emitting device, an organic phosphor device, an organic solar cell, an organic photoconductor (OPC), and an organic transistor.

Hereinafter, the method for preparing the compound represented by the formula (1) of the present invention, the method for producing the organic electronic device using the same, and the performance will be described in detail. However, the following examples are for illustrative purposes only, and the scope of the present invention is not limited by the following examples.

The evaluation method in the examples is as follows.

1. Driving voltage: measured using Kethley 236 (source measure unit)

2. Current efficiency: measured using SpectraScan Pr-650

3. Color Coordinates: Measured using SpectraScan Pr-650

The compound represented by formula (1) according to the present invention can be generally prepared by a multistage chemical reaction. That is, some of the intermediate compounds are first prepared, and the compounds of formula (1) are prepared from the intermediate compounds. Illustrative intermediate compounds are those listed in the following table.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are intended to illustrate the invention and are not intended to limit the scope of the invention.

< Example >

< Synthetic example  1>

1) Preparation of Compound 1A

2- (4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl) benzo [h] quinoline (2- (4,4,5,5- (30.3 g, 100 mmol) and 1-bromo-2-iodobenzene (28.3 g, 100 mmol) were completely dissolved in tetrahydrofuran , 2M aqueous potassium carbonate solution was added, and tetrabistriphenylphosphinopalladium (2.3 g, 2 mmol) was added thereto, followed by heating and stirring for 10 hours. The resulting solution was dried over anhydrous magnesium sulfate and recrystallized from CHCl ₃ / n-Hex to obtain 2- (2-bromophenyl) benzo [h] quinoline (2- bromophenyl) benzo [h] quinoline (24.1 g, yield 72%).

MS: [M + H] &lt; ⁺ &gt; = 334

2) Preparation of compound 1B

Compound A (24.1 g, 72.1 mmol) synthesized in 1) above was added to anhydrous THF (100 mL) under a nitrogen atmosphere, and the reaction temperature was maintained at -78 ^° C. n-BuLi (2.5 M in HEX, 34.6 mL, 87 mmol) was added dropwise to the reaction solution. After stirring for about 40 minutes, 2,7-dibromofluorenone (24.7 g, 35 mmol) was added to the reaction mixture and stirred. After about 1 hour, the temperature was raised to room temperature and stirred for 3 hours. Aqueous ammonium chloride solution was added to the reaction mixture and the THF layer was separated. The organic layer was dried over anhydrous magnesium sulfate, and ethyl ether was added thereto to prepare a solid compound.

3) Preparation of compound 1C

Compound 1B obtained in 2) was not further purified, and 100 mL of acetic acid was added and stirred. 2 mL of sulfuric acid was added dropwise to the reaction solution, and the mixture was heated and stirred at 80 ° C. After stirring for 8 hours, the mixture was cooled to room temperature, and the resulting yellow solid was filtered, washed with water and ethanol, and then dried. The dried compound was stirred with 200 mL of 1 M NaOH solution, washed with water and filtered to obtain Compound 1C (39 g, yield 94%).

MS: [M + H] &lt; ⁺ &gt; = 575

< Synthetic example  2>

1) Preparation of compound 2B

Compound A (12 g, 36 mmol) synthesized in 1) above in Synthesis Example 1 was placed in anhydrous THF (100 mL) under a nitrogen atmosphere, and the reaction temperature was maintained at -78 ^° C. n-BuLi (2.5 M in HEX, 17.2 mL, 43 mmol) was added dropwise to the reaction solution. After stirring for about 40 minutes, 2-bromofluorenone (9.1 g, 35 mmol) was added to the reaction mixture and stirred. After about 1 hour, the temperature was raised to room temperature and stirred for 3 hours. Aqueous ammonium chloride solution was added to the reaction mixture and the THF layer was separated. The organic layer was dried over anhydrous magnesium sulfate, and ethyl ether was added thereto to prepare a solid compound 2B.

2) Preparation of compound 2C

Compound 2B obtained in 1) above was not purified, and 100 mL of acetic acid was added and stirred. 2 mL of sulfuric acid was added dropwise to the reaction solution, and the mixture was heated and stirred at 80 ° C. After stirring for 8 hours, the reaction mixture was cooled to room temperature, and the resulting yellow solid was filtered. The dried compound was dissolved in 120 mL of 1M NaOH solution, stirred, washed with water and filtered to prepare Compound 2C (15.7 g, yield 88%).

MS: [M + H] &lt; ⁺ &gt; = 496

< Synthetic example  3>

1) Preparation of Compound 3A

2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) quinoline (2- (4,4,5,5-tetramethyl- 2-yl) quinoline (26 g, 100 mmol) and 1-bromo-2-iodobenzene (28.3 g, 100 mmol) were dissolved in tetrahydrofuran Tetrabistriphenylphosphinopalladium (2.3 g, 2 mmol) was added thereto, followed by heating and stirring for 10 hours. The temperature was lowered to room temperature, and the resulting solution was dried over anhydrous magnesium sulfate and recrystallized from CHCl ₃ / n-Hex to give 22.2 g (yield, 78%) of the above Formula 3A.

MS: [M + H] &lt; ⁺ &gt; = 284

2) Preparation of compound 3B

To the compound 3A (10 g, 35.2 mmol) synthesized in the above 1) was added anhydrous THF (100 mL) under a nitrogen atmosphere, and the reaction temperature was maintained at -78 ^° C. n-BuLi (2.5 M in HEX, 17.2 mL, 43 mmol) was added dropwise to the reaction solution. After stirring for about 40 minutes, 2,7-dibromofluorenone (9.1 g, 35 mmol) was added to the reaction mixture and stirred. After about 1 hour, the temperature was raised to room temperature and stirred for 3 hours. Aqueous ammonium chloride solution was added to the reaction mixture and the THF layer was separated. The organic layer was dried over anhydrous magnesium sulfate, and ethyl ether was added thereto to prepare a solid compound.

3) Preparation of compound 3C

Compound 3B obtained in 2) was not further purified, and 100 mL of acetic acid was added and stirred. 2 mL of sulfuric acid was added dropwise to the reaction solution, and the mixture was heated and stirred at 80 ° C. After stirring for 8 hours, the reaction mixture was cooled to room temperature, and the resulting yellow solid was filtered, washed with water and ethanol. The dried compound was dissolved in 120 mL of 1M NaOH solution and stirred. After washing with water, Compound 3C (9.9 g, ).

MS: [M + H] &lt; ⁺ &gt; = 446

< Synthetic example  4>

1) Preparation of compound 4A

5- (4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl) quinoline (5- (4,4,5,5,5-tetramethyl- 1-bromo-2-iodobenzene (28.3 g, 100 mmol) was completely dissolved in tetrahydrofuran (400 mL), followed by the addition of a 2 M aqueous potassium carbonate solution , And tetrabistriphenylphosphinopalladium (2.3 g, 2 mmol) were added thereto, followed by heating and stirring for 10 hours. The temperature was lowered to room temperature, and the resulting solution was dried over anhydrous magnesium sulfate and column-purified with CHCl ₃ / n-Hex to give Compound 4A (15.3 g, yield 54%).

MS: [M + H] &lt; ⁺ &gt; = 284

2) Preparation of compound 4B

To the compound 4A (15.3 g, 54 mmol) synthesized in 1) above was added anhydrous THF (100 mL) under a nitrogen atmosphere, and the reaction temperature was maintained at -78 ^° C. n-BuLi (2.5 M in HEX, 26 mL, 65 mmol) was added dropwise to the reaction solution. After stirring for about 40 minutes, 2-bromofluorenone (14.0 g, 35 mmol) was added to the reaction mixture and stirred. After about 1 hour, the temperature was raised to room temperature and stirred for 3 hours. Aqueous ammonium chloride solution was added to the reaction mixture and the THF layer was separated. The organic layer was dried over anhydrous magnesium sulfate, and ethyl ether was added thereto to prepare a solid compound 4B.

3) Preparation of compound 4C

Compound 4B obtained in 2) was not further purified, and 100 mL of acetic acid was added and stirred. 2 mL of sulfuric acid was added dropwise to the reaction solution, and the mixture was heated and stirred at 80 ° C. After stirring for 8 hours, the reaction mixture was cooled to room temperature, and the resulting yellow solid was filtered, washed with water and ethanol. The dried compound was dissolved in 200 mL of 1M NaOH solution and stirred. After washing with water, Compound 4C (24.7 g, yield 87% ).

MS: [M + H] &lt; ⁺ &gt; = 525

< Synthetic example  5>

1) Preparation of compound 5A

6- (4,4,5,5-tetramethyl-1,3,2-dioxabororen-2-yl) phenanthridine (6- (4,4,5,5-tetramethyl-1,3 Bromo-2-iodobenzene (28.3 g, 100 mmol) was completely dissolved in tetrahydrofuran (400 mL), followed by the addition of a 2 M aqueous potassium carbonate solution And tetrabistriphenylphosphinopalladium (2.3 g, 2 mmol) were added thereto, followed by heating and stirring for 10 hours. The temperature was lowered to room temperature, and the resulting solution was dried over anhydrous magnesium sulfate and column-purified with CHCl ₃ / n-Hex to give Compound 5A (28.4 g, yield 85%).

MS: [M + H] &lt; ⁺ &gt; = 334

2) Preparation of compound 5B

Compound A (16.7 g, 50 mmol) synthesized in 1) above was added with anhydrous THF (100 mL) under nitrogen atmosphere, and the reaction temperature was maintained at -78 ^° C. n-BuLi (2.5 M in HEX, 24 mL, 60 mmol) was added dropwise to the reaction solution. After stirring for about 40 minutes, 2-bromofluorenone (13 g, 50 mmol) was added to the reaction mixture and stirred. After about 1 hour, the temperature was raised to room temperature and stirred for 3 hours. Aqueous ammonium chloride solution was added to the reaction mixture and the THF layer was separated. The organic layer was dried over anhydrous magnesium sulfate, and ethyl ether was added thereto to prepare a solid compound 5B.

3) Preparation of compound 5C

Compound 5B obtained in 2) above was not purified, and 100 mL of acetic acid was added and stirred. 2 mL of sulfuric acid was added dropwise to the reaction solution, and the mixture was heated and stirred at 80 ° C. After stirring for 8 hours, the reaction mixture was cooled to room temperature, and the resulting yellow solid was filtered, washed with water and ethanol. The dried compound was dissolved in 200 mL of 1 M NaOH solution and then washed with water, followed by filtration to obtain Compound 5C (17.9 g, ).

MS: [M + H] &lt; ⁺ &gt; = 496

< Synthetic example  6>

1) Preparation of Compound 6A

9-phenyl-9H-carbazol-3-yl-3-boronic acid (19.9 g, 50 mmol), 1-bromo-2-iodo Benzene (14.2 g, 50 mmol) was completely dissolved in tetrahydrofuran (400 mL), 2M potassium carbonate aqueous solution was added, tetrabistriphenylphosphinopalladium (2.3 g, 2 mmol) was added and the mixture was heated with stirring for 10 hours . The temperature was lowered to room temperature, and the resulting solution was dried over anhydrous magnesium sulfate and column-purified with CHCl ₃ / n-Hex to give Compound 6A (10.3 g, yield 52%).

MS: [M + H] &lt; ⁺ &gt; = 398

2) Preparation of compound 6B

Compound 6A (10.3 g, 25.9 mmol) synthesized in 1) above was added anhydrous THF (60 mL) under a nitrogen atmosphere, and the reaction temperature was maintained at -78 ^° C. n-BuLi (2.5 M in HEX, 14.5 mL, 36.3 mmol) was added dropwise to the reaction solution. After stirring for about 40 minutes, 2-bromofluorenone (6.5 g, 25 mmol) was added to the reaction mixture and stirred. After about 1 hour, the temperature was raised to room temperature and stirred for 3 hours. Aqueous ammonium chloride solution was added to the reaction mixture and the THF layer was separated. The organic layer was dried over anhydrous magnesium sulfate, and ethyl ether was added thereto to prepare a solid compound 6B.

3) Preparation of compound 6C

Compound 6B obtained in 2) was not further purified, and 60 mL of acetic acid was added and stirred. 1 mL of sulfuric acid was added dropwise to the reaction solution, and the mixture was heated and stirred at 60 ° C. After stirring for 5 hours, the reaction mixture was cooled to room temperature, and the resulting yellow solid was filtered, washed with water and ethanol. The dried compound was mixed with 100 mL of 1 M NaOH solution, stirred, washed with water and filtered to obtain Compound 6C (6.2 g, ).

MS: [M + H] &lt; ⁺ &gt; = 560

< Manufacturing example  1> Preparation of compound 1-1-25

2- (4,4,5,5-tetramethyl-1,3,2-dioxabororane-2-yl) benzo [h] quinoline (2- (4,4,5,5- (6.7 g, 20.0 mmol) and sodium carbonate (5.5 g, 40.0 mmol) were dissolved in tetrahydrofuran (300 mL) and water (10 mL) 100 mL). Tetrakis (triphenylphosphine) palladium (0.4 g, 0.36 mmol) was added to the suspension. The mixture was stirred at reflux for about 24 hours and then cooled to room temperature. The resulting solid was purified by filtration of THF / EtOH to obtain Compound 1-1-25 (7.1 g, yield 46%).

MS [M + H] &lt; ⁺ &gt; = 772

< Manufacturing example  2> Preparation of compound 1-1-23

Naphthalen-2-yl-2-boronic acid (7.6 g, 44 mmol), Compound 1C (7.0 g, 21 mmol) and sodium carbonate (5.0 g, 35.9 mmol) were dissolved in tetrahydrofuran 300 mL) and water (100 mL). Tetrakis (triphenylphosphine) palladium (0.4 g, 0.36 mmol) was added to the suspension. The mixture was stirred at reflux for about 24 hours and then cooled to room temperature. The resulting solid was purified by filtration with THF / EtOH to give Compound 1-1-23 (10.7 g, yield 76%).

MS [M + H] &lt; ⁺ &gt; = 670

< Manufacturing example  3> Preparation of Compound 1-1-17

In the production example 1-1-25 of Preparation Example 1, 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzo [h] (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzo [h] quinoline instead of 2- Yl) naphthalen-6-yl) -1-phenyl-1H-benzo [d] imidazole (2- (2- (4,4,5,5- 5-tetramethyl-1,3,2-dioxaborolan-2-yl) naphthalen-6-yl) -1-phenyl-1H-benzo [d] imidazole, 4.5 g, 10.0 mmol) g, 10 mmol), the compound 1-1-17 (4.8 g, yield 65%) was prepared.

MS [M + H] &lt; ⁺ &gt; = 736

< Manufacturing example  4> Preparation of Compound 1-1-19

In the production example 1-1-25 of Preparation Example 1, 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzo [h] (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzo [h] quinoline, Yl) phenyl) -4,6-diphenyl-1,3,5-triazine (2- (4- (4,4,5,5-tetramethyl- The reaction was carried out in the same manner except that 5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -4,6-diphenyl-1,3,5-triazine, 4.4 g, 10.0 mmol) 1-1-19 (3.6 g, yield 49%).

MS [M + H] &lt; ⁺ &gt; = 725

< Manufacturing example  5> Preparation of compound 1-5-1

In Production Example 1-1-25 of Production Example 1, 2- [9,10-di-2-naphthalenyl-2-anthracenyl] -4,4,5,5- 9- 10-di-2-naphthalenyl-2-anthracenyl] -4,4,5,5-tetramethyl-1,3,2-dioxaborolane instead of 3- [ (Naphthalen-3-yl) anthracene-10-yl-10-boronic acid (9- (naphthalen-3-yl) anthracen- To give compound 1-5-1 (4.1 g, yield 57%).

MS [M + H] &lt; ⁺ &gt; = 719

< Manufacturing example  6> Preparation of compound 1-6-1

In Production Example 1-1-25 of Production Example 1, 2- [9,10-di-2-naphthalenyl-2-anthracenyl] -4,4,5,5- 2-naphthalenyl-2-anthracenyl] -4,4,5,5-tetramethyl-1,3,2-dioxaborolane instead of 2- [9,10- (4- (4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl) phenyl) Phenyl-1-phenyl-1H-benzo [d] imidazole (4.0 g, 10.0 mmol) was added to a solution of compound 2C Compound 3-6-1 (3.9 g, yield 52%) was prepared by the same procedure except that Compound 3C (5.2 g, 10.0 mmol) was used instead.

MS [M + H] &lt; ⁺ &gt; = 686

< Manufacturing example  7> Preparation of compound 1-6-7

In Production Example 1-1-25 of Production Example 1, 2- [9,10-di-2-naphthalenyl-2-anthracenyl] -4,4,5,5- 4, 5,5-tetramethyl-1,3,2-dioxaborolane instead of 2- [9,10-di-2- naphthalenyl- 2- anthracenyl] 4,5,5-tetramethyl-2- (2- (naphthalen-7-yl) naphthalen-6-yl) -1,3,2-dioxabororane (4,4,5,5- The reaction was carried out in the same manner except that 2- (2- (naphthalen-7-yl) naphthalen-6-yl) -1,3,2-dioxaborolane, 4.0 g, 10.5 mmol) 4.7 g, yield 58%).

MS [M + H] &lt; ⁺ &gt; = 670

< Manufacturing example  8> Preparation of Compound 1-1-29

1.4 g (14 mmol) of sodium-tertiary-butoxide and 0.1 g of Pd [P (t-Bu) ₃ ] _{2 were added to a solution of} 0.1 g (24 mmol) g (0.2 mmol) was added thereto, and the mixture was refluxed in a nitrogen stream for 5 hours. Distilled water was added to the reaction solution, the reaction was terminated, and the organic layer was extracted. And recrystallized with a solvent of n-hexane / CHCl ₃ to obtain Compound 1-1-29 (4.7 g, yield 63%).

MS: [M + H] &lt; ⁺ &gt; = 748

< Manufacturing example  9> Preparation of compound 1-4-21

In Production Example 1-1-25 of Production Example 1, 2- [9,10-di-2-naphthalenyl-2-anthracenyl] -4,4,5,5- 9- 10-di-2-naphthalenyl-2-anthracenyl] -4,4,5,5-tetramethyl-1,3,2-dioxaborolane instead of 3- [ (Naphthalen-1-yl) anthracene-10-yl-10-boronic acid (9.9 g, 25 mmol) To give compound 1-4-21 (15.5 g, yield 79%).

MS [M + H] &lt; ⁺ &gt; = 784

< Experimental Example  1>

The glass substrate coated with ITO (indium tin oxide) film with a thickness of 1,500 Å was immersed in distilled water containing detergent and washed with ultrasonic waves. As a detergent, a product of Fischer Co. was used. Distilled water, which was filtered by a filter of Millipore Co., was used as distilled water. 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 transported to a plasma cleaner. The substrate was cleaned using oxygen plasma for 5 minutes, and then the substrate was transported by a vacuum evaporator.

Hexanitrile hexaazatriphenylene was thermally vacuum deposited on the prepared ITO transparent electrode to a thickness of 500 Å to form a hole injection layer. NPB (400 Å), which is a hole transporting material, was vacuum deposited thereon, and a host H1 and a dopant D1 compound were vacuum deposited as a light emitting layer to a thickness of 300 Å.

[Hexanitrile hexaazatriphenylene]

[NPB]

[H1]

[D1]

Compound 1-1-25 prepared in Preparation Example 1 was vacuum deposited on the light emitting layer to a thickness of 200 Å to form an electron injection and transport layer. Lithium fluoride (LiF) 12 Å thick and aluminum 2,000 Å thick were sequentially deposited on the electron injection and transport layer to form a cathode. In the above process, the deposition rate of the organic material was maintained at 1 Å / sec, the deposition rate of lithium fluoride was 0.2 Å / sec, and the deposition rate of aluminum was 3 to 7 Å / sec.

< Experimental Example  2>

The same experiment was carried out in Experimental Example 1 except that Compound 1-1-23 was used instead of Compound 1-1-25 prepared in Preparation Example 1 on the light emitting layer.

< Experimental Example  3>

The same experiment was conducted as in Experimental Example 1 except that Compound 1-1-17 was used instead of Compound 1-1-25 prepared in Preparation Example 1 on the light emitting layer.

< Experimental Example  4>

The same experiment as in Experimental Example 1 was conducted except that Compound 1-1-19 was used instead of Compound 1-1-25 prepared in Preparation Example 1 on the light emitting layer.

< Experimental Example  5>

In Experimental Example 1, the same experiment was conducted except that Compound 1-5-1 was used instead of Compound 1-1-25 prepared in Preparation Example 1 on the light emitting layer.

< Experimental Example  6>

In Experimental Example 1, the same experiment was carried out except that Compound 1-6-1 was used instead of Compound 1-1-25 prepared in Preparation Example 1 on the light emitting layer.

< Experimental Example  7>

In Experimental Example 1, the same experiment was conducted except that Compound 1-6-7 was used instead of Compound 1-1-25 prepared in Preparation Example 1, on the light-emitting layer.

< Experimental Example  8>

In Experimental Example 1, the same experiment was conducted except that Compound 1-1-29 was used instead of Compound 1-1-25 prepared in Preparation Example 1 on the light emitting layer.

< Experimental Example  9>

In Experimental Example 1, the same experiment was conducted except that Compound 1-4-21 was used instead of Compound 1-1-25 prepared in Preparation Example 1 on the light emitting layer

< Comparative Experimental Example  1>

The same experiment was carried out in Experimental Example 1 except that the following Alq ₃ was used instead of the compound 1-1-25 prepared in Preparation Example 1 on the light emitting layer.

[Alq ₃ ]

Table 1 shows the results of the experiment of the organic light emitting device manufactured by using each compound as an electron injection and transport layer material as in Experimental Examples 1 to 9 and Comparative Experimental Example 1.

As shown in Table 1, it was found that the devices of Experimental Examples 1 to 9 had improved characteristics in terms of low voltage and efficiency as compared with the device of Comparative Experiment Example 1.

Claims (9)

delete delete A compound represented by the following formula (1):
[Chemical Formula 1]

(1) is represented by any one of the following formulas (6) to (8)
[Chemical Formula 6]

(7)

[Chemical Formula 8]

In Formula 6,
At least one of X ₁ -Ar ₁ to X ₈ -Ar ₈ is a nitrogen atom (N) and the others are CH,
In Formula 7,
At least one of X ₁ -Ar ₁ to X ₆ -Ar ₆ is a nitrogen atom (N) and the others are CH,
In Formula 8,
At least one of X ₁ -Ar ₁ to X ₈ -Ar ₈ is a nitrogen atom (N) and the others are each independently CH; Carbon substituted with a naphthalene group; Carbon substituted with a naphthylpyridine group; Or phenyl substituted with a benzimidazolylphenyl group,
In Formulas 6 to 8,
m is 0,
R ₁ and R ₂ may be bonded to each other to form a phenyl group substituted with a diphenyltriazine group, a benzothiazole group, a naphthalene group, a phenylbenzimidazole group, or a benzoxazole group; A naphthalene group substituted with a phenylbenzimidazole group; A naphthalene group; An anthracene group substituted with a phenyl group or a naphthalene group; Phenanthrene; Phenanthrolines; Benzoquinoline group; A pyridine group substituted with a spirobenzoindenoquinoline fluorene group; A triazine group substituted with a phenyl group; A carbazole group substituted with a phenyl group; And a carbazole group to form a substituted or unsubstituted fluorene structure. delete 4. The compound according to claim 3, wherein the compound represented by Formula 1 is selected from the group consisting of the following compounds:

delete 1. An organic electronic device comprising a first electrode, a second electrode, and at least one organic compound layer disposed between the first electrode and the second electrode, wherein the organic compound layer comprises the compound represented by the general formula (1) Wherein the organic electronic device is an organic electronic device. [Claim 7] The organic electronic device according to claim 7, wherein the organic material layer comprises at least one layer selected from the group consisting of a hole injection layer, a hole transporting layer, a light emitting layer, an electron injecting layer and an electron transporting layer. The organic electronic device according to claim 7, wherein the organic electronic device is selected from the group consisting of an organic light emitting device, an organic phosphor device, an organic solar cell, an organic photoconductor (OPC), and an organic transistor.

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