KR101401847B1 - Novel compound derivative, process for preparing the same, and organic electronic device using the same - Google Patents

Abstract

The present invention provides a novel compound derivative and an organic electronic device using the same. The organic electronic device according to the present invention exhibits excellent characteristics in terms of efficiency, driving voltage and lifetime.

Description

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

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

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 generally has a structure including an anode, a cathode, and an organic material layer therebetween. Here, in order to enhance the efficiency and stability of the organic light emitting device, the organic material layer may have a multi-layered 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 the two electrodes in the structure of such an organic light emitting device, holes are injected in the anode, electrons are injected into the organic layer in the cathode, excitons are formed when injected holes and electrons meet, When it falls back to the ground state, the light comes out. 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 light emitting material may be classified into a polymer type and a low molecular type depending on the molecular weight, and may be classified into a phosphorescent material derived from singlet excited state of electrons and a phosphorescent material derived from the triplet excited state of electrons . Further, the light emitting material can be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to realize better natural color depending on the luminescent color.

On the other hand, when only one material is used as a light emitting material, there arises a problem that the maximum light emission wavelength shifts to a long wavelength due to intermolecular interaction, the color purity decreases, or the efficiency of the device decreases due to the light emission attenuating effect. A host / dopant system may be used as the light emitting material in order to increase the light emitting efficiency through the light emitting layer. When the dopant having a smaller energy band gap than the host forming the light emitting layer is mixed with a small amount of the light emitting layer, the excitons generated in the light emitting layer 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. Further, it has been found that when the organic compound layer of the organic electronic device is formed using the compound having the novel structure, the efficiency of the device, the driving voltage drop, and the stability can be imagined.

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

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

The present invention also provides 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 at least one of the organic compound layers is a compound And an organic electroluminescent device.

The compound represented by the formula (I) according to the present invention can act as a hole injecting, hole transporting, electron injecting and transporting or light emitting material in an organic electric device including an organic light emitting device. And exhibits excellent characteristics in terms of stability.

Fig. 1 shows an example of an organic light-emitting device comprising a substrate 1, an anode 2, a light-emitting layer 3 and a cathode 4. Fig.
2 shows an example of an organic light emitting element comprising a substrate 1, an anode 2, a hole injecting layer 5, a hole transporting layer 6, a light emitting layer 7, an electron transporting layer 8 and a cathode 4 It is.

The present invention provides compounds of formula 1:

In Formula 1, R ₁ to R ₄ Are each independently the same or different substituent, and is 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 aryl; Substituted or unsubstituted heteroaryl; Substituted or unsubstituted C ₃ -C ₇ cycloalkyl wherein the carbon atoms in the ring may be optionally replaced by an oxygen, nitrogen or sulfur atom; C ₄ -C ₇ cycloalkenyl wherein the carbon atoms in the ring may be optionally replaced by an oxygen, nitrogen or sulfur atom; 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 aryloxy; A substituted or unsubstituted C ₁ -C ₂₀ alkylamine; Substituted or unsubstituted C ₂ -C ₁₀ alkenylamines; Substituted or unsubstituted C ₂ -C ₇ alkynylamines; Substituted or unsubstituted arylamine; Substituted or unsubstituted alkylarylamines; 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 arylsilyl; Substituted or unsubstituted 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 arylboranyl; Substituted or unsubstituted 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 arylthio group,

Wherein R 1 to R 4 are selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkylamine, alkenylamine, alkynylamine, aryl Alkylarylsilyl, alkylarylsilyl, alkylboranyl, alkenylboranyl, alkynylboranyl, arylboranyl, alkylarylboranyl, alkylthio, alkylthio, alkylthio, A halogen atom, an amino group, a nitrile group, a nitro group, a C ₁ -C ₄₀ alkyl group, a C ₂ -C ₄₀ alkenyl group, a C ₁ -C ₄₀ alkoxy group, an alkenylthio group, an alkynylthio group, , A C ₃ -C ₄₀ cycloalkyl group, a C ₃ -C ₄₀ heterocycloalkyl group, a C ₆ -C ₄₀ aryl group, and a C ₅ -C ₄₀ heteroaryl group.

However, R ₁ To R ₄ and at least one is hydrogen, R ₁ To R ₄ is a substituted or unsubstituted fluorenyl group, a phenyl group, a naphthyl group, an anthracenyl group, a biphenyl group, a pyrenyl group, a perylene group, or a klycenyl group,

n is an integer of 1 to 10;

In Formula 1, R < 1 _> When R ₄ is substituted or unsubstituted aryl, the aryl group preferably has 6 to 20 carbon atoms, and specific examples thereof include aryl groups such as benzene, naphthalene, biphenyl, altracene, phenanthrene, But are not limited to these.

In Formula 1, R < 1 _> When R ₄ is substituted or unsubstituted heteroaryl, the heteroaryl group preferably has 5 to 20 carbon atoms, and specific examples thereof include, but are not limited to, the following structural formulas.

In addition, the R ₁ At least one of R < ₄ > and R < ₄ >

In the above formulas (2), (3) and (4)

L1 is a direct bond; A C ₂ -C ₄₀ alkenylene group unsubstituted or substituted with at least one group selected from the group consisting of a C ₆ -C ₄₀ aryl group and a C ₅ -C ₄₀ heteroaryl group; A halogen, an amino group, a nitrile group, a nitro group, a cycloalkyl group of C ₁ -C ₄₀ alkyl, C ₂ -C ₄₀ alkenyl group, C ₁ -C ₄₀ alkoxy group, C ₃ -C ₄₀ in the, C ₃ -C ₄₀ a heterocycloalkyl group, C ₆ -C ₄₀ aryl groups and C ₅ -C substituted by at least one group selected from the group consisting of a heteroaryl group of ₄₀ or unsubstituted aryl group of C ₆ -C _40; A halogen, an amino group, a nitrile group, a nitro group, a cycloalkyl group of C ₁ -C ₄₀ alkyl, C ₂ -C ₄₀ alkenyl group, C ₁ -C ₄₀ alkoxy group, C ₃ -C ₄₀ in the, C ₃ -C ₄₀ a heterocycloalkyl group, a heteroaryl group of C ₆ -C ₄₀ aryl groups and C ₅ -C substituted by at least one group selected from the group consisting of a heteroaryl group of ₄₀ or unsubstituted C ₅ -C _40; And C ₁ -C ₄₀ alkyl, C ₂ -C ₄₀ alkenyl groups, C ₁ -C ₄₀ alkoxy group, C ₃ -C ₄₀ cycloalkyl group, C ₃ -C ₄₀ heterocycloalkyl group, C ₆ -C of substituted with one or more groups selected from the ₄₀ aryl group and a heteroaryl group the group consisting of C ₅ -C _40, or is selected from the group consisting of an aryl group unsubstituted C ₆ -C _40,

R5 and R6 are the same or different from each other and represent hydrogen; A halogen, an amino group, a nitrile group, a nitro group, a cycloalkyl group of C ₁ -C ₄₀ alkyl, C ₂ -C ₄₀ alkenyl group, C ₁ -C ₄₀ alkoxy group, C ₃ -C ₄₀ in the, C ₃ -C ₄₀ A C ₁ -C ₄₀ alkyl group which is unsubstituted or substituted with at least one group selected from the group consisting of a heterocycloalkyl group, a C ₆ -C ₄₀ aryl group and a C ₅ -C ₄₀ heteroaryl group; A halogen, an amino group, a nitrile group, a nitro group, a cycloalkyl group of C ₁ -C ₄₀ alkyl, C ₂ -C ₄₀ alkenyl group, C ₁ -C ₄₀ alkoxy group, C ₃ -C ₄₀ in the, C ₃ -C ₄₀ A C ₃ -C ₄₀ cycloalkyl group unsubstituted or substituted with at least one group selected from the group consisting of a heterocycloalkyl group, a C ₆ -C ₄₀ aryl group and a C ₅ -C ₄₀ heteroaryl group; A halogen, an amino group, a nitrile group, a nitro group, an alkyl group of C1-C40, C ₂ -C ₄₀ alkenyl groups, C ₁ -C ₄₀ alkoxy group, a C ₃ -C ₄₀ cycloalkyl group, a heterocyclic C ₃ -C ₄₀ A C ₃ -C ₄₀ alkenyl group which is unsubstituted or substituted with at least one group selected from the group consisting of a cycloalkyl group, a C ₆ -C ₄₀ aryl group and a C ₅ -C ₄₀ heteroaryl group; A halogen, an amino group, a nitrile group, a nitro group, a cycloalkyl group of C ₁ -C ₄₀ alkyl, C ₂ -C ₄₀ alkenyl group, C ₁ -C ₄₀ alkoxy group, C ₃ -C ₄₀ in the, C ₃ -C ₄₀ A C ₃ -C ₄₀ alkoxy group unsubstituted or substituted with at least one group selected from the group consisting of a heterocycloalkyl group, a C ₆ -C ₄₀ aryl group, and a C ₅ -C ₄₀ heteroaryl group; A halogen, an amino group, a nitrile group, a nitro group, a cycloalkyl group of C ₁ -C ₄₀ alkyl, C ₂ -C ₄₀ alkenyl group, C ₁ -C ₄₀ alkoxy group, C ₃ -C ₄₀ in the, C ₃ -C ₄₀ A C ₃ -C ₄₀ amino group unsubstituted or substituted with at least one group selected from the group consisting of a heterocycloalkyl group, a C ₆ -C ₄₀ aryl group and a C ₅ -C ₄₀ heteroaryl group; A halogen, an amino group, a nitrile group, a nitro group, a cycloalkyl group of C ₁ -C ₄₀ alkyl, C ₂ -C ₄₀ alkenyl group, C ₁ -C ₄₀ alkoxy group, C ₃ -C ₄₀ in the, C ₃ -C ₄₀ a heterocycloalkyl group, an aryl group of C ₆ -C ₄₀ aryl groups and C ₅ -C substituted by at least one group selected from the group consisting of a heteroaryl group of ₄₀ or unsubstituted C ₆ -C _40; And a halogen, an amino group, a nitrile group, a nitro group, an alkyl group of C1-C40, C ₂ -C ₄₀ alkenyl group, an alkoxy group, a cycloalkyl group of C ₃ -C ₄₀ in _{C 1 -C 40, C 3 -C} 40 heterocycloalkyl group, C ₆ substituted by at least one group selected from the group consisting of a heteroaryl -C ₄₀ aryl groups and C ₅ -C ₄₀ or or heteroaryl selected from the group consisting of unsubstituted C ₅ -C _40, adjacent To form a condensed ring of aliphatic, aromatic, heteroaliphatic or heteroaromatic rings or to form a spiro bond.

Specific examples of the compound of Formula 1 are shown in Table 1 below, but are not limited thereto.

In the compound of formula (1), the compound having the substituent structure including the compound of formula (1) according to the present invention contributes significantly to the improvement of lifetime and the luminous efficiency than the compound of similar structure without formula (1) according to the present invention. This is one of the important characteristics required for both the host and the dopant of the light emitting layer. Therefore, the luminous efficiency of the device can be greatly improved through the novel structure represented by the formula (1).

The compound of the formula (1) according to the present invention can be prepared by using bromobenzene and anthracene boronic acid substituted with a substituted ring group as a starting material, and introducing a substituent thereto by an aryl-aryl coupling method. A specific method for preparing the compound of formula (1) according to the present invention is shown in the examples.

The present invention also provides 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 at least one of the organic compound layers is a compound And an organic electroluminescent device.

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.

Hereinafter, the organic light emitting device will be described.

The compounds of the present invention can act as a hole injecting, hole transporting, electron injecting, electron transporting, or luminescent material in an organic light emitting device. The compounds of the present invention can serve not only as a light emitting material in an organic light emitting device, but also as a light emitting dopant together with an appropriate light emitting dopant as well as an appropriate light emitting host.

In one embodiment of the present invention, the organic light emitting device may have a structure including a first electrode, a second electrode, and an organic material layer interposed therebetween, and the above- The organic light emitting device can be manufactured using a conventional method and materials for manufacturing an organic light emitting device, 1 and 2, the scope of the present invention is not limited to these examples.

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, A hole transporting layer, a light emitting layer, and an electron transporting layer, and then depositing a material usable as a cathode on the organic material layer. In addition to such a method, an organic light emitting device may be fabricated by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate (see International Patent Application Publication No. 2003/012890).

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. In addition, the organic material layer may be formed using a variety of polymer materials by a solvent process such as a spin coating process, a dip coating process, a doctor blading process, a screen printing process, an inkjet printing process or a thermal transfer process, Layer.

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-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (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, quinacridone-based organic materials, perylene-based organic materials, Anthraquinone, polyaniline and a polythiophene-based conductive polymer, but are not limited thereto.

As the hole transporting material, a material having high mobility to holes is suitable for transporting holes from the anode or the hole injection layer to the light emitting layer. 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 can act on a principle similar to that applied to an organic light emitting device in an organic electronic device including an organic solar cell, an organophotoreceptor, an organic transistor and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples. However, the scope of the present invention is not limited by the following Examples and Experimental Examples.

Example  One  : Preparation of Compound (1)

1-A. Preparation of Compound 1a

Copper bromide (18 g, 80.0 mmol) and t-butyl nitrite (12 mL, 101 mmol) were dispersed and stirred in acetonitrile (250 mL) at 65 ° C and then 2-aminoanthraquinone (15 g, 67.2 mmol) Lt; / RTI > When gas evolution was completed, the reaction solution was cooled to room temperature, and the reaction solution was added to a 20% aqueous hydrochloric acid solution (1 L) and extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate to remove residual moisture, and then dried under reduced pressure. The resultant was separated by column chromatography to obtain pale yellow Compound 1a (14.5 g, 75%).

MS [M] = 287

1-B. Preparation of compound 1b

2-Bromonaphthalene (11.0 g, 53.1 mmol) was dissolved in THF (100 mL) dried under nitrogen atmosphere, t-butyllithium (46.8 mL, 1.7 M pentane solution) was added slowly at -78 ° C, And the compound 1a (6.36 g, 22.0 mmol) was added thereto. After the cooling vessel was removed, the mixture was stirred at room temperature for 3 hours. An aqueous ammonium chloride solution was added to the reaction mixture, followed by extraction with methylene chloride. The organic layer was dried over anhydrous magnesium sulfate and the solvent was removed. The resulting mixture was dissolved in a small amount of ethyl ether, petroleum ether was added, and the mixture was stirred for several hours to obtain a solid compound. The solid compound was filtered and dried under vacuum to obtain Compound 1b (11.2 g, 93%).

MS [M] = 543

1-C. Preparation of compound 1c

The compound 1b (11.2 g, 20.5 mmol) was dispersed in acetic acid (200 mL) under a nitrogen atmosphere, potassium iodide (34 g, 210 mmol) and sodium hypophosphite hydrate (37 g, 420 mmol) were added and the mixture was stirred for 3 hours while boiling. After cooling at room temperature, the mixture was filtered, washed with water and methanol, and then vacuum-dried to obtain pale yellow Compound 1c (7.2 g, 64%).

MS [M] = 509

1-D. Preparation of compound 1d

(2.75 g, 10.9 mmol), potassium acetate (2.89 g, 29.4 mmol), palladium (diphenylphosphinoferrocene) chloride (0.24 g, 3 mol%) was placed in a 250 mL flask, and dioxane (50 mL) was added thereto, followed by reflux at 80 ° C for 6 hours. After cooling the reaction solution at room temperature, distilled water (50 mL) was added and extracted with methylene chloride (50 mL x 3). The methylene chloride was removed under reduced pressure to give a pale yellow solid. The pale yellow solid was washed with ethanol and dried to obtain Compound 1d (5.46 g, 92%).

MS [M] = 556

1-E. Preparation of Compound 1e

Dissolve the compound 1d (15 g, 26.9 mmol) and 1-bromo-3-iodobenzene (7.6 g, 26.9 mmol) prepared in the step 1-D in dry THF (200 mL), Pd ( PPh 3) 4 ( 0.3 g, 0.27 mmol), and 100 mL of 2M K ₂ CO ₃ (aq) was added thereto, followed by refluxing with stirring. After 3 hours, the mixture was washed with brine, and the organic layer was extracted with ethyl acetate. The filtrate was concentrated under reduced pressure and the solvent was removed. The residue was purified by column chromatography to obtain Compound 1e (14 g, 88%).

MS [M] = 585

1-F. Preparation of compound 1f

(7.3g, 28.7mmol), potassium acetate (7.0g, 71.7mmol), palladium (diphenylphosphinoferrocene) chloride (0.59mmol) were added to a solution of the compound 1e (14g, 23.91mmol), bis (pinacolato) diboron g, 3 mol%) was placed in a 500 mL flask, and dioxane (200 mL) was added thereto, followed by reflux at 80 ° C for 6 hours. After cooling the reaction solution at room temperature, distilled water (50 mL) was added and extracted with methylene chloride (100 mL x 3). The methylene chloride was removed under reduced pressure to give a pale yellow solid. The pale yellow solid was washed with ethanol and dried to give Compound 1f (12.2 g, 81%).

MS [M] = 632

1-G. Preparation of 1 g compound

3-bomo put thiophene (11.5 ml, 122.7 mmol) and phenylboronic acid (16.45 g, 134.9 mmol) in anhydrous _{THF, Pd (PPh 3) 4} (1.42 g, 1.2 mmol) is dissolved in (200 mL), 2M 100 mL of K ₂ CO ₃ (aq) was added and the mixture was refluxed with stirring. After 3 hours, the mixture was washed with brine, and the organic layer was extracted with ethyl acetate. The filtrate was concentrated under reduced pressure and the solvent was removed. The residue was separated by column chromatography to obtain 1 g (17.1 g, 87%) of the compound.

 MS [M] = 160

1-H. Preparation of compound 1h

1 g (12.0 g, 74.88 mmol) of the above compound was dissolved in dimethylformamide (DMF, 200 mL) and N-bromosuccinimide (NBS, 13.3 g, 74.88 mmol) was added thereto. The reaction mixture was reacted at 50 to 60 ° C for 2 hours and then water (200 mL) was added thereto. The resulting precipitate was filtered, washed with water and then recrystallized in dichloromethane / n-hexane to obtain compound 1h (16.5 g, 92%).

MS [M] = 239

1-I. Preparation of compound 1i

Dissolve 1h (16.5 g, 68.9 mmol) and phenylboronic acid (10.0 g, 82.36 mmol) the above compound in anhydrous THF (200 mL), placed _{Pd (PPh 3) 4 (0.86} g, 0.74 mmol), 2M K 2 100 mL of CO ₃ (aq) was added and the mixture was refluxed with stirring. After 3 hours, the mixture was washed with brine, and the organic layer was extracted with ethyl acetate. The filtrate was concentrated under reduced pressure to remove the solvent, and the residue was purified by column chromatography to obtain Compound 1i (15.3 g, 94%).

MS [M] = 236

1-J. Preparation of compound 1j

The compound 1i (15.3 g, 64.73 mmol) was dissolved in dimethylformamide (DMF, 200 mL) and N-bromosuccinimide (NBS, 11.5 g, 64.73 mmol) was added. The reaction mixture was reacted at 50 to 60 ° C for 2 hours and then water (200 mL) was added thereto. The resulting precipitate was filtered, washed with water and then recrystallized from dichloromethane / n-hexane to obtain compound 1j (19.38 g, 95%).

MS [M] = 315

1-K. Preparation of Compound (1)

Dissolve 1f (3.78 g, 5.98 mmol) and the compound 1j (1.9 g, 5.98 mmol) the above compound in anhydrous THF (100 mL), placed _{Pd (PPh 3) 4 (0.2} g, 0.18 mmol), 2M K 2 50 mL of CO ₃ (aq) was added, and the mixture was refluxed with stirring. After 24 hours, the mixture was washed with brine, and the organic layer was extracted with ethyl acetate. After removing water with magnesium sulfate and filtering under reduced pressure, the solvent was removed by concentration, and the resultant product was separated by column chromatography to obtain Compound 1 (3.14 g, 71%).

 MS [M] = 740

Example  2  : Preparation of compound 2

2-A. Preparation of Compound 2a

Compound 1j (9.86 g, 31.3 mmol) prepared in the above 1-J was dissolved in anhydrous THF (200 mL), the temperature was lowered to -10 ° C and n-butyllithium (15 mL, 37.5 mmol) . After stirring for 1 hour, the temperature was lowered to -78 ° C, boronic acid trimethyl ester (10.5 mL, 93.75 mmol) was slowly added thereto, and the mixture was stirred for 12 hours. After the temperature was lowered to 0 占 폚, a 10 wt% aqueous solution of sulfuric acid (16 mL) was added and stirred to obtain a white precipitate. The organic layer was extracted with THF, dried over magnesium sulfate and filtered under reduced pressure. The filtrate was concentrated to remove the solvent and dissolved in THF. An excess amount of 2M aqueous NaOH solution was added thereto, and the organic layer was separated with dimethylchloromethane. A hydrochloric acid aqueous solution was added to the separated aqueous layer to form a precipitate, which was then filtered to obtain Compound 2a (7.3 g, 83%).

2-B. Preparation of compound 2b

2,6-di-bromo-naphthalene (14.9g, 52.11mmol) and 2a (7.3 g, 26.06mmol) was dissolved in anhydrous THF (200mL), Pd (PPh 3) 4 (0.9g, 0.78mmol) and 2M K ₂ CO ₃ aqueous solution, and refluxed for 24 hours. The organic layer was extracted with ethyl acetate, and water was removed with magnesium sulfate. The organic layer was filtered under reduced pressure, concentrated to remove the solvent, purified by column chromatography, and recrystallized in THF and ethanol to obtain a white solid compound 2b (8.16 g, 71%).

MS [M + H] < + > = 441

2-C. Preparation of Compound 2

Dissolve the compound 1d (7.06 g, 12.69 mmol) and the compound 2b (5.6 g, 12.69 mmol) in anhydrous THF (150 mL), placed _{Pd (PPh 3) 4 (0.44} g, 0.38 mmol), 2M K 2 70 mL of CO ₃ (aq) was added and the mixture was refluxed with stirring. After 24 hours, the mixture was washed with brine, and the organic layer was extracted with ethyl acetate. After removing water with magnesium sulfate and filtering under reduced pressure, the solvent was removed by concentration and separated by column chromatography to obtain Compound 2 (8.5 g, 85%).

 MS [M] = 790

Example  3  : Preparation of compound 3

3-A. Preparation of Compound 3a

Dissolve the compound 1d (15 g, 26.9 mmol) and 1-bromo-4-iodobenzene (7.6 g, 26.9 mmol) prepared in the step 1-D in dry THF (200 mL), Pd ( PPh 3) 4 ( 0.3 g, 0.27 mmol), and 100 mL of 2M K ₂ CO ₃ (aq) was added thereto, followed by refluxing with stirring. After 3 hours, the mixture was washed with brine, and the organic layer was extracted with ethyl acetate. After removing water with magnesium sulfate and filtering under reduced pressure, the solvent was removed by concentration, and the product was separated by column chromatography to obtain Compound 3a (14 g, 88%).

MS [M] = 585

3-B. Preparation of compound 3b

(7.3g, 28.7mmol), potassium acetate (7.0g, 71.7mmol), palladium (diphenylphosphinoferrocene) chloride (0.59mmol) were added under nitrogen atmosphere to a solution of the above compound 3a (14g, 23.91mmol), bis (pinacolato) diboron g, 3 mol%) was placed in a 500 mL flask, and dioxane (200 mL) was added thereto, followed by reflux at 80 ° C for 6 hours. After cooling the reaction solution at room temperature, distilled water (50 mL) was added and extracted with methylene chloride (100 mL x 3). The methylene chloride was removed under reduced pressure to give a pale yellow solid. The pale yellow solid was washed with ethanol and dried to obtain Compound 3b (12.2 g, 81%).

MS [M] = 632

3-C. Preparation of Compound 3

Dissolve 3b (3.78 g, 5.98 mmol) and the compound 1j (1.9 g, 5.98 mmol) the above compound in anhydrous THF (100 mL), placed _{Pd (PPh 3) 4 (0.2} g, 0.18 mmol), 2M K 2 50 mL of CO ₃ (aq) was added, and the mixture was refluxed with stirring. After 24 hours, the mixture was washed with brine, and the organic layer was extracted with ethyl acetate. After removing water with magnesium sulfate and filtering under reduced pressure, the solvent was removed by concentration, and the resultant product was separated by column chromatography to obtain Compound 3 (3.94 g, 89%).

 MS [M] = 740

Example  4  : Preparation of compound 5

4-B. Preparation of compound 5b

Into the compound 5a (20 g, 52 mmol) and 3-bromophenyl boronic acid (10.4 g, 52 mmol) was dissolved in anhydrous THF (200 mL), Pd ( PPh 3) 4 (3.0 g, 2.6 mmol) , 2 mL of K ₂ CO ₃ (aq), and the mixture was refluxed with stirring. After 3 hours, the mixture was washed with brine, and the organic layer was extracted with ethyl acetate. After removing water with magnesium sulfate and filtering under reduced pressure, the solvent was removed by concentration and separated by column chromatography to obtain Compound 5b (12 g, 50%).

MS [M] = 459

4-C. Preparation of compound 5c

(10 g, 21.77 mmol), bis (pinacolato) diboron (6.6 g, 26.12 mmol), potassium acetate (6.41 g, 65.31 mmol), palladium (diphenylphosphinoferrocene) chloride 0.53 g, 3 mol%) was placed in a 500 mL flask, and dioxane (200 mL) was added thereto, followed by reflux at 80 ° C for 6 hours. After cooling the reaction solution at room temperature, distilled water (50 mL) was added and extracted with methylene chloride (100 mL x 3). The methylene chloride was removed under reduced pressure to give a pale yellow solid. The pale yellow solid was washed with ethanol and dried to obtain Compound 5c (8.93 g, 81%).

MS [M] = 506

4-D. Preparation of Compound 5

Dissolve the compound 5c (6.4 g, 12.69 mmol) and the compound 1j (4.0 g, 12.69 mmol) in anhydrous THF (150 mL), placed _{Pd (PPh 3) 4 (0.44} g, 0.38 mmol), 2M K 2 70 mL of CO ₃ (aq) was added and the mixture was refluxed with stirring. After 24 hours, the mixture was washed with brine, and the organic layer was extracted with ethyl acetate. After removing water with magnesium sulfate and filtering under reduced pressure, the solvent was removed by concentration and separated by column chromatography to obtain Compound 5 (4.0 g, 51%).

 MS [M] = 614

Example  5  : Preparation of compound 6

5-B. Preparation of compound 6b

Into the compound 6a (20 g, 52 mmol) and 3-bromophenyl boronic acid (10.4 g, 52 mmol) was dissolved in anhydrous THF (200 mL), Pd ( PPh 3) 4 (3.0 g, 2.6 mmol) , 2 mL of K ₂ CO ₃ (aq), and the mixture was refluxed with stirring. After 3 hours, the mixture was washed with brine, and the organic layer was extracted with ethyl acetate. Water was removed with magnesium sulfate, and the mixture was filtered under reduced pressure. The filtrate was concentrated to remove the solvent. The residue was separated by column chromatography to obtain Compound 6b (12 g, 50%).

MS [M] = 459

5-C. Preparation of Compound 6c

(10 g, 21.77 mmol), bis (pinacolato) diboron (6.6 g, 26.12 mmol), potassium acetate (6.41 g, 65.31 mmol), palladium (diphenylphosphinoferrocene) chloride 0.53 g, 3 mol%) was placed in a 500 mL flask, and dioxane (200 mL) was added thereto, followed by reflux at 80 ° C for 6 hours. After cooling the reaction solution at room temperature, distilled water (50 mL) was added and extracted with methylene chloride (100 mL x 3). The methylene chloride was removed under reduced pressure to give a pale yellow solid. The pale yellow solid was washed with ethanol and dried to obtain Compound 6c (8.93 g, 81%).

MS [M] = 506

5-D. Preparation of Compound 6

Dissolve the compound 6c (6.4 g, 12.69 mmol) and the compound 1j (4.0 g, 12.69 mmol) in anhydrous THF (150 mL), placed _{Pd (PPh 3) 4 (0.44} g, 0.38 mmol), 2M K 2 70 mL of CO ₃ (aq) was added and the mixture was refluxed with stirring. After 24 hours, the mixture was washed with brine, and the organic layer was extracted with ethyl acetate. After removing water with magnesium sulfate and filtering under reduced pressure, the solvent was removed by concentration and separated by column chromatography to obtain Compound 6 (6.08 g, 78%).

 MS [M] = 614

Example  6  : Preparation of compound 7

6-A. Preparation of Compound 7a

Dissolve the 9,10-dibromo-anthracene (2 g, 5.95 mmol) and 3-bromophenyl boronic acid (2.4 g, 11.9 mmol) in anhydrous THF (60 mL), Pd ( PPh 3) 4 (0.34 g, 0.30 mmol), K ₂ CO ₃ (1.8 g, 13.09 mmol) was dissolved in H ₂ O (60 mL), and the mixture was refluxed with stirring. After 3 hours, the mixture was washed with brine, and the organic layer was extracted with ethyl acetate. After removing water with magnesium sulfate and filtering under reduced pressure, the solvent was removed by concentration and separated by column chromatography to obtain Compound 7a (1.5 g, 50%).

MS [M] = 488

6-B. Preparation of Compound 7

The 6-A compound 7a (1.5 g, 3.07 mmol) , Example 1 2-A of the compound 2a (1.89 g, 6.76 mmol) , and _{Pd (PPh 3) 4 (0.18} g, 0.15 manufactured by the manufactured by mmol) were dissolved in anhydrous THF (50 mL), 2M aqueous K ₂ CO ₃ solution (50 mL) was added, and the mixture was refluxed with stirring for 3 hours. After completion of the reaction, the organic layer of the reaction solution was extracted with ethyl acetate, the water was removed with magnesium sulfate, and the filtrate was filtered under reduced pressure, followed by concentration and separation by column chromatography to obtain Compound 7 (2.08 g, 85%). MS [M] = 798

Example  7 : Preparation of compound 8

Dissolve the compound 1d (7.06 g, 12.69 mmol) and the compound 1j (4.0 g, 12.69 mmol) in anhydrous THF (150 mL), placed _{Pd (PPh 3) 4 (0.44} g, 0.38 mmol), 2M K 2 70 mL of CO ₃ (aq) was added and the mixture was refluxed with stirring. After 24 hours, the mixture was washed with brine, and the organic layer was extracted with ethyl acetate. After removing water with magnesium sulfate and filtering under reduced pressure, the solvent was removed by concentration, and the product was separated by column chromatography to obtain Compound 8 (5.65 g, 67%).

 MS [M] = 664

Example  8  : Preparation of compound 39

39-B. Preparation of compound 39b

Into the compound 5a (20 g, 52 mmol) and 4-bromophenyl boronic acid (10.4 g, 52 mmol) was dissolved in anhydrous THF (200 mL), Pd ( PPh 3) 4 (3.0 g, 2.6 mmol) , 2 mL of K ₂ CO ₃ (aq), and the mixture was refluxed with stirring. After 3 hours, the mixture was washed with brine, and the organic layer was extracted with ethyl acetate. After removing water with magnesium sulfate and filtering under reduced pressure, the solvent was removed by concentration, and the product was separated by column chromatography to obtain Compound 39b (14.4 g, 60%).

MS [M] = 459

39-C. Preparation of compound 39c

(10 g, 21.77 mmol), bis (pinacolato) diboron (6.6 g, 26.12 mmol), potassium acetate (6.41 g, 65.31 mmol), palladium (diphenylphosphinoferrocene) chloride 0.53 g, 3 mol%) was placed in a 500 mL flask, and dioxane (200 mL) was added thereto, followed by reflux at 80 ° C for 6 hours. After cooling the reaction solution at room temperature, distilled water (50 mL) was added and extracted with methylene chloride (100 mL x 3). The methylene chloride was removed under reduced pressure to give a pale yellow solid. The pale yellow solid was washed with ethanol and dried to obtain the compound 39c (10.71 g, 97%).

MS [M] = 506

39-D. Preparation of Compound 39

Into the compound 39c (6.4 g, 12.69 mmol) and the compound 1j (4.0 g, 12.69 mmol) was dissolved in anhydrous THF (150 mL), Pd ( PPh 3) 4 (0.44 g, 0.38 mmol), 2M K 2 70 mL of CO ₃ (aq) was added and the mixture was refluxed with stirring. After 24 hours, the mixture was washed with brine, and the organic layer was extracted with ethyl acetate. After removal of water with magnesium sulfate and filtration under reduced pressure, the solvent was removed by concentration and separated by column chromatography to obtain Compound 39 (6.6 g, 85%).

 MS [M] = 614

Experimental Example  One

The glass substrate coated with ITO (indium tin oxide) thin film with a thickness of 1500 Å was immersed in distilled water containing detergent and washed with ultrasonic waves. At this time, a product of Fischer Co. was used as a detergent, and distilled water, which was secondly filtered by a filter manufactured by 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 ANGSTROM), which is a hole transporting material, was vacuum-deposited thereon, and Compound 1 prepared in Example 1 was vacuum deposited as a host dopant D1 compound to a thickness of 300 ANGSTROM as a light emitting layer. E1 was vacuum deposited on the light emitting layer to a thickness of 200 ANGSTROM to form an electron injection and transport layer. Lithium fluoride (LiF) having a thickness of 12 Å and aluminum having a thickness of 2000 Å were sequentially deposited on the electron transport layer to form a cathode, thereby preparing an organic light emitting device.

[Hexanitrile hexaazatriphenylene] [NPB]

[D1] [D2]

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

An organic electronic device was prepared in the same manner as in Example 1, except that the compound 2 prepared in Example 2 was used instead of the compound 1.

Experimental Example  3

An organic electronic device was prepared in the same manner as in Example 1, except that the compound 3 prepared in Example 3 was used instead of the compound 1.

Experimental Example  4

An organic electronic device was prepared in the same manner as in Example 1, except that the compound 5 prepared in Example 4 was used instead of the compound 1.

Experimental Example  5

An organic electronic device was prepared in the same manner as in Example 1, except that the compound 6 prepared in Example 5 was used instead of the compound 1.

Experimental Example  6

An organic electronic device was prepared in the same manner as in Example 1, except that the compound 7 prepared in Example 6 was used instead of the compound 1.

Experimental Example  7

An organic electronic device was prepared in the same manner as in Example 1, except that the compound 8 prepared in Example 7 was used instead of the compound 1.

Experimental Example  8

An organic electronic device was prepared in the same manner as in Example 1, except that the compound 39 prepared in Example 8 was used instead of the compound 1.

The physical properties of the organic light emitting device manufactured in Experimental Examples 1 to 8 when a current of 10 mA is applied are shown in Table 2 below.

Claims (10)

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

In the above formula (1)
R < ₂ > is hydrogen,
R ₃ and R ₄ are phenyl groups,
R ₁ is represented by the following general formula (2) or (3)
(2)

(3)

In the general formulas (2) and (3)
L1 is a direct bond; A C ₂ -C ₄₀ alkenylene group unsubstituted or substituted with at least one group selected from the group consisting of a C ₆ -C ₄₀ aryl group and a C ₅ -C ₄₀ heteroaryl group; A halogen, an amino group, a nitrile group, a nitro group, a cycloalkyl group of C ₁ -C ₄₀ alkyl, C ₂ -C ₄₀ alkenyl group, C ₁ -C ₄₀ alkoxy group, C ₃ -C ₄₀ in the, C ₃ -C ₄₀ a heterocycloalkyl group, C ₆ -C ₄₀ aryl groups and C ₅ -C substituted by at least one group selected from the group consisting of a heteroaryl group of ₄₀ or unsubstituted aryl group of C ₆ -C _40; A halogen, an amino group, a nitrile group, a nitro group, a cycloalkyl group of C ₁ -C ₄₀ alkyl, C ₂ -C ₄₀ alkenyl group, C ₁ -C ₄₀ alkoxy group, C ₃ -C ₄₀ in the, C ₃ -C ₄₀ a heterocycloalkyl group, a heteroaryl group of C ₆ -C ₄₀ aryl groups and C ₅ -C substituted by at least one group selected from the group consisting of a heteroaryl group of ₄₀ or unsubstituted C ₅ -C _40; And C ₁ -C ₄₀ alkyl, C ₂ -C ₄₀ alkenyl groups, C ₁ -C ₄₀ alkoxy group, C ₃ -C ₄₀ cycloalkyl group, C ₃ -C ₄₀ heterocycloalkyl group, C ₆ -C of substituted with one or more groups selected from the ₄₀ aryl group and a heteroaryl group the group consisting of C ₅ -C _40, or is selected from the group consisting of an aryl group unsubstituted C ₆ -C _40,
R5 and R6 are the same or different from each other and represent hydrogen; A halogen, an amino group, a nitrile group, a nitro group, a cycloalkyl group of C ₁ -C ₄₀ alkyl, C ₂ -C ₄₀ alkenyl group, C ₁ -C ₄₀ alkoxy group, C ₃ -C ₄₀ in the, C ₃ -C ₄₀ A C ₁ -C ₄₀ alkyl group which is unsubstituted or substituted with at least one group selected from the group consisting of a heterocycloalkyl group, a C ₆ -C ₄₀ aryl group and a C ₅ -C ₄₀ heteroaryl group; A halogen, an amino group, a nitrile group, a nitro group, a cycloalkyl group of C ₁ -C ₄₀ alkyl, C ₂ -C ₄₀ alkenyl group, C ₁ -C ₄₀ alkoxy group, C ₃ -C ₄₀ in the, C ₃ -C ₄₀ A C ₃ -C ₄₀ cycloalkyl group unsubstituted or substituted with at least one group selected from the group consisting of a heterocycloalkyl group, a C ₆ -C ₄₀ aryl group and a C ₅ -C ₄₀ heteroaryl group; A halogen, an amino group, a nitrile group, a nitro group, a cycloalkyl group of C ₁ -C ₄₀ alkyl, C ₂ -C ₄₀ alkenyl group, C ₁ -C ₄₀ alkoxy group, C ₃ -C ₄₀ in the, C ₃ -C ₄₀ A C ₃ -C ₄₀ alkenyl group which is unsubstituted or substituted with at least one group selected from the group consisting of a heterocycloalkyl group, a C ₆ -C ₄₀ aryl group and a C ₅ -C ₄₀ heteroaryl group; A halogen, an amino group, a nitrile group, a nitro group, a cycloalkyl group of C ₁ -C ₄₀ alkyl, C ₂ -C ₄₀ alkenyl group, C ₁ -C ₄₀ alkoxy group, C ₃ -C ₄₀ in the, C ₃ -C ₄₀ A C ₃ -C ₄₀ alkoxy group unsubstituted or substituted with at least one group selected from the group consisting of a heterocycloalkyl group, a C ₆ -C ₄₀ aryl group, and a C ₅ -C ₄₀ heteroaryl group; A halogen, an amino group, a nitrile group, a nitro group, a cycloalkyl group of C ₁ -C ₄₀ alkyl, C ₂ -C ₄₀ alkenyl group, C ₁ -C ₄₀ alkoxy group, C ₃ -C ₄₀ in the, C ₃ -C ₄₀ A C ₃ -C ₄₀ amino group unsubstituted or substituted with at least one group selected from the group consisting of a heterocycloalkyl group, a C ₆ -C ₄₀ aryl group and a C ₅ -C ₄₀ heteroaryl group; A halogen, an amino group, a nitrile group, a nitro group, a cycloalkyl group of C ₁ -C ₄₀ alkyl, C ₂ -C ₄₀ alkenyl group, C ₁ -C ₄₀ alkoxy group, C ₃ -C ₄₀ in the, C ₃ -C ₄₀ a heterocycloalkyl group, an aryl group of C ₆ -C ₄₀ aryl groups and C ₅ -C substituted by at least one group selected from the group consisting of a heteroaryl group of ₄₀ or unsubstituted C ₆ -C _40; And a halogen, an amino group, a nitrile group, a nitro group, C ₁ -C ₄₀ alkyl, C ₂ -C ₄₀ alkenyl group, an alkoxy group, a cycloalkyl group of C ₃ -C ₄₀ in C ₁ -C _40, C ₃ -C ₄₀ heterocycloalkyl group, C ₆ -C ₄₀ aryl groups and C ₅ -C substituted with one or more groups selected from the group consisting of heteroaryl or ₄₀ or selected from the group consisting of heteroaryl, unsubstituted C ₅ -C ₄₀ , To form a fused ring of adjacent groups and an aliphatic, aromatic, heteroaliphatic or heteroaromatic ring or to form a spiro bond,
In Formula 1, n is an integer of 1 to 10. delete delete delete Is a compound of formula < RTI ID = 0.0 >

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 at least one of the organic compound layers comprises a compound according to any one of claims 1 and 5 Organic electronic device. The organic electronic device according to claim 6, wherein the organic layer includes a light emitting layer, and the light emitting layer comprises the compound. The organic electronic device according to claim 6, wherein the organic layer includes an electron transporting layer, and the electron transporting layer comprises the compound. 7. The organic electronic device according to claim 6, wherein the organic material layer includes a hole injecting layer and a hole transporting layer, and the hole injecting layer and the hole transporting layer comprise the compound. The organic electronic device according to claim 6, 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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