KR20070063354A - New compounds, preparation method thereof and organic light emitting diode using the same - Google Patents

Abstract

Novel compounds, a preparation method thereof and an organic light emitting diode by using the same compounds are provided to improve surface properties and electric charge transport ability of the compounds when they operate as an electron-transporting and electron-introducing layer in the organic light emitting diode. The novel compounds represented by the formula(1) and being useful for organic light emitting diode are provided. In the formula(1), R^1 to R^19 are each independently hydrogen; optionally substituted alkyl group; optionally substituted alkoxy group; optionally substituted alkenyl group; optionally substituted aryl group; optionally substituted arylamine group; optionally substituted hetero ring group containing O, N or S, wherein the substituent is halogen group, alkyl group, alkenyl group, alkoxy group, optionally substituted arylamine group, optionally substituted aryl group, optionally substituted arylalkyl group, optionally substituted arylalkenyl group, optionally substituted hetero ring group, nitrile group or acetylene group; amino group optionally substituted by alkyl group, alkenyl group, optionally substituted aryl group, optionally substituted arylalkyl group or optionally substituted arylalkenyl group; nitrile group; nitro group; halogen group; amide group; or ester group. The organic light emitting diode comprises a first electrode, a second electrode and an organic layer containing novel compounds represented by the formula(1) disposed between the first and second electrodes.

Description

New compounds, preparation method thereof and organic electroluminescent device using the same

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

The present invention relates to a novel compound that can be used in an organic electric device, a method for preparing the same, and an organic electric device using the same.

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

Examples of the organic electric element include an organic light emitting element, an organic solar cell, an organic photoconductor (OPC), an organic transistor, and the like, all of which are used to inject or transport holes, inject or transport electrons, or light emitting materials to drive the device. need. Hereinafter, the organic light emitting device will be described in detail. However, in the organic electronic devices, a hole injection or transport material, an electron injection or transport material, or a light emitting material functions on a similar principle.

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

Materials used as the organic material layer in the organic light emitting device may be classified into light emitting materials and charge transport materials such as hole injection materials, hole transport materials, electron transport materials, electron injection materials and the like depending on their functions. In addition, the light emitting material may be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to achieve a better natural color according to the light emitting color. On the other hand, when only one material is used as the light emitting material, the maximum emission wavelength is shifted to a long wavelength due to the intermolecular interaction, and the color purity decreases or the efficiency of the device decreases due to the emission attenuation effect. In order to increase the light emitting efficiency through the light emitting material, a host / dopant system may be used.

In order for the organic light emitting device to fully exhibit the above-mentioned excellent characteristics, it is supported that a material that forms the organic material layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, etc. is supported by a stable and efficient material. Although it should be preceded, the development of a stable and efficient organic material layer for an organic light emitting device has not been made yet. Therefore, the development of new materials continues to be demanded, and the necessity of such material development is the same in the other organic electric devices described above.

Thus, the present inventors synthesized a compound having a novel structure, and confirmed that these compounds are excellent in interfacial properties and charge transport ability when acting as an electron transport and electron injection layer in the organic electrical device, and completed the present invention.

The present invention is to provide a novel compound that can be used in the organic electric device.

In addition, the present invention is to provide a method for preparing the compound.

In addition, the present invention is to provide an organic electric device using the compound.

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

In Chemical Formula 1,

X is C or Si,

R ¹ to R ¹⁹ are each independently hydrogen; Halogen, alkyl, alkenyl, alkoxy, substituted or unsubstituted arylamine groups, substituted or unsubstituted aryl groups, substituted or unsubstituted arylalkyl groups, substituted or unsubstituted arylalkenyl groups, substituted or unsubstituted An alkyl group unsubstituted or substituted with one or more substituents selected from the group consisting of a heterocyclic group, a nitrile group and an acetylene group; Halogen, alkyl, alkenyl, alkoxy, substituted or unsubstituted arylamine groups, substituted or unsubstituted aryl groups, substituted or unsubstituted arylalkyl groups, substituted or unsubstituted arylalkenyl groups, substituted or unsubstituted An alkoxy group unsubstituted or substituted with one or more substituents selected from the group consisting of a heterocyclic group, a nitrile group and an acetylene group; Halogen, alkyl, alkenyl, alkoxy, substituted or unsubstituted arylamine groups, substituted or unsubstituted aryl groups, substituted or unsubstituted arylalkyl groups, substituted or unsubstituted arylalkenyl groups, substituted or unsubstituted Alkenyl groups unsubstituted or substituted with one or more substituents selected from the group consisting of a heterocyclic group, a nitrile group and an acetylene group; Halogen, alkyl, alkenyl, alkoxy, substituted or unsubstituted arylamine groups, substituted or unsubstituted aryl groups, substituted or unsubstituted arylalkyl groups, substituted or unsubstituted arylalkenyl groups, substituted or unsubstituted An aryl group unsubstituted or substituted with one or more substituents selected from the group consisting of a heterocyclic group, a nitrile group and an acetylene group; Halogen, alkyl, alkenyl, alkoxy, substituted or unsubstituted arylamine groups, substituted or unsubstituted aryl groups, substituted or unsubstituted arylalkyl groups, substituted or unsubstituted arylalkenyl groups, substituted or unsubstituted An arylamine group unsubstituted or substituted with one or more substituents selected from the group consisting of a heterocyclic group, a nitrile group and an acetylene group; Halogen, alkyl, alkenyl, alkoxy, substituted or unsubstituted arylamine groups, substituted or unsubstituted aryl groups, substituted or unsubstituted arylalkyl groups, substituted or unsubstituted arylalkenyl groups, substituted or unsubstituted A heterocyclic group which is unsubstituted or substituted with one or more substituents selected from the group consisting of a heterocyclic group, a nitrile group and an acetylene group and contains O, N or S as a hetero atom; An amino group substituted with one or more substituents selected from the group consisting of an alkyl group, an alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, a substituted or unsubstituted arylalkenyl group; Nitrile group; Nitro group; Halogen group; Amide group; And ester groups, where they may form a condensed ring of aliphatic or hetero with groups adjacent to each other.

Preferably, the compound of Formula 1 may be a compound represented by the following Formula 2.

In Chemical Formula 2, X, R ¹ to R ¹¹ , And R ¹⁴ to R ¹⁹ Is as defined in formula (1).

The steric structure of the compound of Formula 2 is described by dividing A and B portions.

In the compound of Formula 2, the core of the compound has a three-dimensional structure in which plane A and plane B are perpendicular to each other spatially about X. When the three-dimensional structure as described above, the pi-pi interaction between the compound structure is reduced, it can have the effect of inhibiting the formation of exciters or excitons (exciplex).

Also, no conjugation between the A and B portions around X occurs. The conjugation length of the compound and the energy bandgap 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 of Formula 2 includes limited conjugation, it has a large energy band gap.

In the present invention, a compound having various energy band gaps may be synthesized by introducing various substituents into the R ¹ to R ¹⁹ positions of the core structure having a large energy band gap as described above. In general, it is easy to control the energy band gap by introducing a substituent into the core structure having a large energy band gap, but when the core structure has a small energy band gap, it is difficult to largely control the energy band gap by introducing a substituent. In the present invention, the HOMO and LUMO energy levels of the compound can also be controlled by introducing various substituents at the R ¹ to R ¹⁹ positions of the core structure of the above structure.

In the compound of Formula 2, the A part has a carbazole unit, thereby basically having a p-type property. Here, the p-type property means a property having a conductive property along the HOMO level and having a cationic property by hole formation. Diazafluorene in the B portion has a low reduction potential to facilitate the injection of electrons and basically has n-type properties. Here, the n-type property generally means a property having anion characteristics along the LUMO level and having an anion characteristic by electron formation.

Since the compound of Formula 2 has an amphoteric property by the A and B portions, the compound of Formula 2 is excellent in interfacial properties and charge transport ability in the light emitting layer to which holes and electrons are bonded. In addition, a large band gap is suitable for a blue fluorescent host or a phosphorescent host, and may be used as a green or red host by introducing a substituent, and may also be used as a dopant. In addition, by introducing a variety of substituents it is possible to strengthen the character of the overall molecule to n-type or p-type.

In addition, in the compound of Formula 2, compounds having various energy band gaps may be synthesized by introducing various substituents at positions R ¹ to R ¹⁹ which are substituents in the A moiety. Therefore, the compound of Formula 2 may be compounds that more suitably meet the conditions required in the hole transport layer, the light emitting layer, the electron injection and transport layer, the hole blocking layer by a variety of substituents. In the present invention, a device having a low driving voltage and high light efficiency may be realized by selecting a compound having an appropriate energy level according to the substituent of the compound of Formula 2 and using the compound in an organic light emitting device.

Hereinafter, the substituents in Chemical Formulas 1 and 2 will be described in detail.

It is preferable that the alkyl group does not give a steric hindrance of 1 to 20 carbon atoms. Specific examples are selected from the group consisting of methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, pentyl group, hexyl group and heptyl group, but are not limited thereto.

It is preferable that the alkoxy group and the alkenyl group have 1 to 20 carbon atoms.

The aryl group includes, but is not limited to, those selected from the group consisting of phenyl group, naphthyl group, anthracenyl group, biphenyl group, pyrenyl group and perylene group.

The aryl amine group includes one selected from the group consisting of diphenyl amine group, phenyl naphthyl amine group, ditolyl amine group, phenyl tolyl amine group, carbazole and triphenyl amine group, but is not limited thereto.

The heterocyclic group includes, but is not limited to, those selected from the group consisting of pyridyl group, bipyridyl group, acridil group, thiophene group, imidazole group, oxazole group, thiazole group and quinolinyl group.

Examples of the silane group include a silole group, a silylene group, and the like, but are not limited thereto.

The halogen group includes fluorine, chlorine, bromine or iodine.

Specific examples of the compound of Formula 1 are shown in Table 1 and Table 2, and specific examples of the compound of Formula 2 are shown in Tables 3 to 6 below, but are not limited thereto.

In addition, the present invention provides a method for preparing a compound represented by Formula 1 or Formula 2.

The method for preparing the compound represented by Formula 1 or Formula 2 may be prepared by two methods.

In the first method, a compound of any one of compounds e to compound h and boronic acid compound (1 equivalent or 2 equivalents) represented by the following structural formulae is K ₂ CO ₃ The compound represented by the formula (1) or (2) may be prepared by reacting in the presence of a solution, tetrakis (triphenylphosphine) palladium (0) [tetrakis (triphenylphosphine) palladium (0)].

In the second method, n-BuLi is added dropwise to an iodine compound (1 equivalent or 2 equivalents) and reacted with compound c or compound d to prepare a compound represented by Formula 1 or Formula 2.

Compounds e to h used as the starting materials are prepared by the following method.

Compound e or Compound f as starting material,

1) reacting carbazole (or diphenylamine) with 1-bromo-2-iodobenzene to prepare monobromo compound a or monobromo compound b,

2) reacting the monobromo compound a or monobromo compound b prepared in step 1) with magnesium and 4,5-diazafluoren-9-one (4,5-diazafluoren-9-one) c or compound d, and

3) 2,7-dibromo-4,5-diazafluoren-9-one (2,7-dibromo-4,5-diazafluoren-9- reacting with one) to produce compound e or compound f,

Compound g or compound h as starting material,

Step 2) using 2-bromo-4,5-diazafluorene-9-one instead of 2,7-dibromo-4,5-diazafluorene-9-one in step 3) When reacted with the compound (c or d) prepared in the to obtain a compound (g or h).

In addition, the present invention provides an organic electronic device using the compound of Formula 1 or Formula 2.

The organic electric device of the present invention can be manufactured by a conventional method and material for manufacturing an organic electric device except for forming one or more organic material layers using the above-described compounds. Hereinafter, an organic light emitting diode will be exemplified.

In one embodiment of the present invention, the organic light emitting device may have a structure including a first electrode and a second electrode and an organic material layer disposed therebetween, the above-described compound according to the invention the organic material layer of the organic light emitting device Except for use in at least one of the layers can be prepared using a conventional method and material for manufacturing an organic light emitting device. The structure of the organic light emitting device according to the present invention is illustrated in FIG.

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

The organic material layer may have a multilayer structure including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer, but is not limited thereto and may have a single layer structure. In addition, the organic layer may be prepared by using a variety of polymer materials, and by using a method such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer, rather than a deposition method. It can be prepared in layers.

As the cathode material, a material having a large work function is usually preferred to facilitate hole injection into the organic material layer. Specific examples of the positive electrode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO: Al or SnO ₂ : Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline, and the like, but are not limited thereto.

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

The hole injection material is a material capable of well injecting holes from the anode at low voltage, and the highest occupied molecular orbital (HOMO) of the hole injection material is preferably between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of hole injection materials include metal porphyrine, oligothiophene, arylamine-based organics, hexanitrile hexaazatriphenylene, quinacridone-based organics, perylene-based organics, Anthraquinone, polyaniline and polythiophene-based conductive polymers, but are not limited thereto.

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

The light emitting material is a material capable of emitting light in the visible region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency with respect to fluorescence or phosphorescence is preferable. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole series compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compound; Benzoxazole, benzthiazole and benzimidazole series compounds; Poly (p-phenylenevinylene) (PPV) -based polymers; Spiro compounds; Polyfluorene, rubrene and the like, but are not limited thereto.

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

The organic light emitting device according to the present invention may be a top emission type, a bottom emission type or a double-sided emission type according to the material used.

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

Hereinafter, preferred examples are provided to aid in understanding the present invention. However, the following examples are merely provided to more easily understand the present invention, and the contents of the present invention are not limited thereto.

Production Example

The following compounds a to h can be used as starting materials for the preparation of the compounds represented by Formula 1 and Formula 2.

Production Example  One  Preparation of Compound a

Carbazole (1.672 g, 10 mmol), 1-bromo-2-iodobenzene (1.5 mL, 12 mmol), potassium carbonate (K ₂ CO ₃ , 2.7646 g, 20 mmol ), Copper iodide (CuI, 95 mg, 0.5 mmol) and 25 mL of xylene were refluxed under nitrogen atmosphere. After cooling to room temperature, the product was extracted with ethyl acetate, water was removed with anhydrous magnesium sulfate (MgSO ₄ ), and then the solvent was removed under reduced pressure. After passing through a silica gel column using a hexane solvent to obtain a compound, the solvent was removed under reduced pressure and dried in vacuo to give the desired compound a (800 mg, 25% yield) as a white solid. MS: [M + H] ⁺ = 323.

Production Example  2  Preparation of Compound b

Diphenylamine (1.692 g, 10 mmol), 1-bromo-2-iodobenzene (1.5 mL, 12 mmol), potassium carbonate (K ₂ CO ₃ , 2.7646 g, 20 mmol), copper iodide (CuI, 95 mg, 0.5 mmol) and 25 mL of xylene were refluxed under nitrogen atmosphere. After cooling to room temperature, the product was extracted with ethyl acetate, water was removed with anhydrous magnesium sulfate (MgSO ₄ ), and then the solvent was removed under reduced pressure. After passing through a silica gel column using a hexane solvent to obtain a compound, the solvent was removed under reduced pressure and dried in vacuo to give compound b (810 mg, 25% yield) of the desired white solid. MS: [M + H] ⁺ = 325.

Production Example  3  Preparation of Compound c

Compound a (6.96 g, 21.6 mmol) prepared in Preparation Example 1 and magnesium (Mg, 525 mg, 21.6 mmol) were dissolved in 300 ml of purified THF, and heated for 1 hour to form arylmagnesium bromide. Prepared. After lowering the temperature to room temperature, 4,5-diazafluoren-9-one (3.28 g, 18.0 mmol) was slowly added dropwise thereto. The reaction mixture was heated for 12 hours. After lowering the temperature to room temperature, the reaction was terminated with water and extracted with chloroform (CHCl ₃ ). The organic layer was dried with anhydrous magnesium sulfate (MgSO ₄ ), and then an organic solvent was removed. The resulting solid was dispersed in ethyl ether, stirred for one day, filtered and dried in vacuo to yield 7.28 g (95% yield) of intermediate. The resulting solid was dispersed in 10 ml of acetic acid and then 10 drops of concentrated sulfuric acid was added to reflux for 4 hours. The obtained solid was filtered, washed with ethanol and dried in vacuo to give 5.23 g (75% yield) of compound c. MS: [M + H] ⁺ = 408.

Production Example  4  Preparation of Compound d

Compound b (6.99 g, 21.6 mmol) prepared in Preparation Example 2 and magnesium (Mg, 525 mg, 21.6 mmol) were dissolved in 300 ml of purified THF, and heated for 1 hour to form arylmagnesium bromide. Prepared. After lowering the temperature to room temperature, 4,5-diazafluoren-9-one (3.28 g, 18.0 mmol) was slowly added dropwise thereto. The reaction mixture was heated for 12 hours. After lowering the temperature to room temperature, the reaction was terminated with water and extracted with chloroform (CHCl ₃ ). The organic layer was dried with anhydrous magnesium sulfate (MgSO ₄ ), and then an organic solvent was removed. The resulting solid was dispersed in hexane, stirred for one day, filtered and dried in vacuo to give 6.54 g (85% yield) of intermediate. The resulting solid was dispersed in 10 ml of acetic acid and then 10 drops of concentrated sulfuric acid was added to reflux for 4 hours. The obtained solid was filtered, washed with ethanol and dried in vacuo to give 4.69 g (75% yield) of compound d. MS: [M + H] ⁺ = 410.

Production Example  5  Preparation of Compound e

2,7-dibromo-4,5-diazafluorene-9-one (2,7-dibromo-4,5- instead of 4,5-diazafluorene-9-one in Preparation Example 3 Compound e was prepared in the same manner as in Preparation Example 3, except that diazafluoren-9-one) was used. MS: [M + H] ⁺ = 566

Production Example  6  Preparation of Compound f

Except for using 2,7-dibromo-4,5-diazafluorene-9-one in place of 4,5-diazafluorene-9-one in Preparation Example 4, Compound f was prepared in the same manner. MS: [M + H] ⁺ = 568.

Production Example  7  : Preparation of Compound g

2-bromo-4,5-diazafluorene-9-one (2-bromo-4,5-diazafluoren-9-one instead of 4,5-diazafluorene-9-one in Preparation Example 3 Compound g was prepared in the same manner as in Preparation Example 3, except that was used. MS: [M + H] ⁺ = 487.

Production Example  8  : Preparation of Compound h

In the same manner as in Preparation Example 4, except that 2-bromo-4,5-diazafluorene-9-one was used instead of 4,5-diazafluorene-9-one in Preparation Example 4. Compound h was prepared. MS: [M + H] ⁺ = 489.

Example  One  : Preparation of Compound (2-2)

Compound e (1.0 g, 1.78 mmol) prepared in Preparation Example 5 was completely dissolved in 50 ml of THF, and boronic acid compound (I) (1.17 g, 3.74 mmol) and 2M K ₂ CO ₃ Aqueous solution, tetrakis (triphenylphosphine) palladium (0) [tetrakis (triphenylphosphine) palladium (0)] (0.1 g, 5 mol%) and ethanol 3 ml were added and refluxed for 24 hours. After the reaction, the mixture was cooled to room temperature and filtered. Washed several times with water and ethanol. Recrystallization from ethanol and vacuum drying gave compound (2-2) (1.43 g, 85% yield). MS: [M + H] ⁺ = 944.

Example  2  : Preparation of Compound (2-4)

Compound (2-4) (1.74 g, 85% yield) was obtained by the same method as Example 1 except for using boronic acid compound (II) instead of boronic acid compound (I) in Example 1. . MS: [M + H] ⁺ = 1144.

Example  3  Preparation of Compound (2-48)

Iodine Compound (III) (2.04 g, 5.15 mmol) was dissolved in 50 ml of purified THF, cooled to -78 ° C and n-BuLi (2.5M in hexane, 2.1 ml, 5.15 mmol) was slowly added dropwise. After stirring for 30 minutes at the same temperature, Compound c (1.0 g, 2.45 mmol) prepared in Preparation Example 3 was added. After stirring for 40 minutes at the same temperature, the temperature was raised to room temperature and stirred for 3 hours. The reaction was terminated with an aqueous solution of ammonium chloride (NH ₄ Cl) and extracted with chloroform (CHCl ₃ ). Water was removed from the organic layer with anhydrous magnesium sulfate (MgSO ₄ ), and then the organic solvent was also removed. The resulting solid was dispersed in ethanol, stirred for one day, filtered and dried in vacuo to give 1.39 g (60% yield) of compound (2-48). MS: [M + H] ⁺ = 944.

Example  4  : Preparation of Compound (2-40)

Compound (2-40) (1.27 g, 90% yield) was obtained in the same manner as in Example 1, except that Boronic Acid Compound (IV) was used instead of Boronic Acid Compound (I) in Example 1 . MS: [M + H] ⁺ = 795.

Example  5  : Preparation of Compound (2-84)

Compound (2-84) (1.39 g, 60% yield) was obtained by the same method as Example 3 except for using the iodine compound (V) instead of the iodine compound (III) in Example 3. MS: [M + H] ⁺ = 1035.

Example  6  : Preparation of Compound (2-107)

Compound (2-107) (1.08 g, 90% yield) was obtained in the same manner as in Example 1 except that Compound g was used instead of Compound e in Example 1. MS: [M + H] ⁺ = 675.

Example  7  : Preparation of Compound (2-151)

Compound (2-151) (0.71 g, 40% yield) in the same manner as in Example 3, except that 1 equivalent of iodine compound (V) was used instead of 2 equivalents of iodine compound (III) in Example 3. Got. MS: [M + H] ⁺ = 721.

Experimental Example  One  :

A glass substrate (corning 7059 glass) coated with a thin film of ITO (Indium Tin Oxide) at a thickness of 1000 Å was placed in distilled water in which a dispersant was dissolved, and washed with ultrasonic waves. Fischer Co. products were used for the detergent, and Millipore Co. Secondly filtered distilled water was used as a filter of the product. After washing ITO for 30 minutes, ultrasonic washing was performed twice with distilled water for 10 minutes. After washing the distilled water, the ultrasonic washing in the order of isopropyl alcohol, acetone, methanol solvent and dried.

Hexanitrile hexaazatriphenylene (500 Pa), 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPB) (400 Pa), Alq ₃ ( 300 Å), Compound (2-34) (50 Å) and electron transport material (200 Å) of the following structural formulas are sequentially thermally vacuum deposited to form a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, and an electron transport layer in this order. I was.

[E-transport material]

12 전자 thick lithium fluoride (LiF) and 2000 Å thick aluminum were deposited on the electron transport layer to form a cathode, thereby manufacturing an organic light emitting device.

In the above process, the deposition rate of the organic material was maintained at 0.4 ~ 0.7 Å / sec, the lithium fluoride of the cathode was maintained at a deposition rate of 0.3 Å / sec, aluminum is 2 Å / sec, the vacuum degree during deposition is 2 x 10 ^-7 to 5 x 10 ^-8 torr was maintained.

As a result of applying a forward electric field of 4.5 V to the organic light emitting device, green light corresponding to x = 0.32, y = 0.56 was observed based on 1931 CIE color coordinate at a current density of 50 mA / cm 2, and 5.4 V As a result of the forward electric field, green light of 3.3 cd / A was observed at a current density of 100 mA / cm 2.

Experimental Example  2  :

Hexanitrile hexaazatriphenylene (500 mV), 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPB) (400 mV), Alq ₃ (300) on the ITO electrode Iii), Compound (2-48) (200 kPa) prepared in Example 3 was sequentially vacuum-deposited to form a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer in that order. An organic light emitting diode was manufactured according to the same method as Experimental Example 1 except that a cathode was formed by sequentially depositing 12 라이드 thick lithium fluoride (LiF) and 2000 2000 thick aluminum on the electron transport layer.

As a result of applying a forward electric field of 4.7 V to the organic light emitting device, green light corresponding to x = 0.34, y = 0.56 was observed based on 1931 CIE color coordinate at a current density of 50 mA / cm 2, and 6.2 V of As a result of applying the forward electric field, green light of 3.0 cd / A was observed at a current density of 100 mA / cm 2.

Experimental Example  3  :

Two layers of hole injection layers were formed on the ITO electrode with hexanitrile hexaazatriphenylene (80 Pa) and a hole injection material (800 Pa) of the following structural formula. A hole transport layer was formed thereon using 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPB) (400 kPa). The compound (2-84) (300 kV) prepared in Example 5 and the electron transport material (200 kV) of the following structural formula were sequentially thermally vacuum-deposited to form a light emitting layer and an electron transport layer. An organic light emitting diode was manufactured according to the same method as Experimental Example 1 except that a cathode was formed by sequentially depositing 12 플루오 of lithium fluoride (LiF) and 2000 Å of aluminum on the electron transport layer.

As a result of applying a forward electric field of 6.9 V to the organic light emitting device manufactured above, blue light corresponding to x = 0.16 and y = 0.20 was observed based on 1931 CIE color coordinate at a current density of 50 mA / cm 2, and 7.8 V of As a result of the forward electric field, green light of 1.4 cd / A was observed at a current density of 100 mA / cm 2.

The compound according to the present invention may play a role of hole injection, hole transport, electron injection and transport, or a light emitting material in an organic electric device including an organic light emitting device, the device according to the present invention is excellent in efficiency, driving voltage, stability Characteristics.

Claims (11)

A compound represented by the following formula (1). <Formula 1>

In Chemical Formula 1, X is C or Si, R ¹ to R ¹⁹ Are each independently hydrogen; Halogen, alkyl, alkenyl, alkoxy, substituted or unsubstituted arylamine groups, substituted or unsubstituted aryl groups, substituted or unsubstituted arylalkyl groups, substituted or unsubstituted arylalkenyl groups, substituted or unsubstituted An alkyl group unsubstituted or substituted with one or more substituents selected from the group consisting of a heterocyclic group, a nitrile group and an acetylene group; Halogen, alkyl, alkenyl, alkoxy, substituted or unsubstituted arylamine groups, substituted or unsubstituted aryl groups, substituted or unsubstituted arylalkyl groups, substituted or unsubstituted arylalkenyl groups, substituted or unsubstituted An alkoxy group unsubstituted or substituted with one or more substituents selected from the group consisting of a heterocyclic group, a nitrile group and an acetylene group; Halogen, alkyl, alkenyl, alkoxy, substituted or unsubstituted arylamine groups, substituted or unsubstituted aryl groups, substituted or unsubstituted arylalkyl groups, substituted or unsubstituted arylalkenyl groups, substituted or unsubstituted Alkenyl groups unsubstituted or substituted with one or more substituents selected from the group consisting of a heterocyclic group, a nitrile group and an acetylene group; Halogen, alkyl, alkenyl, alkoxy, substituted or unsubstituted arylamine groups, substituted or unsubstituted aryl groups, substituted or unsubstituted arylalkyl groups, substituted or unsubstituted arylalkenyl groups, substituted or unsubstituted An aryl group unsubstituted or substituted with one or more substituents selected from the group consisting of a heterocyclic group, a nitrile group and an acetylene group; Halogen, alkyl, alkenyl, alkoxy, substituted or unsubstituted arylamine groups, substituted or unsubstituted aryl groups, substituted or unsubstituted arylalkyl groups, substituted or unsubstituted arylalkenyl groups, substituted or unsubstituted An arylamine group unsubstituted or substituted with one or more substituents selected from the group consisting of a heterocyclic group, a nitrile group and an acetylene group; Halogen, alkyl, alkenyl, alkoxy, substituted or unsubstituted arylamine groups, substituted or unsubstituted aryl groups, substituted or unsubstituted arylalkyl groups, substituted or unsubstituted arylalkenyl groups, substituted or unsubstituted A heterocyclic group which is unsubstituted or substituted with one or more substituents selected from the group consisting of a heterocyclic group, a nitrile group and an acetylene group and contains O, N or S as a hetero atom; An amino group substituted with one or more substituents selected from the group consisting of an alkyl group, an alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, a substituted or unsubstituted arylalkenyl group; Nitrile group; Nitro group; Halogen group; Amide group; And ester groups, where they may form a condensed ring of aliphatic or hetero with groups adjacent to each other. The compound of claim 1, wherein the compound of Chemical Formula 1 is a compound represented by the following Chemical Formula 2. <Formula 2>

In Chemical Formula 2, X, R ¹ to R ¹¹ , And R ¹⁴ to R ¹⁹ Is as defined in formula (1). The compound of claim 1, wherein the compound of Formula 1 is selected from the group consisting of the following structural formulas.

The compound of claim 2, wherein the compound of Formula 2 is selected from the group consisting of the following structural formulas.

The compound of any one of compounds e to compound h and boronic acid compound (1 equivalent or 2 equivalents) represented by the following structural formulae is K ₂ CO ₃ A solution, tetrakis (triphenylphosphine) palladium (0) [tetrakis (triphenylphosphine) palladium (0)], which is prepared by reacting in the presence of a process for producing the compound of claim 1 or 2.

A method for producing the compound of claim 1 or 2, wherein n-BuLi is added dropwise to an iodine compound (1 equivalent or 2 equivalents) and reacted with compound c or compound d.

An organic electric device comprising a first electrode, a second electrode, and at least one organic material layer disposed between the first electrode and the second electrode, wherein at least one of the organic material layers is any one of claims 1 to 4. An organic electric device comprising the compound of claim. The organic electronic device of claim 7, wherein the organic material layer includes a hole injection layer and a hole transport layer, and the hole injection layer and the hole transport layer include the compound of any one of claims 1 to 4. The organic electroluminescent device according to claim 7, wherein the organic material layer comprises a light emitting layer, and the light emitting layer comprises the compound of any one of claims 1 to 4. The organic electronic device of claim 7, wherein the organic material layer comprises an electron transport layer, and the electron transport layer comprises the compound of any one of claims 1 to 4. The organic electronic device of claim 7, wherein the organic electronic device is selected from the group consisting of an organic light emitting device, an organic solar cell, an organic photoconductor (OPC), and an organic transistor.

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