KR20100112903A - New compounds and organic electronic device using the same - Google Patents

Abstract

PURPOSE: A compound and an organic electronic device using thereof are provided to apply the compound as a hole transport and injecting material, an electron transport and injecting material, and a luminescent material for the organic electronic device. CONSTITUTION: A manufacturing method of a compound marked with chemical formula 1 comprises the following steps: suzuki coupling arylboronic acid based or aryl boronate based compound, with a halide aryl compound under the presence of a palladium catalyst to form a compound B marked with chemical formula 3; lithiating the compound B after melting into an anhydrous solvent, and reacting with a ketone compound to form a compound C marked with chemical formula 4; and linking the rings of the compound C at the acidic condition.

Description

Novel compounds and organic electronic device using the same {NEW COMPOUNDS AND ORGANIC ELECTRONIC DEVICE USING THE SAME}

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

Examples of organic electronic devices include organic light emitting devices, organic solar cells, organic photoconductor (OPC) drums, and organic transistors, all of which are electron / hole injection materials, electron / hole extraction materials, and electron / hole transport materials for driving the devices. Requires material or luminescent material. Hereinafter, the organic light emitting device will be described in detail. However, in the organic electronic devices, an electron / hole injection material, an electron / hole extraction material, an electron / hole transport material, or a light emitting material may all operate 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. In this case, the organic material layer is often formed of a multilayer structure composed of different materials to increase the efficiency and stability of the organic light emitting device, and may include, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. When the voltage is applied between the two electrodes in the structure of the organic light emitting device, 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, and the excitons are at the bottom. When it falls to the state, it becomes light. Such organic light emitting devices are known to have characteristics such as self-luminous, high brightness, high efficiency, low driving voltage, wide viewing angle, high contrast, and high speed response.

Materials used as the organic material layer in the organic light emitting device may be classified into light emitting materials and charge transport materials such as hole injection materials, hole transport materials, electron transport materials, electron injection materials and the like depending on their functions. The luminescent material includes blue, green, and red luminescent materials and yellow and orange luminescent materials necessary to realize better natural colors depending on the emission color. In addition, in order to increase luminous efficiency through increase in color purity and energy transfer, a host / dopant system may be used as the light emitting material. The principle is that when a small amount of dopant having a smaller energy band gap and excellent luminous efficiency than the host mainly constituting the light emitting layer is mixed in the light emitting layer, excitons generated in the host are transported to the dopant to produce high efficiency light. At this time, since the wavelength of the host shifts to the wavelength of the dopant, light having a desired wavelength can be obtained according to the type of dopant to be used.

In order to fully exhibit the excellent characteristics of the above-described organic light emitting device, a material forming the organic material layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, etc., is supported by a stable and efficient material. Although this should be preceded, the development of a stable and efficient organic material layer for an organic light emitting device has not been sufficiently achieved, and therefore, the development of new materials is continuously required.

We have found compounds with novel structures. In addition, it has been found that when the organic compound layer of the organic electronic device is formed using the novel compound, effects such as efficiency increase, driving voltage drop, and stability increase of the device may be exhibited.

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 Chemical Formula 1,

Q is a C ₁₀ ~ C ₃₀ condensed aromatic polycyclic group,

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

Ar and Ar 'are the same as or different from each other, and each independently 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 A substituted 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 ₂₀ aryloxy group, substituted or unsubstituted C ₁ to C ₃₀ alkylthioxy group, substituted or unsubstituted C ₅ to C ₂₀ arylthioxy group, substituted or unsubstituted C ₁ to C ₃₀ alkylamine group , Substituted or unsubstituted C ₅ to C ₃₀ arylamine group, substituted or unsubstituted C ₆ to C ₃₀ aryl group, substituted or unsubstituted C ₃ to C ₃₀ having a hetero atom O, N or S Heteroaryl group, substituted or unsubstituted boron group, substituted or unsubstituted silane group, carbonyl group, phosphoryl group, amino group, nitrile group, Selected from the group consisting of a tro group, a hydroxyl group, a halogen group, an amide group, and an ester group, and may form a condensed ring or form a spiro bond of an aliphatic, aromatic, aliphatic hetero, or aromatic hetero group with adjacent groups, wherein n is two or more; In the case of an integer, the two or more Ars may be the same or different from each other. When m is an integer of two or more, the two or more Ar ′ may be the same or different from each other.

R1 and R2 are the same as or different from each other, and each independently 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 A substituted 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, and a substituted or unsubstituted hetero atom O, N Or a C ₃ to C ₃₀ heteroaryl group having S.

In addition,

1) Compound A represented by the following Formula 3 is reacted by Suzuki coupling with a halide aryl compound under the palladium (Pd) catalyst to Compound A represented by the following formula (2) as an arylboronic acid-based or arylboronate-based compound: Manufacturing step,

2) After dissolving Compound B in an anhydrous solvent, lithiating with n-, sec- or tert-BuLi, and reacting with R1COR2, a substituted or unsubstituted ketone compound, as a monoalcohol-based compound Preparing compound C represented by 4, and

3) reacting the compound C under acidic conditions to link a ring

It provides a method for producing a compound represented by the formula (1) comprising a.

(Ar) nQB (OR) ₂

Ar, Ar ', Q, n and m are as defined in the formula (1), R, R1 and R2 are the same as the definition of R1 and R2 in the formula (1).

In addition, 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 layer of the organic layer is the novel compound It provides an organic electronic device comprising.

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, arylamine groups, arylcarbonyl groups, arylphosphoryl groups, and the like. The organic electronic device including the organic light emitting device using the compound according to the present invention as a material of the organic material layer exhibits excellent characteristics in efficiency, driving voltage, lifetime, and the like.

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

Compound according to the invention is characterized in that represented by the formula (1).

In the compound according to the present invention, the substituents of Chemical Formula 1 will be described in more detail.

Q may be a C ₁₀ to C ₃₀ condensed aromatic polycyclic group, which may be an aromatic polycyclic group having 3 to 4 condensed benzene rings. Specific examples of Q may include, but are not limited to, phenanthrene, pyrene, anthracene, chrysene, and the like.

The alkyl group may be straight or branched chain, carbon number is not particularly limited, but is preferably 1 to 20. Specific examples include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, heptyl, and the like.

The alkenyl group may be linear or branched, and the carbon number is not particularly limited, but is preferably 2 to 20. Specific examples thereof include alkenyl groups in which aryl groups such as stylbenyl and styrenyl are connected, but are not limited thereto.

It is preferable that the said cycloalkyl group does not give a three-dimensional interference of C3-C20. Specific examples include a cyclopentyl group and a cyclohexyl group, but are not limited thereto.

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

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

The substituted or unsubstituted C ₅ to C ₃₀ amine group may be in the form of -N (Z 1) (Z 2), wherein Z 1 and Z 2 are each independently a substituted or unsubstituted C ₁ to C ₅₀ alkyl group. , Substituted or unsubstituted C ₂ ~ C ₅₀ alkenyl group, substituted or unsubstituted C ₅ ~ C ₅₀ cycloalkyl group, substituted or unsubstituted C ₅ ~ C ₅₀ cycloalkenyl group, substituted or unsubstituted C ₅ to C ₅₀ heterocycloalkyl group, substituted or unsubstituted C ₆ to C ₅₀ aryl group, substituted or unsubstituted C ₂ to C ₅₀ heteroaryl group and the like. In the arylamine group, the aryl group is preferably 5 to 30 carbon atoms, and more specific examples of the arylamine group include a diphenylamine group, a phenylnaphthylamine group, a phenylbiphenylamine group, a naphthylbiphenylamine group, Dinaphthylamine group, dibiphenylamine group, dianthracenylamine group, 3-methyl-phenylamine group, 4-methyl-naphthylamine group, 2-methyl- biphenylamine group, 9-methyl- anthracenylamine Groups, ditolyl amine groups, phenyl tolyl amine groups, triphenylaminophenyl amine groups, phenyl biphenylamino phenyl amine groups, naphthyl phenylaminophenyl biphenylamine groups, and the like, but are not limited thereto.

The aryl group may be monocyclic or polycyclic, and the carbon number is not particularly limited, but is preferably 6 to 30. Examples of the monocyclic aryl group include phenyl group, biphenyl group, terphenyl group, stilbene, and the like. Examples of the polycyclic aryl group include naphthyl group, anthracenyl group, phenanthrene group, pyrenyl group, perrylenyl group, and cryo. But may be mentioned, but is not limited thereto.

The heteroaryl group is a ring group containing O, N or S as a hetero atom, and the number of carbon atoms is not particularly limited, but is preferably 3 to 30 carbon atoms. Examples of the heterocyclic group include a carbazole group, a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a pyridazine group, a quinolinyl group, an isoquinoline group , Acridil group and the like, but is not limited thereto.

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

Substituents that may be substituted with Ar, Ar ′, R1, and R2 of Formula 1 may 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, a hydroxy group, an alkyl group, and alkoxy. Group, arylthioxy group, alkylthioxy group, alkylamine group, aralkylamine group, arylamine group, alkenyl group, cycloalkyl group, cycloalkenyl group, silane group, boron group, C ₆ ~ C ₃₀ aryl group, C ₃ And C ₃₀ a heteroaryl group, but are not limited thereto.

In the compound according to the present invention, Chemical Formula 1 may be represented by the following Chemical Formulas 5 to 13.

In Formulas 5 to 13, R1, R2, Ar 'and m are the same as defined in Formula 1,

Ar ₁ to Ar ₈ are each independently the same as the definition of Ar of the formula (1).

Preferred specific examples of the compound represented by Formula 1 include the following compounds, but are not limited thereto.

In addition, the method for preparing a compound represented by Chemical Formula 1 according to the present invention includes: 1) Compound A represented by Chemical Formula 2 as an arylboronic acid-based or arylboronate-based compound under a palladium (Pd) catalyst; Coupling (Suzuki coupling) to prepare a compound B represented by the formula (3), 2) After dissolving the compound B in an anhydrous solvent, after lithiation with n-, sec- or tert-BuLi Preparing a compound C represented by Formula 4 as a monoalcohol-based compound by reacting with a substituted or unsubstituted ketone compound R1COR2, and 3) connecting the ring by reacting the compound C in an acidic condition. It is characterized by including.

When Q is typically a phenanthrene group among the compounds represented by Formula 1, it may be prepared as in the reaction process of Scheme 1 below. Reaction Scheme 1 is only an example for synthesizing the compound represented by Formula 1, but is not limited thereto.

Scheme 1

Spiro derivatives represented by Formula 1 according to Scheme 1

1) Suzuki bonds 1,2-dibromo benzene or 1-bromo-2-iodobenzene compound to a 9-phenanthrene boronic acid or 9-phenanthrene boronate compound A derivative under a palladium (Pd) catalyst ( Suzuki coupling) to prepare compound B.

2) After dissolving the compound B derivative prepared in step 1) in anhydrous solvent, lithiation with n-, sec-, tert-BuLi, and reacting with a substituted or unsubstituted ketone compound, R1COR2, monoalcohol (monoalcohol) Preparing a compound C derivative, and

3) The compound of Formula 1 may be prepared by connecting a ring by reacting the compound C derivative prepared in step 2) under acidic conditions.

In Reaction Scheme 1, Ar ', R1, R2 and m are as defined in Formula 1, Ar ₁ to Ar ₉ is the same as the definition of Ar in Formula 1.

The compound represented by Chemical Formula 1 may have properties suitable for use as an organic material layer used in an organic light emitting device by introducing various substituents into the core structure represented by the chemical formula. The compound represented by Chemical Formula 1 may exhibit properties in any layer of the organic light emitting device, but may exhibit the following properties in particular.

Compounds in which substituted or unsubstituted arylamine groups are introduced are suitable as light emitting layer, hole injection and hole transport layer materials, and when heterocyclic ring substituents containing N are introduced, they are suitable as electron injection, electron transport layer and hole blocking layer materials. .

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 represented by Chemical Formula 1 includes limited conjugation, it has a property from small to large energy bandgap.

Moreover, the compound which has the intrinsic property of the introduced substituent can be synthesize | combined by introducing various substituents into the core structure of the above structure. For example, the hole injection layer material and the hole transport layer material used in manufacturing the organic light emitting device have an energy level sufficient to transfer holes along the highest occupied molecular orbital (HOMO), and the low unoccupied molecular orbital (LUMO) from the light emitting layer. It can be a compound that can have an energy level enough to block the electrons coming along. In particular, the core structure of the compound exhibits stable properties to the electrons and may contribute to improving the life of the device. Derivatives made by introducing substituents to be used in the light emitting layer and the electron transport layer material may be manufactured to have an appropriate energy band gap in various arylamine dopants, aryl dopants, metal dopants, and the like.

In addition, by introducing a variety of substituents in the core structure it is possible to finely control the energy band gap, on the other hand to improve the interfacial properties between the organic material and to vary the use of the material.

On the other hand, the compound represented by Formula 1 has a high glass transition temperature (Tg) is excellent in thermal stability. This increase in thermal stability is an important factor in providing drive stability to the device.

In addition, the organic electronic device according to the present invention is an organic electronic device comprising a first electrode, a second electrode, and one or more organic material layers disposed between the first electrode and the second electrode, at least one layer of the organic material layer. Is characterized in that it comprises a compound of formula (1).

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

The compound of Chemical Formula 1 may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method in manufacturing an organic electronic device. Here, the solution coating method means spin coating, dip coating, inkjet printing, screen printing, spraying method, 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 injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and the like as an organic material layer. However, the structure of the organic electronic device is not limited thereto and may include a smaller number of organic material layers.

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

In addition, the organic material layer may include a light emitting layer, and the light emitting layer may include a compound represented by Chemical Formula 1.

In the organic layer of the multilayer structure, the compound of Chemical Formula 1 may be included in a light emitting layer, a layer for simultaneously injecting / holes transporting and emitting light, a layer for simultaneously transporting holes and emitting light, or a layer for simultaneously transporting electrons and emitting 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.

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 transport and light emitting layer 105, an electron transport 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 transport and the light emitting layer 105.

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

4 illustrates a structure of an organic light emitting device in which a substrate 101, an anode 102, a hole injection layer 103, a hole transport layer 104, an electron transport and light emitting layer 105, and a cathode 107 are sequentially stacked. It is. In such a structure, the compound of Formula 1 may be included in the electron transport and emission layer 105.

For example, the organic light emitting device according to the present invention uses a metal vapor deposition (PVD) method such as sputtering or e-beam evaporation, and has a metal oxide or a metal oxide or an alloy thereof on a substrate. It can be prepared by depositing an anode to form an anode, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer and 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 material layer may be formed by using a variety of polymer materials, and by using a method such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer method, rather than a deposition method. It can be prepared in layers.

As the anode 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); A combination of a metal and an oxide such as ZnO: Al or SnO ₂ : Sb; Conductive polymers such as poly (3-methyl compound), poly [3,4- (ethylene-1,2-dioxy) compound] (PEDT), polypyrrole and polyaniline, and the like, but are not limited thereto.

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

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

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

The light emitting material is a material capable of emitting light in the visible region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency with respect to fluorescence or phosphorescence is preferable. Specific examples thereof include 8-hydroxyquinoline 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.

The electron transporting material is a material capable of injecting electrons well from the cathode and transferring the electrons to the light emitting layer. A material having high mobility to electrons 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 depending on the material used.

The compound according to the present invention may also operate 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.

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

Hereinafter, the method of preparing the compounds represented by Chemical Formula 1 of the present invention and the method and performance of the organic electronic device using the same will be described in detail through Examples. However, the following examples are for illustrative purposes, and the scope of the present invention is not limited by the following examples.

In the Example, the evaluation method 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 may generally be prepared by a multistage chemical reaction. That is, some intermediate compounds are prepared first, and compounds of formula 1 are prepared from the intermediate compounds. Exemplary intermediate compounds are compounds such as compounds 1A, 1B, 1C, 2B, 2C, 3A, 3B, 3C, 4A, 4B, 5A, 5B and the like shown in the synthesis examples below.

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, whereby the scope of the invention is not limited.

<Examples>

Synthesis Example 1

1) Preparation of Compound 1A

Phenanthren-9-yl-9-boronic acid (22.2 g, 100 mmol) and 1-bromo-2-iodobenzene (28.3 g, 100 mmol) were added to tetrahydrofuran ( After completely dissolved in 400mL), 2M aqueous potassium carbonate solution was added, tetrabistriphenylphosphino palladium (2.3 g, 2 mmol) was added thereto, and the mixture was heated and stirred for 10 hours. The temperature was lowered to room temperature, the resulting solution was dried over anhydrous magnesium sulfate, and recrystallized with CHCl ₃ / n-Hex to give 9- (2-bromophenyl) phenanthrene (9- (2-bromophenyl) phenanthrene, which is Compound 1A. , 27.3 g, yield 82%) was prepared.

MS: [M + H] ⁺ = 333

2) Preparation of Compound 1B

Compound 1A (12 g, 36 mmol) synthesized in 1) above was put in anhydrous THF (100 mL) under a nitrogen atmosphere, and the reaction temperature was maintained at -78 ^° C. n-BuLi (2.5M in HEX, 17.2 mL, 43 mmol) was added dropwise to the reaction solution. After stirring for about 40 minutes, 2,7-dibromofluorenone (2,7-dibromofluorenone, 12 g, 35 mmol) was added to the reaction mixture and stirred. After about 1 hour to warm up 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 then ethyl ether was added to prepare solid compound 1B.

MS: [M + H] ⁺ = 592

3) Preparation of Compound 1C

The compound 1B obtained in the above 2) was no longer purified, but 100 mL of acetic acid was added and stirred. 2 mL of sulfuric acid was added dropwise to the reaction solution, followed by heating and stirring at 80 ° C. After stirring for 8 hours to cool to room temperature, the resulting yellow solid was filtered, washed with water and ethanol and dried to prepare compound 1C (18.3g, 91% yield).

MS: [M + H] ⁺ = 574

Synthesis Example 2

1) Preparation of Compound 2B

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

MS: [M + H] ⁺ = 513

2) Preparation of Compound 2C

The compound 2B obtained in the above 1) was no longer purified, but 100 mL of acetic acid was added and stirred. 2 mL of sulfuric acid was added dropwise to the reaction solution, followed by heating and stirring at 80 ° C. After stirring for 8 hours, the yellow solid produced by cooling to room temperature was filtered, washed with water and ethanol and dried to prepare a compound (13.7g, yield 79%).

MS: [M + H] ⁺ = 495

&Lt; Synthesis Example 3 &

1) Preparation of Compound 3A

Pyren-1-yl-1-boronic acid (28.1 g, 100 mmol) and 1-bromo-2- iodobenzene (28.3 g, 100 mmol) were added to tetrahydrofuran ( After completely dissolved in 400mL), 2M aqueous potassium carbonate solution was added, tetrabistriphenylphosphino palladium (2.3 g, 2 mmol) was added thereto, and the mixture was heated and stirred for 10 hours. The temperature was lowered to room temperature, the resulting solution was dried over anhydrous magnesium sulfate, and recrystallized with CHCl ₃ / n-Hex to prepare the compound 3A (23.6 g, 66% yield).

MS: [M + H] ⁺ = 357

2) Preparation of Compound 3B

Compound 3A (10 g, 36 mmol) synthesized in 1) was added anhydrous THF (100 mL) under a nitrogen atmosphere, and the reaction temperature was maintained at -78 ^° C. n-BuLi (2.5M in HEX, 17.2 mL, 43 mmol) was added dropwise to the reaction solution. After stirring for about 40 minutes, 2-bromofluorenone (2-bromofluorenone, 9.1 g, 35 mmol) was added to the reaction mixture and stirred. After about 1 hour to warm up to room temperature and stirred for 3 hours. Aqueous ammonium chloride solution was added to the reaction mixture, and the THF layer was separated. After drying the organic layer with anhydrous magnesium sulfate, ethyl ether was added to prepare a solid compound 3B.

MS: [M + H] ⁺ = 537

3) Preparation of Compound 3C

The compound 3B obtained in the above 2) was no longer purified, but 100 mL of acetic acid was added and stirred. 2 mL of sulfuric acid was added dropwise to the reaction solution, followed by heating and stirring at 80 ° C. After stirring for 8 hours, the yellow solid produced by cooling to room temperature was filtered, washed with water and ethanol and dried to prepare compound 3C (9.9 g, yield 53%).

MS: [M + H] ⁺ = 519

Preparation Example 1 Preparation of Compound 1-2-28

2- [9,10-di-2-naphthalenyl-2-anthracenyl] -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2- [9,10 -di-2-naphthalenyl-2-anthracenyl] -4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 10 g, 18.0 mmol), compound 2C (8.9 g, 18.0 mmol) and sodium carbonate (5.0 g) , 35.9 mmol) was suspended in a mixture of 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 filtered THF / EtOH to give compound 1-2-28 (11.6 g, 76% yield).

MS: [M + H] ⁺ = 845

Preparation Example 2 Preparation of Compound 1-2-66

In the preparation of compound 1-2-28 of Preparation Example 1, 2- [9,10-di-2-naphthalenyl-2-anthracenyl] -4,4,5,5-tetramethyl-1 Pi instead of 3,2-dioxaborolane (2- [9,10-di-2-naphthalenyl-2-anthracenyl] -4,4,5,5-tetramethyl-1,3,2-dioxaborolane) Compound 1-2-66 (19.3 g, yield 87) by reaction in the same manner except that pyren-1-yl-1-boronic acid (8.9 g, 36.0 mmol) was used. %) Was prepared.

MS: [M + H] ⁺ = 617

Preparation Example 3 Preparation of Compound 1-2-29

In the production example of 1-2-28 of Preparation Example 1, 2- [9,10-di-2-naphthalenyl-2-anthracenyl] -4,4,5,5-tetramethyl-1, 4, instead of 3,2-dioxaborolane (2- [9,10-di-2-naphthalenyl-2-anthracenyl] -4,4,5,5-tetramethyl-1,3,2-dioxaborolane) 4,5,5-tetramethyl-2- (4- (10- (naphthalen-1-yl) anthracene-9-yl) phenyl) -1,3,2-dioxaborolane (4,4,5 Same method except for using 5-tetramethyl-2- (4- (10- (naphthalen-1-yl) anthracen-9-yl) phenyl) -1,3,2-dioxaborolane, 5.1 g, 10.0 mmol) Compound 1-2-29 (7.0 g, yield 88%) was prepared by reaction.

MS: [M + H] ⁺ = 795

Preparation Example 4 Preparation of Compound 1-2-31

In the production example of 1-2-28 of Preparation Example 1, 2- [9,10-di-2-naphthalenyl-2-anthracenyl] -4,4,5,5-tetramethyl-1, The anthracene instead of 3,2-dioxaborolane (2- [9,10-di-2-naphthalenyl-2-anthracenyl] -4,4,5,5-tetramethyl-1,3,2-dioxaborolane) The reaction was carried out in the same manner except using the boronic acid compound (3.5 g, 10.0 mmol) to prepare compound 1-2-31 (4.1 g, yield 57%).

MS: [M + H] ⁺ = 719

Preparation Example 5 Preparation of Compound 1-2-32

In the production example of 1-2-28 of Preparation Example 1, 2- [9,10-di-2-naphthalenyl-2-anthracenyl] -4,4,5,5-tetramethyl-1, The anthracene instead of 3,2-dioxaborolane (2- [9,10-di-2-naphthalenyl-2-anthracenyl] -4,4,5,5-tetramethyl-1,3,2-dioxaborolane) The compound 1-2-32 (4.9 g, yield 64%) was prepared by reaction in the same manner except that the boronic acid compound (4.0 g, 10.0 mmol) was used.

MS: [M + H] ⁺ = 769

Preparation Example 6 Preparation of Compound 1-2-15

In the production example of 1-2-28 of Preparation Example 1, 2- [9,10-di-2-naphthalenyl-2-anthracenyl] -4,4,5,5-tetramethyl-1, 4, instead of 3,2-dioxaborolane (2- [9,10-di-2-naphthalenyl-2-anthracenyl] -4,4,5,5-tetramethyl-1,3,2-dioxaborolane) 4,5,5-tetramethyl-2- (2- (naphthalen-7-yl) naphthalen-6-yl) -1,3,2-dioxaborolan (4,4,5,5-tetramethyl- 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) was used. 4.7 g, yield 58%) was prepared.

MS: [M + H] ⁺ = 669

Preparation Example 7 Preparation of Compound 1-2-18

In the production example of 1-2-28 of Preparation Example 1, 2- [9,10-di-2-naphthalenyl-2-anthracenyl] -4,4,5,5-tetramethyl-1, 2, instead of 3,2-dioxaborolane (2- [9,10-di-2-naphthalenyl-2-anthracenyl] -4,4,5,5-tetramethyl-1,3,2-dioxaborolane) -Naphthalene boronic acid compound (4.1 g, 24.0 mmol) was reacted in the same manner except using compound 1C instead of compound 2C to give compound 1-2-18 (4.9 g, yield 73%).

MS: [M + H] ⁺ = 669

Preparation Example 8 Preparation of Compound 1-3-2

1) Preparation of Compound 4A

2- [9,10-di-2-naphnalenyl-2-anthracenyl] -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2- [9,10 -di-2-naphthalenyl-2-anthracenyl] -4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 56 g, 100 mmol), 1-bromo-2-iodobenzene (28.3 g, 100 mmol) ) Was completely dissolved in tetrahydrofuran (400 mL), 2M aqueous potassium carbonate solution was added, tetrabistriphenylphosphino palladium (2.3 g, 2 mmol) was added thereto, and the mixture was heated and stirred for 10 hours. The temperature was lowered to room temperature, the resulting solution was dried over anhydrous magnesium sulfate, and recrystallized with CHCl ₃ / n-Hex to prepare the compound 4A (23.6 g, yield 66%).

MS: [M + H] ⁺ = 585

2) Preparation of Compound 4B

Compound 4A (12 g, 20.5 mmol) synthesized in 1) above was added with anhydrous THF (100 mL) under a nitrogen atmosphere, and the reaction temperature was maintained at -78 ^° C. n-BuLi (2.5M in HEX, 11.5 mL, 28.7 mmol) was added dropwise to the reaction solution. After stirring for about 40 minutes, fluorenone (3.6g, 20mmol) was added to the reaction mixture and stirred. After about 1 hour to warm up to room temperature and stirred for 3 hours. Aqueous ammonium chloride solution was added to the reaction mixture, and the THF layer was separated. After drying the organic layer with anhydrous magnesium sulfate, ethyl ether was added to prepare a solid compound 4B.

MS: [M + H] ⁺ = 686

3) Preparation of Compound 1-3-2

The compound 4B obtained in the above 2) was no longer purified, and 100 mL of acetic acid was added thereto and stirred. 2 mL of sulfuric acid was added dropwise to the reaction solution, followed by heating and stirring at 80 ° C. After stirring for 8 hours, the yellow solid produced by cooling to room temperature was filtered, washed with water and ethanol and dried to prepare compound 1-3-2 (12.2g, 91% yield).

MS: [M + H] ⁺ = 669

Preparation Example 9 Preparation of Compound 1-2-38

Carbazole (4.0 g, 24 mmol), Compound 1C (5.7 g, 10 mmol) were dissolved in 200 ml of xylene, sodium-tertiary-butoxide 1.4 g (14 mmol), Pd [P (t-Bu) ₃ ] ₂ 0.1 g (0.2 mmol) was added and then refluxed under nitrogen stream for 5 hours. Distilled water was added to the reaction solution to terminate the reaction, and the organic layer was extracted. Compound 1-2-38 (4.7 g, yield 63%) was prepared by recrystallization with a normal-hexane / CHCl ₃ solvent.

MS: [M + H] ⁺ = 747

Preparation Example 10 Preparation of Compound 1-2-45

Compound 1C (5.1 g, 8.8 mmol), 1-naphthylphenylamine (4.2 g, 19.4 mmol) was dissolved in 150 ml of xylene, sodium-tertiary-butoxide (1.27 g, 13.26 mmol), Pd [P ( t-Bu) ₃ ] ₂ 0.045 g (0.088 mmol) was added and then refluxed under nitrogen stream for 5 hours. Distilled water was added to the reaction solution to terminate the reaction, and the organic layer was extracted. After dissolving in ethyl acetate, crystallized with ethanol, filtered and dried in vacuo to give compound 1-2-45 (4.1g, 55% yield).

MS: [M + H] ⁺ = 851

Preparation Example 11 Preparation of Compound 1-2-68

Compound 1C (5.7 g, 10 mmol), di- (2-methylphenyl) amine (3.9 g, 20 mmol) was dissolved in 120 ml of xylene, sodium-tertiary-butoxide (1.27 g, 13.26 mmol), Pd [P ( t-Bu) ₃ ] ₂ 0.045 g (0.088 mmol) was added and then refluxed under nitrogen stream for 5 hours. Distilled water was added to the reaction solution to terminate the reaction, and the organic layer was extracted. After dissolving in ethyl acetate, crystallized with ethanol, filtered and dried in vacuo to give compound 1-2-68 (4.8g, yield 60%).

MS: [M + H] ⁺ = 807

Preparation Example 12 Preparation of Compound 1-2-64

In the production example of 1-2-28 of Preparation Example 1, 2- [9,10-di-2-naphthalenyl-2-anthracenyl] -4,4,5,5-tetramethyl-1, 2- instead of 3,2-dioxaborolane (2- [9,10-di-2-naphthalenyl-2-anthracenyl] -4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) naphthalen-6-yl) -1-phenyl-1H-benzo [d] imidazole (2- (2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) naphthalen-6-yl) -1-phenyl-1H-benzo [d] imidazole, 4.5 g , 10.0 mmol) was reacted in the same manner to prepare a compound 1-2-64 (5.3 g, yield 73%).

MS: [M + H] ⁺ = 735

Preparation Example 13 Preparation of Compound 1-2-54

In the production example of 1-2-28 of Preparation Example 1, 2- [9,10-di-2-naphthalenyl-2-anthracenyl] -4,4,5,5-tetramethyl-1, 2- instead of 3,2-dioxaborolane (2- [9,10-di-2-naphthalenyl-2-anthracenyl] -4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) benzo [h] quinoline (2- (4- (4,4,5 , 5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) benzo [h] quinoline, 4.6 g, 12.0 mmol), except that compound 1-2-54 (7.1 g) was used. , Yield 88%) was prepared.

MS: [M + H] ⁺ = 670

Preparation Example 14 Preparation of Compound 1-2-41

Compound 2C (8.6 g, 19.4 mmol), 4- (dibiphenylamino) phenylboronic acid (4- (dibiphenylamino) phenylboronic acid, 9.6 g, 19.4 mmol) was dissolved in 150 ml of xylene and sodium-butyric-butoxide (1.27 g, 13.26 mmol) and Pd [P (t-Bu) ₃ ] ₂ 0.045 g (0.088 mmol) were added and then refluxed under nitrogen stream for 5 hours. Distilled water was added to the reaction solution to terminate the reaction, and the organic layer was extracted. It was dissolved in chloroform, crystallized with ethanol, filtered and dried in vacuo to give compound 1-2-41 (11.3 g, yield 72%).

MS: [M + H] ⁺ = 812

Preparation Example 15 Preparation of Compound 1-2-43

Compound 1C (5.7 g, 10 mmol) and bisbiphenylamine (7.1 g, 22 mmol) were dissolved in 120 ml of xylene, sodium-tertiary-butoxide (1.27 g, 13.26 mmol), Pd [P (t-Bu) ₃ ] ₂ 0.045 g (0.088 mmol) was added and then refluxed under nitrogen stream for 5 hours. Distilled water was added to the reaction solution to terminate the reaction, and the organic layer was extracted. After dissolving in ethyl acetate, crystallized with ethanol, filtered and dried in vacuo to give compound 1-2-43 (5.1g, yield 57%).

MS: [M + H] ⁺ = 1055

Preparation Example 16 Preparation of Compound 1-1-39

In the preparation of compound 1-2-28 of Preparation Example 1, 2- [9,10-di-2-naphthalenyl-2-anthracenyl] -4,4,5,5-tetramethyl-1 2, instead of 3,2-dioxaborolane (2- [9,10-di-2-naphthalenyl-2-anthracenyl] -4,4,5,5-tetramethyl-1,3,2-dioxaborolane) -(2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenylen-6-yl) -1-phenyl-1H-benzo [d] Imidazole (2- (2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenylen-6-yl) -1-phenyl-1H-benzo [d] imidazole, Compound 1-1-39 (5.2 g, yield 73%) was prepared by reaction in the same manner except that 4.0 g, 10.0 mmol) was used.

MS: [M + H] ⁺ = 709

Preparation Example 17 Preparation of Compound 1-2-49

In the preparation of compound 1-2-28 of Preparation Example 1, 2- [9,10-di-2-naphthalenyl-2-anthracenyl] -4,4,5,5-tetramethyl-1 2, instead of 3,2-dioxaborolane (2- [9,10-di-2-naphthalenyl-2-anthracenyl] -4,4,5,5-tetramethyl-1,3,2-dioxaborolane) -(4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -4,6-diphenyl-1,3,5-triazine, 4.8 g, 11.0 mmol) Compound 1-2-49 (3.4 g, yield 45%) was prepared in the same manner except using.

MS: [M + H] ⁺ = 748

Preparation Example 18 Preparation of Compound 1-3-5

1) Preparation of Compound 5A

2- [9,10-di-2-naphnalenyl-2-anthracenyl] -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4,4,5, 5-tetramethyl-2- (9,10-diphenylanthracen-3-yl) -1,3,2-dioxaborolane, 9.1 g, 20 mmol), 1-bromo-2-iodobenzene (5.7 g, 20 mmol) After completely dissolved in hydrofuran (150 mL), 2M aqueous potassium carbonate solution was added, tetrabistriphenylphosphino palladium (0.46 g, 0.4 mmol) was added thereto, and the mixture was heated and stirred for 10 hours. The temperature was lowered to room temperature, the resulting solution was dried over anhydrous magnesium sulfate, and recrystallized with CHCl ₃ / n-Hex to prepare the compound 5A (7.4 g, yield 76%).

MS: [M + H] ⁺ = 485

2) Preparation of Compound 5B

Compound 5A (7.4 g, 15.2 mmol) synthesized in 1) was added with anhydrous THF (80 mL) under a nitrogen atmosphere, and the reaction temperature was maintained at −78 ^° C. n-BuLi (2.5 M in HEX, 9.1 mL, 22.8 mmol) was added dropwise to the reaction solution. After stirring for about 40 minutes, 6.1 g of 2- (naphthalen-6-yl) -9H-fluorene-9-one (2- (naphthalen-6-yl) -9H-fluoren-9-one, 6.1 g was added to the reaction mixture solution. , 20 mmol) was added and stirred. After about 1 hour to warm up to room temperature and stirred for 3 hours. Aqueous ammonium chloride solution was added to the reaction mixture, and the THF layer was separated. After drying the organic layer with anhydrous magnesium sulfate, ethyl ether was added to prepare a solid compound 5B.

MS: [M + H] ⁺ = 712

3) Preparation of Compound 1-3-5

The compound 5B obtained in the above 2) was no longer purified, but 100 mL of acetic acid was added and stirred. 2 mL of sulfuric acid was added dropwise to the reaction solution, followed by heating and stirring at 80 ° C. After stirring for 8 hours, the yellow solid produced by cooling to room temperature was filtered, washed with water and ethanol and dried to prepare compound 1-3-5 (13.1 g, yield 94%).

MS: [M + H] ⁺ = 695

<Experimental Example 1-1>

The glass substrate coated with ITO (indium tin oxide) to a thickness of 1,500 kPa was put in distilled water in which detergent was dissolved and ultrasonically washed. At this time, a product of Fischer Co. was used as a detergent, and distilled water filtered secondly as a filter of Millipore Co. was used as distilled water. After ITO was washed for 30 minutes, ultrasonic washing was performed twice with distilled water for 10 minutes. After washing the distilled water, ultrasonic washing with a solvent of isopropyl alcohol, acetone, methanol, dried and transported to a plasma cleaner. The substrate was cleaned for 5 minutes using an oxygen plasma and then transferred to a vacuum evaporator.

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

Compound 1-2-54 prepared in Preparation Example 13 was vacuum deposited on the light emitting layer to a thickness of 200 kPa to form an electron injection and transport layer. The cathode was formed by sequentially depositing 12 라이드 thick lithium fluoride (LiF) and 2,000 Å thick aluminum on the electron injection and transport layer. In the above process, the deposition rate of the organic material was maintained at 1 Å / sec, the lithium fluoride was 0.2 Å / sec, and the aluminum was maintained at a deposition rate of 3 to 7 Å / sec.

<Experimental Example 1-2>

Except for using the compound 1-1-39 instead of the compound 1-2-54 prepared in Preparation Example 13 on the light emitting layer in Experimental Example 1-1.

<Experimental Example 1-3>

Except for using the compound 1-2-49 instead of the compound 1-2-54 prepared in Preparation Example 13 on the emission layer in Experimental Example 1-1.

<Experimental Example 1-4>

Except for using the compound 1-2-64 instead of the compound 1-2-54 prepared in Preparation Example 13 on the emission layer in Experimental Example 1-1.

Comparative Example 1

Except that Alq ₃ was used instead of Compound 1-2-54 prepared in Preparation Example 13 on the light emitting layer in Experimental Example 1-1 was the same experiment.

Experimental results of the organic light emitting device manufactured by using the respective compounds as electron injection and transport layer materials as in Experimental Examples 1-1 to 1-4 are shown in Table 1 below.

As can be seen in Table 1, it can be seen that the device of Experimental Examples 1-1 to 1-4 has improved characteristics in terms of low voltage and efficiency than the device of Comparative Experimental Example 1.

Experimental Example 2-1

The glass substrate coated with ITO (indium tin oxide) to a thickness of 1,500 kPa was put in distilled water in which detergent was dissolved and ultrasonically washed. At this time, a product of Fischer Co. was used as a detergent, and distilled water filtered secondly as a filter of Millipore Co. was used as distilled water. After ITO was washed for 30 minutes, ultrasonic washing was performed twice with distilled water for 10 minutes. After washing the distilled water, ultrasonic washing with a solvent of isopropyl alcohol, acetone, methanol, dried and transported to a plasma cleaner. The substrate was cleaned for 5 minutes using an oxygen plasma and then transferred to a vacuum evaporator.

Hexanitrile hexaazatriphenylene was thermally vacuum deposited to a thickness of 500 kPa on the prepared ITO transparent electrode to form a hole injection layer. NPB (400 kV), which is a material for transporting holes, was vacuum deposited thereon, and the compound was vacuum deposited to a thickness of 300 kPa using Compound 1-2-28 prepared in Preparation Example 1 as a host as a light emitting layer and doped with dopant D2. . The E1 was vacuum deposited to a thickness of 200 kPa on the light emitting layer to form an electron injection and transport layer. 12 전자 thick lithium fluoride (LiF) and 2,000 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 2 Å / sec, the vacuum degree during deposition is 2 × 10 ⁻⁷ to 5 × 10 ⁻⁸ torr was maintained.

Experimental Example 2-2

Except for using the compound 1-3-2 instead of compound 1-2-28 in Experimental Example 2-1 was the same experiment.

Experimental Example 2-3

Except for using the compound 1-2-66 instead of compound 1-2-28 in Experimental Example 2-1 was the same experiment.

Experimental Example 2-4

Except for using the compound 1-2-29, dopant D2 in place of compound 1-2-28 in Experimental Example 2-1 was the same experiment.

Experimental Example 2-5

Except for using the compound 1-2-31, dopant D2 in place of compound 1-2-28 in Experimental Example 2-1 was the same experiment.

Experimental Example 2-6

Except for using the compound 1-2-32, dopant D2 instead of compound 1-2-28 in Experimental Example 2-1 was the same experiment.

Experimental Example 2-7

Except for using the compound 1-2-15, dopant D2 in place of compound 1-2-28 in Experimental Example 2-1 was the same experiment.

Experimental Example 2-8

Except for using the compound 1-2-18, dopant D2 in place of compound 1-2-28 in Experimental Example 2-1 was the same experiment.

Comparative Example 2

Except for using the compound H1 compound instead of compound 1-2-28 in Experimental Example 2-1 was the same experiment.

Comparative Example 3

Except for using the compound H1 as a host of the blue light emitting layer instead of the compound 1-2-28 in Experimental Example 2-1 and D1 instead of D2 was the same experiment.

Experimental results of the organic light emitting device manufactured by using the respective compounds as emission layers as in Experimental Examples 2-1 to 2-8 are shown in Table 2 below.

As can be seen in Table 2, Experimental Examples 2-1 to 2-2 can be used as a host of the green light emitting layer, Experimental Examples 2-3 to 2-8 can be used as the blue and green light emitting layer, and suitable substituents When introduced, it showed superior properties than Comparative Experiments 2 to 3.

Experimental Example 3-1

Except for using the compound 1-2-41 instead of compound NPB in Experimental Example 2-3 was the same experiment.

Experimental Example 3-2

Except for using the compound 1-2-43 instead of compound NPB in Experimental Example 2-3 was the same experiment.

Experimental Example 3-3

Except for using the compound 1-2-45 instead of compound NPB in Experimental Example 2-3 was the same experiment.

Experimental Example 3-4

Except for using the compound 1-2-68 instead of compound NPB in Experimental Example 2-3 was the same experiment.

Table 3 shows the results of experimenting with the organic light-emitting device manufactured as in Experimental Examples 3-1 to 3-4.

As can be seen in Table 3, Experimental Examples 3-1 to 3-4 can be used as the hole transport layer, when introduced into a suitable substituent, it showed superior properties than Comparative Experiment 3.

1 illustrates 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 illustrates an organic light emitting device structure in which an anode 102, a hole injection / hole transport and light emitting layer 105, an electron transport 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 injection layer 103, a hole transport and light emitting layer 105, an electron transport 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 injection layer 103, a hole transport layer 104, an electron transporting and emitting layer 105, and a cathode 107 are sequentially stacked. .

5 is 1H-NMR (in CDCl ₃ ) of Compound 1C.

6 is a mass spectrum of Compound 1-2-29

7 is a mass spectrum of Compound 1-2-31.

8 is a mass spectrum of Compound 1-2-18.

Claims (13)

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

In Chemical Formula 1, Q is a C ₁₀ ~ C ₃₀ condensed aromatic polycyclic group, n is an integer of 1 to 8, m is an integer of 1 to 4, Ar and Ar 'are the same as or different from each other, and each independently 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 ₃₀ alkenyl group, a substituted or unsubstituted A substituted C ₃ to C ₃₀ 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 ₃₀ An aryloxy group, a substituted or unsubstituted C ₁ to C ₃₀ alkylthioxy group, a substituted or unsubstituted C ₅ to C ₃₀ arylthioxy group, a substituted or unsubstituted C ₁ to C ₃₀ alkylamine group, Substituted or unsubstituted C ₅ to C ₃₀ arylamine group, substituted or unsubstituted C ₆ to C ₅₀ aryl group, substituted or unsubstituted C ₃ to C ₅₀ hetero having O, N or S as a hetero atom Aryl group, substituted or unsubstituted silicone group, substituted or unsubstituted boron group, substituted or unsubstituted silane group, carbonyl group, phos Selected from the group consisting of a aryl group, an amino group, a nitrile group, a hydroxy group, a nitro group, a hydroxy group, a halogen group, an amide group and an ester group, and form a condensed ring of an aliphatic, aromatic, aliphatic hetero or aromatic hetero group with adjacent groups, When n is an integer of 2 or more, the two or more Ars may be the same or different from each other, and when the m is an integer of 2 or more, the two or more Ar ′ may be the same or different from each other, R1 and R2 are the same as or different from each other, and each independently 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 ₃₀ alkenyl group, a substituted or unsubstituted A substituted C ₃ to C ₃₀ cycloalkyl group, a substituted or unsubstituted C ₃ to C ₃₀ cycloalkenyl group, a substituted or unsubstituted C ₆ to C ₅₀ aryl group, and a substituted or unsubstituted hetero hetero atom O, N Or a C ₃ ~ C ₅₀ heteroaryl group having S. The compound of claim 1, wherein Q in Formula 1 is an aromatic polycyclic group having 3 to 4 condensed benzene rings. The compound of claim 1, wherein Q in Formula 1 is phenanthrene, pyrene, anthracene or chrysene. The compound according to claim 1, wherein Chemical Formula 1 is represented by any one of Chemical Formulas 5 to 13. [Chemical Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

In Formulas 5 to 13, R1, R2, Ar 'and m are the same as defined in Formula 1, Ar ₁ to Ar ₈ are each independently the same as the definition of Ar of the formula (1). The method of claim 1, wherein the substituents that may be substituted in Ar, Ar ', R1 and R2 of the formula (1) is deuterium, halogen atoms, carbonyl group, ester group, phosphoryl group, imide group, amino group, nitro group, hydroxy group, cyano group , Alkyl group, alkoxy group, arylthioxy group, alkylthioxy group, alkylamine group, aralkylamine group, arylamine group, alkenyl group, cycloalkyl group, cycloalkenyl group, silane group, boron group, C ₆ ~ C ₅₀ aryl And at least one member selected from the group consisting of C ₃ to C ₅₀ heteroaryl groups. The compound of claim 1, wherein the compound represented by Chemical Formula 1 is selected from the group consisting of the following compounds:

1) Compound A represented by the following Formula 3 is reacted by Suzuki coupling with a halide aryl compound under the palladium (Pd) catalyst to Compound A represented by the following formula (2) as an arylboronic acid-based or arylboronate-based compound: Manufacturing step, 2) After dissolving Compound B in an anhydrous solvent, lithiating with n-, sec- or tert-BuLi, and reacting with R1COR2, a substituted or unsubstituted ketone compound, as a monoalcohol-based compound Preparing compound C represented by 4, and 3) reacting the compound C under acidic conditions to link a ring Method for preparing a compound represented by the following formula (1) comprising: [Formula 1]

[Formula 2] (Ar) nQB (OR) ₂ (3)

[Formula 4]

In Chemical Formulas 1 to 4, Q is a C ₁₀ ~ C ₃₀ condensed aromatic polycyclic group, n is an integer of 1 to 8, m is an integer of 1 to 4, Ar and Ar 'are the same as or different from each other, and each independently 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 ₃₀ alkenyl group, a substituted or unsubstituted A substituted C ₃ to C ₃₀ 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 ₃₀ An aryloxy group, a substituted or unsubstituted C ₁ to C ₃₀ alkylthioxy group, a substituted or unsubstituted C ₅ to C ₃₀ arylthioxy group, a substituted or unsubstituted C ₁ to C ₃₀ alkylamine group, Substituted or unsubstituted C ₅ to C ₃₀ arylamine group, substituted or unsubstituted C ₆ to C ₅₀ aryl group, substituted or unsubstituted C ₃ to C ₅₀ hetero having O, N or S as a hetero atom Aryl group, substituted or unsubstituted silicone group, substituted or unsubstituted boron group, substituted or unsubstituted silane group, carbonyl group, phos Selected from the group consisting of a aryl group, an amino group, a nitrile group, a nitro group, a hydroxyl group, a halogen group, an amide group, and an ester group, and may form a condensed ring of an aliphatic, aromatic, aliphatic hetero, or aromatic hetero group with adjacent groups or form a spiro bond When n is an integer of 2 or more, the two or more Ars may be the same as or different from each other. When m is an integer of 2 or more, the two or more Ar ′ may be the same or different from each other. R, R1 and R2 are the same as or different from each other, and each independently 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 ₃₀ alkenyl group, a substituted or Unsubstituted C ₃ to C ₃₀ cycloalkyl group, substituted or unsubstituted C ₃ to C ₃₀ cycloalkenyl group, substituted or unsubstituted C ₆ to C ₅₀ aryl group, and substituted or unsubstituted heteroatomic O , N ₃ or C ₅₀ having a heteroaryl group. The method according to claim 7, wherein the substituents that can be substituted in Ar, Ar ', R, R1 and R2 of Formula 1 to Formula 4 are deuterium, halogen atoms, carbonyl group, ester group, phosphoryl group, imide group, amino group, nitro group , Hydroxy group, cyano group, alkyl group, alkoxy group, arylthioxy group, alkylthioxy group, alkylamine group, aralkylamine group, arylamine group, alkenyl group, cycloalkyl group, cycloalkenyl group, silane group, boron group, C ₆ A method for producing a compound represented by Formula 1, characterized in that it comprises at least one member selected from the group consisting of an aryl group of C _{30 and} a heteroaryl group of C ₃ to C ₃₀ . 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 the organic material layer is represented by Chemical Formula 1 according to any one of claims 1 to 6. An organic electronic device comprising a compound represented by. The method according to claim 9, wherein the organic material layer comprises at least one layer of a hole injection layer and a hole transport layer, at least one layer of the hole injection layer and the hole transport layer comprises an organic electron compound characterized in that device. The organic electronic device of claim 9, wherein the organic material layer includes a light emitting layer, and the light emitting layer includes a compound represented by Chemical Formula 1. 11. 10. The organic electron of claim 9, wherein the organic material layer includes at least one layer of an electron injection layer and an electron transport layer, and at least one layer of the electron injection layer and the electron transport layer includes a compound represented by Formula 1. device. The organic electronic device of claim 9, wherein the organic electronic device is selected from the group consisting of an organic light emitting device, an organic phosphorescent device, an organic solar cell, an organic photoconductor (OPC), and an organic transistor.

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