WO2012128509A2 - Compound and organic electric element using same, and electronic device thereof - Google Patents

Compound and organic electric element using same, and electronic device thereof Download PDF

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WO2012128509A2
WO2012128509A2 PCT/KR2012/001905 KR2012001905W WO2012128509A2 WO 2012128509 A2 WO2012128509 A2 WO 2012128509A2 KR 2012001905 W KR2012001905 W KR 2012001905W WO 2012128509 A2 WO2012128509 A2 WO 2012128509A2
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organic
indolyl
compound
aryl
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WO2012128509A3 (en
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박정환
김대성
백장열
문성윤
정화순
김원삼
변지훈
최연희
이범성
최대혁
김동하
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덕산하이메탈(주)
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    • C07—ORGANIC CHEMISTRY
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    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
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    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
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    • C07—ORGANIC CHEMISTRY
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    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
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    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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    • C09K2211/1018—Heterocyclic compounds
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
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    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to a compound, an organic electronic device using the same, and an electronic device thereof.
  • organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material.
  • An organic electric element 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 formed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic electric device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.
  • Materials used as the organic material layer in the organic electric element may be classified into light emitting materials and charge transport materials such as hole injection materials, hole transport materials, electron transport materials, electron injection materials and the like depending on their functions.
  • the light emitting material may be classified into a polymer type and a low molecular type according to molecular weight, and may be classified into a fluorescent material derived from a singlet excited state of electrons and a phosphorescent material derived from a triplet excited state of electrons according to a light emitting mechanism. Can be.
  • 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.
  • 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.
  • a host / dopant system may be used.
  • the principle is that when a small amount of dopant having an energy band gap smaller than that of a host forming the light emitting layer is mixed in the light emitting layer, excitons generated in the light emitting layer are transported to the dopant, thereby producing high-efficiency light. At this time, since the wavelength of the host is shifted to the wavelength of the dopant, light having a desired wavelength can be obtained according to the type of dopant to be used.
  • a material constituting 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.
  • a stable and efficient organic material layer for an organic electric element has not yet been made sufficiently, and therefore, the development of new materials is continuously required.
  • the present invention provides a compound represented by the following formula.
  • the present invention provides an organic electric device and an electronic device including the compound represented by the above formula.
  • the present invention is a novel compound, which is useful as a hole injection material, a hole transport material, a light emitting material and / or an electron transport material suitable for fluorescence and phosphorescent devices of all colors, such as red, green, blue, white, etc. Provides useful effects as a transport material.
  • the present invention provides an effect of increasing the efficiency of the organic electronic device, lowering the driving voltage, increasing the life and stability.
  • 1 to 6 show examples of the organic light emitting display device to which the compound of the present invention can be applied.
  • the present invention is a compound represented by the following formula (1) or (2).
  • R 1 , R 2 , R 3 and R 4 are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C One Through C 50 Alkyl group; C 6 ⁇ C 60 aryl group; It may be a heteroaryl group of C 2 ⁇ C 50 containing at least one hetero atom, sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si), but is not limited thereto.
  • n and m may be an integer of 1 to 4.
  • R 1 , R 2 , R 3 and R 4 may be bonded to adjacent groups to form a saturated or unsaturated ring.
  • R 2 and R 3 , R 2 and R 4 , R 3 and R 4 may combine with each other to form a saturated or unsaturated ring.
  • L is a single bond; Halogen group, C 1 ⁇ C 20 alkyl group, C 2 ⁇ C 20 alkenyl group, C 1 ⁇ C 20 alkoxy group, C 6 ⁇ C 20 aryl group, C 7 ⁇ C 20 arylalkyl group, C 8 ⁇ C 6 ⁇ C 60 arylene group unsubstituted or substituted with one or more substituents selected from the group consisting of C 20 arylalkenyl group, C 2 ⁇ C 20 heterocyclic group, nitrile group and acetylene group; A halogen group, a C 1 to C 20 alkyl group, a C 2 to C 20 alkenyl group, a C 1 to C 20 alkoxy group, a C 6 to C 20 arylamine group, a C 6 to C 20 aryl group, C 7 Or an unsubstituted or substituted with one or more substituents in the group consisting of arylalkyl group of -C 20 , C 8 -
  • Ar 1 and Ar 2 are each independently C 1 ⁇ C 20 Alkyl group, C 2 ⁇ C 20 Alkenyl group, C 1 ⁇ C 20 Alkoxy group, C 6 ⁇ C 20 Aryl group, C 7 ⁇ C 20 C 1 ⁇ C 50 Alkyl group unsubstituted or substituted with a substituent selected from the group consisting of an arylalkyl group, C 8 ⁇ C 20 aryl alkenyl group, C 2 ⁇ C 20 hetero ring group, a nitrile group and an acetylene group; Halogen, amino group, nitrile group, nitro group, C 1 ⁇ C 20 alkyl group, C 1 ⁇ C 20 alkoxy group, C 1 ⁇ C 20 alkylamine group, C 1 ⁇ C 20 alkylthiophene group, C 6 C 20 -C 20 arylthiophene group, C 2 -C 20 alkenyl group, C 2 -C 20 alkynyl group, C 3 -C 20
  • aryl group, heteroaryl group of Ar 1 , Ar 2 may be represented as follows, but is not limited thereto.
  • the hetero ring group is a heterocyclic group containing O, N or S as a hetero atom, carbon number is not particularly limited, but may be 2-60 carbon atoms.
  • the heterocyclic group include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, triazine group, acridil group, pyridazine group , Quinolinyl group, isoquinoline group, indole group, carbazole group, benzoxazole group, benzimidazole group, benzthiazole group, benzcarbazole group, benzthiophene group, dibenzothiophene group, benzfuranyl group, dibenzofura Although there exist a nil group etc., it is not limited to these.
  • the substituents may be bonded to each other to form a substituted or unsubstituted saturated or unsaturated ring or ring, for example, an aliphatic, aromatic, or heteroaromatic monocyclic or polycyclic ring.
  • the present invention may include two or more structures of Formula 1 or 2.
  • the compound having the structural formula may be used in a solution process.
  • the compound may form an organic material layer of an organic electric device, which will be described later, by a soluble process.
  • the organic material layer may be formed by using various polymer materials, rather than a solution process or a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer. It can be produced in fewer layers by the method.
  • the compound represented by the formula (1) or (2) may be divided and represented by the formula (3) to the formula (6) according to the type of the substituents.
  • R 1 to R 4 and Ar 1 , Ar 2 , and L may be the same as those of Formulas 1 and 2 described above.
  • the compounds represented by Formulas 1 to 6 may each be one or more than one of the compounds represented by Formula 7.
  • the intermediate E synthesized in the above step was dissolved in anhydrous THF, and the temperature of the reaction was lowered to -78 ° C. After slowly adding dropwise n-BuLi (2.5 M in hexane), the reaction was stirred at 0 ° C. for 1 hour. Then, the temperature of the reaction was lowered to -78 °C, triisopropyl borate solution was added dropwise and stirred at room temperature for 12 hours. After the reaction was completed, 1N-HCl aqueous solution was added thereto, stirred for 30 minutes, and extracted with CH 2 Cl 2 . After removing a small amount of water with anhydrous MgSO 4 and filtered under reduced pressure, the organic solvent was concentrated and the resulting product was separated by column chromatography to give the desired intermediate G (yield: 74%).
  • the intermediate G, 4-bromoaniline, Pd (PPh 3 ) 4 , and K 2 CO 3 synthesized in the above step were dissolved in THF and H 2 O, and refluxed for 24 hours. After the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH 2 Cl 2 , and washed with water. After removal of a small amount of water with anhydrous MgSO 4 and filtration under reduced pressure, the organic solvent was concentrated and the resulting product was separated using column chromatography to give the desired intermediate I (yield: 62%).
  • the intermediate J and the intermediate 5, Pd 2 (dba) 3 , P (tBu) 3 and NaOtBu synthesized in the above step were dissolved in a toluene solvent and then stirred at 110 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired compound 2 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 58%).
  • the intermediate J and the intermediate 6, Pd 2 (dba) 3 , P (tBu) 3 and NaOtBu synthesized in the above step were dissolved in a toluene solvent and then stirred at 110 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired compound 3 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 55%).
  • the intermediate K and the intermediate 3, Pd 2 (dba) 3 , P (tBu) 3 and NaOtBu synthesized in the above step were dissolved in a toluene solvent and then stirred at 110 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired product 61 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 55%).
  • the intermediate K and the intermediate 5, Pd 2 (dba) 3 , P (tBu) 3 and NaOtBu synthesized in the above step were dissolved in a toluene solvent and stirred at 110 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired product 62 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 49%).
  • the intermediate K and the intermediate 6, Pd 2 (dba) 3 , P (tBu) 3 and NaOtBu synthesized in the above step were dissolved in a toluene solvent and then stirred at 110 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired product 63 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 42%).
  • the intermediate L and the intermediate 3, Pd 2 (dba) 3 , P (tBu) 3 and NaOtBu synthesized in the above step were dissolved in a toluene solvent and then stirred at 110 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired compound 88 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 81%).
  • the intermediate L and the intermediate 5, Pd 2 (dba) 3 , P (tBu) 3 and NaOtBu synthesized in the above step were dissolved in a toluene solvent and stirred at 110 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired compound 89 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 79%).
  • the intermediate L and the intermediate 6, Pd 2 (dba) 3 , P (tBu) 3 and NaOtBu synthesized in the above step were dissolved in a toluene solvent and then stirred at 110 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired compound 90 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 77%).
  • the intermediate B synthesized in the above step under nitrogen was dissolved in a solvent of CH 2 Cl 2 , and then N- bromosuccinimide was added and stirred at room temperature for 12 hours. At the end of the reaction, the mixture was extracted with CH 2 Cl 2 and washed with water. After removal of a small amount of water with anhydrous MgSO 4 and filtration under reduced pressure, the product obtained by concentrating the organic solvent was recrystallized using CH 2 Cl 2 and methanol solvent to obtain the desired intermediate P (yield: 90%).
  • the intermediate Q and the intermediate 5, Pd 2 (dba) 3 , P (tBu) 3 and NaOtBu synthesized in the above step were dissolved in a toluene solvent and then stirred at 110 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired product 176 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 62%).
  • Synthesis of other compounds is substantially the same as the method for synthesizing compounds that specifically describes the preparation examples, except that some of the starting materials or intermediates are replaced with starting materials or intermediates of the corresponding compounds.
  • Synthesis of the chemicals 4, 7, 10, 13, 16, 19, 22, 25, 28, 31, 34, 37, in the intermediate J, instead of phenyl at the N atom of the amine group, naphthyl or biphenyl group Synthesis method is substantially the same as that of Compound 1 except that Intermediate 3, which is substituted with an anthryl group, a carbazole group, a fluorene group, and the like are reacted.
  • Synthesis of chemicals 40, 43, 46, 49, 53, 55, 58 replaces the naphthyl group, biphenyl group, anthryl group, carbazole group, fluorene group, etc. instead of phenyl in N atom of amine group in intermediate J.
  • the method of synthesis is substantially the same as that of compound 1, except that the intermediate of the naphthyl group of the N atom of carbazole reacts with intermediate 3.
  • the compound which has the intrinsic property of the introduced substituent can be synthesize
  • the compound according to the present invention can be used for various purposes in the organic light emitting electronic device according to the type and nature of the substituent.
  • the compounds of the present invention can act as various layers other than the host of the phosphorescent or fluorescent light emitting layer because they are freely controlled by the core and the substituents.
  • 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 at least one organic material layer is formed using the above-described compounds.
  • the compounds of the present invention are used in other organic material layers of the organic light emitting device, for example, a light emitting auxiliary layer, an electron injection layer, an electron transport layer, and a hole injection layer, it is obvious that the same effect can be obtained.
  • the compound of the present invention can be used in a soluble process.
  • the compound may form an organic material layer of an organic electronic device, which will be described later, by a solution process.
  • the organic material layer may be formed by using various polymer materials, rather than a solution process or a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer. It can be produced in fewer layers by the method.
  • Organic electroluminescent devices in which the compounds of the present invention can be used include, for example, organic electroluminescent devices (OLEDs), organic solar cells, organic photoconductor (OPC) drums, organic transistors (organic TFTs), and the like.
  • organic electroluminescent device As an example of the organic electroluminescent device to which the compounds of the present invention can be applied, an organic light emitting diode (OLED) will be described.
  • OLED organic light emitting diode
  • the present invention is not limited thereto, and the above-described compounds may be applied to various organic electroluminescent devices.
  • Another embodiment of the present invention is an organic electroluminescent device comprising a first electrode, a second electrode and an organic material layer disposed between the electrodes, wherein at least one of the organic material layer comprises an organic electroluminescent device comprising the compounds of the present invention to provide.
  • 1 to 6 show examples of the organic light emitting display device to which the compound of the present invention can be applied.
  • the organic light emitting device except that at least one layer of an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer to include the compound of the present invention.
  • an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer to include the compound of the present invention.
  • the structure of the organic electroluminescent device according to another embodiment of the present invention is illustrated in Figures 1 to 6, but is not limited to these structures.
  • the organic electroluminescent device includes a substrate 101, 201, 301, 401, 501, 601, an anode 102, 202, 302, 402, 502, 602, a hole injection layer 103, 203, 303, hole transport layer 104, 204, 304, 404, light emitting layer 105, 205, 305, 405, 505, 605, electron transport layer 106, 206, 406, 506, electron injection layer 107 2 to 6, at least one layer of the organic material layer except for the light emitting layer may be omitted.
  • the organic light emitting diode further includes a hole blocking layer (HBL) that blocks hole movement, an electron blocking layer (EBL) that blocks electrons from moving, a light emitting auxiliary layer that helps or assists light emission, and a protective layer. It may be located.
  • the protective layer may be formed to protect the organic material layer or the cathode at the uppermost layer.
  • the compound of the present invention may be included in one or more of an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer.
  • the compound of the present invention is used in place of or in combination with one or more of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a hole blocking layer, an electron blocking layer, a light emitting auxiliary layer and a protective layer It may be used to form.
  • the organic layer may be used not only in one layer but also in two or more layers.
  • it can be used as a hole injection material, a hole transport material, an electron injection material, an electron transport material, a luminescent material and a passivation (kepping) material according to the compound of the present invention, in particular a host or in a luminescent material and host / dopant alone Can be used as a dopant, can be used as a hole injection, a hole transport layer.
  • the organic light emitting device is a metal having a metal or conductivity on a substrate by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation
  • PVD physical vapor deposition
  • An oxide or an alloy thereof is deposited to form an anode, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer is formed thereon, and then a material that can be used as a cathode is deposited thereon.
  • PVD physical vapor deposition
  • an organic electronic device may be fabricated 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, an electron transport layer and an electron injection layer, but is not limited thereto and may have a single layer structure.
  • the organic layer may be formed using a variety of polymer materials, but not by a deposition process or a solvent process, such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer. It can be made with a small number of layers.
  • the organic light emitting device according to another embodiment of the present invention may be used in a solution process such as spin coating or ink jet process.
  • the substrate is a support of the organic light emitting device, and a silicon wafer, quartz or glass plate, metal plate, plastic film or sheet, or the like can be used.
  • the positive electrode material may be a material having a large work function 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 oxides with metals 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.
  • the hole injection layer is located on the anode.
  • the conditions required for the material of the hole injection layer are high hole injection efficiency from the anode, it should be able to transport the injected holes efficiently. This requires a small ionization potential, high transparency to visible light, and excellent hole stability.
  • the hole injection material is a material that can be injected well from the anode at a low voltage, the highest occupied molecular orbital (HOMO) of the hole injection material may be between the work function of the positive electrode material and the HOMO of the surrounding organic material layer.
  • HOMO occupied molecular orbital
  • 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.
  • the hole transport layer is positioned on the hole injection layer.
  • the hole transport layer receives holes from the hole injection layer and transports the holes to the organic light emitting layer located thereon, and serves to prevent high hole mobility, hole stability, and electrons.
  • applications for vehicle body display require heat resistance to the device, and may be a material having a glass transition temperature (Tg) of 70 ° C. or higher.
  • NPD NPB
  • spiro-arylamine compounds perylene-arylamine compounds
  • azacycloheptatriene compounds bis (diphenylvinylphenyl) anthracene and silicon germanium oxide.
  • the organic light emitting layer is positioned on the hole transport layer.
  • the organic light emitting layer is a layer for emitting light by recombination of holes and electrons injected from the anode and the cathode, respectively, and is made of a material having high quantum efficiency.
  • 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 may be a material having good quantum efficiency for fluorescence or phosphorescence.
  • Substances or compounds that satisfy these conditions include Alq3 for green, Balq (8-hydroxyquinoline beryllium salt) for blue, DPVBi (4,4'-bis (2,2-diphenylethenyl) -1,1'- biphenyl) series, Spiro material, Spiro-DPVBi (Spiro-4,4'-bis (2,2-diphenylethenyl) -1,1'-biphenyl), LiPBO (2- (2-benzoxazoyl) -phenollithium salt ), Bis (diphenylvinylphenylvinyl) benzene, aluminum-quinoline metal complex, metal complexes of imidazole, thiazole and oxazole, and the like, perylene, and BczVBi (3,3 '[ (1,1'-biphenyl) -4,4'-diyldi-2,1-ethenediyl] bis (9-ethyl) -9H-carbazole; D
  • DCJTB [2- (1,1-dimethylethyl) -6- [2- (2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H, 5H
  • doping such as -benzo (ij) quinolizin-9-yl) ethenyl] -4H-pyran-4-ylidene] -propanedinitrile
  • an organic light emitting layer is formed of a polymer of polyphenylene vinylene (PPV) or a polymer such as poly fluorene.
  • PPV polyphenylene vinylene
  • a polymer such as poly fluorene can be used for
  • the electron transport layer is positioned on the organic light emitting layer.
  • the electron transport layer needs a material having high electron injection efficiency from the cathode positioned thereon and capable of efficiently transporting the injected electrons. To this end, it must be made of a material having high electron affinity and electron transfer speed and excellent stability to electrons.
  • Examples of the electron transport material that satisfies such conditions include Al complexes of 8-hydroxyquinoline; Complexes including Alq3; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto.
  • the electron injection layer is stacked on the electron transport layer.
  • the electron injection layer is a metal complex compound such as Balq, Alq3, Be (bq) 2, Zn (BTZ) 2, Zn (phq) 2, PBD, spiro-PBD, TPBI, Tf-6P, aromatic compound with imidazole ring, It can be produced using a low molecular material containing a boron compound and the like.
  • the electron injection layer may be formed in a thickness range of 100 ⁇ 300 ⁇ .
  • the cathode is positioned on the electron injection layer. This cathode serves to inject electrons.
  • the material used as the cathode may use the material used for the anode, and may be a metal having a low work function for efficient electron injection.
  • a suitable metal such as tin, magnesium, indium, calcium, sodium, lithium, aluminum, silver, or a suitable alloy thereof can be used.
  • electrodes having a two-layer structure such as lithium fluoride and aluminum, lithium oxide and aluminum, strontium oxide and aluminum having a thickness of 100 ⁇ m or less may also be used.
  • the compound of the present invention can be used as a hole injection material, a hole transport material, a light emitting material, an electron transport material, and an electron injection material suitable for fluorescence and phosphorescent devices of all colors such as red, green, blue, and white, It can be used as a host or dopant material of various colors.
  • the organic light emitting device may be a top emission type, a bottom emission type or a double-sided emission type according to the material used.
  • the present invention includes a display device including the organic electric element described above, and a terminal including a control unit for driving the display device.
  • This terminal means a current or future wired or wireless communication terminal.
  • the terminal according to the present invention described above may be a mobile communication terminal such as a mobile phone, and includes all terminals such as a PDA, an electronic dictionary, a PMP, a remote control, a navigation device, a game machine, various TVs, various computers, and the like.
  • the compounds were synthesized according to the synthesis method described above, and the examples in which the compounds were applied to an organic material layer of an organic electroluminescent device, for example, an organic electroluminescent device, were compared with those of commonly used compounds.
  • a copper phthalocyanine (hereinafter abbreviated as CuPc) film was vacuum-deposited as a hole injection layer on the ITO layer (anode) formed on the organic substrate to form a thickness of 10 nm.
  • the inventive compound and the comparative example were vacuum deposited with a hole transport layer to a thickness of 20 nm. Vacuum deposition was carried out for comparative experiments.
  • BD-052X (Idemitsu Co., Ltd.) was used as a light emitting dopant, and the host material was 9,10-di- (naphthalene-2-anthracene) (hereinafter abbreviated as ADN), and the doping concentration was fixed at 4%.
  • a comparative experiment was conducted. Subsequently, tris (8-quinolinol) aluminum was deposited to a thickness of 40 nm with an electron injection layer. Subsequently, LiF, which is an alkyl halide metal, was deposited to a thickness of 0.2 nm, and then Al was deposited to a thickness of 150 nm to prepare an organic light emitting device by using Al / LiF as a cathode.
  • LiF which is an alkyl halide metal
  • the electroluminescent (EL) characteristics of the Example and Comparative Example organic electroluminescent devices manufactured as described above were applied to the PR-650 of photoresearch by applying a forward bias DC voltage, and the measurement result was 1000 cd / m 2.
  • the T95 lifetime was measured using a life measurement instrument manufactured by McScience Inc. at the reference luminance.
  • an organic electroluminescent device having the same structure was manufactured using the compound represented by the following formula instead of the compound of the present invention as the hole transport layer material.
  • the organic light emitting device using the organic light emitting device material of the present invention can not only improve color purity but also improve driving voltage significantly.
  • the driving voltage, luminous efficiency, emission color, and lifespan are not only higher than those of the comparative example, but also higher in color purity and improved in driving voltage. It confirmed that there was.

Abstract

The present invention provides a compound, an organic electric element using same, and an electronic device thereof.

Description

화합물 및 이를 이용한 유기전기소자, 그 전자장치Compound, organic electric element using same, electronic device thereof
본 발명은 화합물 및 이를 이용한 유기전기소자, 그 전자장치에 관한 것이다.The present invention relates to a compound, an organic electronic device using the same, and an electronic device thereof.
일반적으로 유기 발광 현상이란 유기 물질을 이용하여 전기에너지를 빛에너지로 전환시켜주는 현상을 말한다. 유기 발광 현상을 이용하는 유기전기소자는 통상 양극과 음극 및 이 사이에 유기물층을 포함하는 구조를 가진다. 여기서 유기물층은 유기전기소자의 효율과 안정성을 높이기 위하여 각기 다른 물질로 구성된 다층의 구조로 이루어진 경우가 많으며, 예컨대 정공주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층 등으로 이루어질 수 있다.In general, organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material. An organic electric element 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 multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic electric device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.
유기전기소자에서 유기물층으로 사용되는 재료는 기능에 따라, 발광 재료와 전하 수송 재료, 예컨대 정공주입 재료, 정공수송 재료, 전자수송 재료, 전자주입재료 등으로 분류될 수 있다. 그리고, 상기 발광 재료는 분자량에 따라 고분자형과 저분자형으로 분류될 수 있고, 발광 메커니즘에 따라 전자의 일중항 여기상태로부터 유래되는 형광 재료와 전자의 삼중항 여기상태로부터 유래되는 인광 재료로 분류될 수 있다. 또한, 발광 재료는 발광색에 따라 청색, 녹색, 적색 발광 재료와 보다 나은 천연색을 구현하기 위해 필요한 노란색 및 주황색 발광 재료로 구분될 수 있다.Materials used as the organic material layer in the organic electric element may be classified into light emitting materials and charge transport materials such as hole injection materials, hole transport materials, electron transport materials, electron injection materials and the like depending on their functions. The light emitting material may be classified into a polymer type and a low molecular type according to molecular weight, and may be classified into a fluorescent material derived from a singlet excited state of electrons and a phosphorescent material derived from a triplet excited state of electrons according to a light emitting mechanism. Can be. 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.
한편, 발광 재료로서 하나의 물질만 사용하는 경우 분자간 상호 작용에 의하여 최대 발광 파장이 장파장으로 이동하고 색순도가 떨어지거나 발광 감쇄 효과로 소자의 효율이 감소되는 문제가 발생하므로, 색순도의 증가와 에너지 전이를 통한 발광 효율을 증가시키기 위하여 발광 재료로서 호스트/도판트 계를 사용할 수 있다. 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.
그 원리는 발광층을 형성하는 호스트 보다 에너지 대역 간극이 작은 도판트를 발광층에 소량 혼합하면, 발광층에서 발생한 엑시톤이 도판트로 수송되어 효율이 높은 빛을 내는 것이다. 이때 호스트의 파장이 도판트의 파장대로 이동하므로, 이용하는 도판트의 종류에 따라 원하는 파장의 빛을 얻을 수 있다.The principle is that when a small amount of dopant having an energy band gap smaller than that of a host forming the light emitting layer is mixed in the light emitting layer, excitons generated in the light emitting layer are transported to the dopant, thereby producing high-efficiency light. At this time, since the wavelength of the host is shifted to the wavelength of the dopant, light having a desired wavelength can be obtained according to the type of dopant to be used.
전술한 유기전기소자가 갖는 우수한 특징들을 충분히 발휘하기 위해서는 소자 내 유기물층을 이루는 물질, 예컨대 정공주입 물질, 정공수송 물질, 발광 물질, 전자수송 물질, 전자주입 물질 등이 안정하고 효율적인 재료에 의하여 뒷받침되는 것이 선행되어야 하나, 아직까지 안정하고 효율적인 유기전기소자용 유기물층 재료의 개발이 충분히 이루어지지 않은 상태이며, 따라서 새로운 재료의 개발이 계속 요구되고 있다.In order to fully exhibit the excellent characteristics of the above-described organic electroluminescent device, a material constituting 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 electric element has not yet been made sufficiently, and therefore, the development of new materials is continuously required.
본 발명은 아래 화학식으로 표시되는 화합물을 제공한다. The present invention provides a compound represented by the following formula.
Figure PCTKR2012001905-appb-I000001
Figure PCTKR2012001905-appb-I000001
또한 본 발명은 위 화학식으로 표시되는 화합물을 포함하는 유기전기소자 및 그 전자장치를 제공한다. In another aspect, the present invention provides an organic electric device and an electronic device including the compound represented by the above formula.
본 발명은, 신규한 화합물로 적색, 녹색, 청색, 흰색 등의 모든 칼라의 형광과 인광소자에 적합한 정공주입 재료, 정공수송 재료, 발광 재료 및/또는 전자수송 재료로 유용하며, 정공주입 및 정공수송 물질로 유용한 효과를 제공한다.The present invention is a novel compound, which is useful as a hole injection material, a hole transport material, a light emitting material and / or an electron transport material suitable for fluorescence and phosphorescent devices of all colors, such as red, green, blue, white, etc. Provides useful effects as a transport material.
본 발명은 유기 전자 소자의 효율 상승, 구동전압 하강, 수명 상승 및 안정성 상승 효과를 제공하기 위한 것이다.The present invention provides an effect of increasing the efficiency of the organic electronic device, lowering the driving voltage, increasing the life and stability.
도 1 내지 도 6은 본 발명의 화합물을 적용할 수 있는 유기전계발광소자의 예를 도시한 것이다.1 to 6 show examples of the organic light emitting display device to which the compound of the present invention can be applied.
이하, 본 발명의 일부 실시예들을 예시적인 도면을 통해 상세하게 설명한다.Hereinafter, some embodiments of the present invention will be described in detail through exemplary drawings.
각 도면의 구성요소들에 참조부호를 부가함에 있어서, 동일한 구성요소들에 대해서는 비록 다른 도면상에 표시되더라도 가능한 한 동일한 부호를 가지도록 하고 있음에 유의해야 한다. 또한, 본 발명을 설명함에 있어, 관련된 공지 구성 또는 기능에 대한 구체적인 설명이 본 발명의 요지를 흐릴 수 있다고 판단되는 경우에는 그 상세한 설명은 생략한다.In adding reference numerals to the components of each drawing, it should be noted that the same reference numerals are assigned to the same components as much as possible even though they are shown in different drawings. In addition, in describing the present invention, when it is determined that the detailed description of the related well-known configuration or function may obscure the gist of the present invention, the detailed description thereof will be omitted.
또한, 본 발명의 구성 요소를 설명하는 데 있어서, 제 1, 제 2, A, B, (a),(b) 등의 용어를 사용할 수 있다. 이러한 용어는 그 구성 요소를 다른 구성 요소와 구별하기 위한 것일 뿐, 그 용어에 의해 해당 구성 요소의 본질이나 차례 또는 순서 등이 한정되지 않는다. 어떤 구성 요소가 다른 구성요소에 "연결", "결합" 또는 "접속"된다고 기재된 경우, 그 구성 요소는 그 다른 구성요소에 직접적으로 연결되거나 또는 접속될 수 있지만, 각 구성 요소 사이에 또 다른 구성 요소가 "연결", "결합" 또는 "접속"될 수도 있다고 이해되어야 할 것이다.In addition, in describing the component of this invention, terms, such as 1st, 2nd, A, B, (a), (b), can be used. These terms are only for distinguishing the components from other components, and the nature, order or order of the components are not limited by the terms. If a component is described as being "connected", "coupled" or "connected" to another component, that component may be directly connected to or connected to that other component, but there may be another configuration between each component. It is to be understood that the elements may be "connected", "coupled" or "connected".
본 발명은 하기 화학식 1 또는 2로 표시되는 화합물이다.The present invention is a compound represented by the following formula (1) or (2).
화학식 1
Figure PCTKR2012001905-appb-C000001
 Formula 1
Figure PCTKR2012001905-appb-C000001
화학식 2
Figure PCTKR2012001905-appb-C000002
 Formula 2
Figure PCTKR2012001905-appb-C000002
위 화학식들에서 R1, R2, R3 및 R4는 각각 독립적으로 수소; 중수소; 치환 또는 비치환된 C1~C50의 알킬기; C6~C60의 아릴기; 이종원자인 황(S), 질소(N), 산소(O), 인(P) 및 규소(Si)를 적어도 하나 이상 포함하는 C2~C50의 헤테로아릴기일 수 있으나 이에 제한되지 않는다. 이때 n 과 m은 1~4의 정수일 수 있다. In the above formula, R 1 , R 2 , R 3 and R 4 are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C One Through C 50 Alkyl group; C 6 ~ C 60 aryl group; It may be a heteroaryl group of C 2 ~ C 50 containing at least one hetero atom, sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si), but is not limited thereto. In this case, n and m may be an integer of 1 to 4.
이때 R1, R2, R3 및 R4는 인접한 기와 결합하여 포화 또는 불포화 고리를 형성할 수 있다. 예를 들어 R2과 R3, R2과 R4, R3과 R4는 서로 결합하여 포화 또는 불포화 고리를 형성할 수 있다. In this case, R 1 , R 2 , R 3 and R 4 may be bonded to adjacent groups to form a saturated or unsaturated ring. For example, R 2 and R 3 , R 2 and R 4 , R 3 and R 4 may combine with each other to form a saturated or unsaturated ring.
한편 L은 단일결합; 할로겐기, C1~C20의 알킬기, C2~C20의 알케닐기, C1~C20의 알콕시기, C6~C20의 아릴기, C7~C20의 아릴알킬기, C8~C20의 아릴알케닐기, C2~C20의 헤테로 고리기, 니트릴기 및 아세틸렌기로 이루어진 군에서 선택된 1개 이상의 치환기로 치환 또는 비치환된 C6~C60의 아릴렌기; 할로겐기, C1~C20의 알킬기, C2~C20의 알케닐기, C1~C20의 알콕시기, C6~C20의 아릴아민기, C6~C20의 아릴기, C7~C20의 아릴알킬기, C8~C20의 아릴알케닐기, C2~C20의 헤테로 고리기, 니트릴기 및 아세틸렌기로 이루어진 군에서 1개 이상의 치환기로 치환 또는 비치환 되고 O, N, S 중 적어도 하나를 포함하는 C2~C50의 헤테로아릴렌기일 수 있으나 이에 제한되지 않는다. 또한 l 은 0~2의 정수일 수 있으며 o 는 1~2의 정수일 수 있다. L is a single bond; Halogen group, C 1 ~ C 20 alkyl group, C 2 ~ C 20 alkenyl group, C 1 ~ C 20 alkoxy group, C 6 ~ C 20 aryl group, C 7 ~ C 20 arylalkyl group, C 8 ~ C 6 ~ C 60 arylene group unsubstituted or substituted with one or more substituents selected from the group consisting of C 20 arylalkenyl group, C 2 ~ C 20 heterocyclic group, nitrile group and acetylene group; A halogen group, a C 1 to C 20 alkyl group, a C 2 to C 20 alkenyl group, a C 1 to C 20 alkoxy group, a C 6 to C 20 arylamine group, a C 6 to C 20 aryl group, C 7 Or an unsubstituted or substituted with one or more substituents in the group consisting of arylalkyl group of -C 20 , C 8 -C 20 arylalkenyl group, C 2 -C 20 heterocyclic group, nitrile group and acetylene group It may be a C 2 ~ C 50 heteroarylene group including at least one of, but is not limited thereto. In addition, l may be an integer of 0 to 2 and o may be an integer of 1 to 2.
한편 Ar1 및 Ar2는 각각 독립적으로 C1~C20의 알킬기, C2~C20의 알케닐기, C1~C20의 알콕시기, C6~C20의 아릴기, C7~C20의 아릴알킬기, C8~C20의 아릴알케닐기, C2~C20의 헤테로 고리기, 니트릴기 및 아세틸렌기로 이루어진 군에서 선택된 치환기로 치환 또는 비치환된 C1~C50의 알킬기; 할로겐, 아미노기, 니트릴기, 니트로기, C1~C20의 알킬기, C1~C20의 알콕시기, C1~C20의 알킬아민기, C1~C20의 알킬티오펜기, C6~C20의 아릴티오펜기, C2~C20의 알케닐기, C2~C20의 알키닐기, C3~C20의 시클로알킬기, 중수소로 치환된 C6~C20의 아릴기, C6~C20의 아릴기, C8~C20의 아릴알케닐기, 실란기, 붕소기, 게르마늄기, C5~C20의 헤테로고리기로 이루어진 군으로부터 선택되는 하나 이상의 기로 치환 또는 비치환된 C6~C20의 아릴기; 할로겐기, C1~C20의 알킬기, C2~C20의 알케닐기, C1~C20의 알콕시기, C6~C20의 아릴아민기, C6~C20의 아릴기, C7~C20의 아릴알킬기, C8~C20의 아릴알케닐기, C2~C20의 헤테로 고리기, 니트릴기 및 아세틸렌기로 이루어진 군에서 1개 이상의 치환기로 치환 또는 비치환되고 O, N, S 중 적어도 하나를 포함하는 치환 또는 비치환된 C2~C50의 헤테로아릴기일 수 있으나 이에 제한되지 않는다.Ar 1 and Ar 2 are each independently C 1 ~ C 20 Alkyl group, C 2 ~ C 20 Alkenyl group, C 1 ~ C 20 Alkoxy group, C 6 ~ C 20 Aryl group, C 7 ~ C 20 C 1 ~ C 50 Alkyl group unsubstituted or substituted with a substituent selected from the group consisting of an arylalkyl group, C 8 ~ C 20 aryl alkenyl group, C 2 ~ C 20 hetero ring group, a nitrile group and an acetylene group; Halogen, amino group, nitrile group, nitro group, C 1 ~ C 20 alkyl group, C 1 ~ C 20 alkoxy group, C 1 ~ C 20 alkylamine group, C 1 ~ C 20 alkylthiophene group, C 6 C 20 -C 20 arylthiophene group, C 2 -C 20 alkenyl group, C 2 -C 20 alkynyl group, C 3 -C 20 cycloalkyl group, C 6 -C 20 aryl group substituted with deuterium, C C unsubstituted or substituted with one or more groups selected from the group consisting of 6 to C 20 aryl groups, C 8 to C 20 aryl alkenyl groups, silane groups, boron groups, germanium groups, and C 5 to C 20 heterocyclic groups Aryl groups of 6 to C 20 ; A halogen group, a C 1 to C 20 alkyl group, a C 2 to C 20 alkenyl group, a C 1 to C 20 alkoxy group, a C 6 to C 20 arylamine group, a C 6 to C 20 aryl group, C 7 ~ C 20 aryl group, C 8 ~ C 20 aryl alkenyl group, C 2 ~ C 20 of the hetero ring group, nitrile group and acetylene group is unsubstituted or substituted with one or more substituents from the group consisting of O, N, S It may be a substituted or unsubstituted C 2 ~ C 50 heteroaryl group containing at least one of, but is not limited thereto.
이때 Ar1, Ar2 의 아릴기, 헤테로아릴기는 아래와 같이 나타낼 수 있으며, 이에 한정되는 것은 아니다. At this time, the aryl group, heteroaryl group of Ar 1 , Ar 2 may be represented as follows, but is not limited thereto.
아릴기로써 페닐기, 1-나프틸기, 2-나프틸기, 1-안트릴기, 2-안트릴기, 9-안트릴기, 1-페난트릴기, 2-페난트릴기, 3-페난트릴기, 4-페난트릴기, 1-페날리닐기, 2-페날리닐기, 9-페난트릴기, 1-피렌일기, 2-피렌일기, 4-피렌일기, 2-바이페닐릴기, 3-바이페닐릴기, 4-바이페닐릴기, p-터페닐-4-일기, p-터페닐-3-일기, p-터페닐-2-일기, m-터페닐-4-일기, m-터페닐-3-일기, m-터페닐-2-일기, o-톨릴기, m-톨릴기, p-톨릴기, p-t-뷰틸페닐기, p-(2-페닐프로필)페닐기, 3-메틸-2-나프틸기, 4-메틸-1-나프틸기, 4-메틸-1-안트릴기, 4’-메틸바이페닐릴기, 4”-t-뷰틸-p-터페닐-4-일기, 플루오렌일기 등을 들 수 있으며, 헤테로아닐기로서 2-피롤릴기, 3-피롤릴기, 2-피라진일기, 2-피리딘일기, 3-피리딘일기, 4-피리딘일기, 1-인돌릴기, 2-인돌릴기, 3-인돌릴기, 4-인돌릴기, 5-인돌릴기, 6-인돌릴기, 7-인돌릴기, 1-아이소인돌릴기, 3-아이소인돌릴기, 4-아이소인돌릴기, 5-아이소인돌릴기, 6-아이소인돌릴기, 7-아이소인돌릴기, 2-퓨릴기, 3-퓨릴기, 2-벤조퓨란일기, 3-벤조퓨란일기, 4-벤조퓨란일기, 5-벤조퓨란일기, 6-벤조퓨란일기, 7-벤조퓨란일기, 1-아이소벤조퓨란일기, 3-아이소벤조퓨란일기, 4-아이소벤조퓨란일기, 5-아이소벤조퓨란일기, 6-아이소벤조퓨란일기, 7-아이소벤조퓨란일기, 2-퀴놀릴기, 3-퀴놀릴기, 4-퀴놀릴기, 5-퀴놀릴기, 6-퀴놀릴기, 7-퀴놀릴기, 8-퀴놀릴기, 1-아이소퀴놀릴기, 3-아이소퀴놀릴기, 4-아이소퀴놀릴기, 5-아이소퀴놀릴기, 6-아이소퀴놀릴기, 7-아이소퀴놀릴기, 8-아이소퀴놀릴기, 2-퀴녹살린일기, 5-퀴녹살린일기, 6-퀴녹살린일기, 1-카바졸릴기, 2-카바졸릴기, 3-카바졸릴기, 4-카바졸릴기, 1-아크리딘일기, 2-아크리딘일기, 3-아크리딘일기, 4-아크리딘일기, 9-아크리딘일기, 1,10-페난트롤린-2-일기, 1,10-페난트롤린-3-일기, 1,10-페난트롤린-4-일기, 1,10-페난트롤린-5-일기,1-페나진일기, 2-페나진일기, 1-페노티아진일기, 2-페노티아진일기, 3-페노티아진일기, 4-페노티아진일기, 1-페녹사진일기, 2-페녹사진일기, 3-페녹사진일기, 4-페녹사진일기, 2-옥사졸릴기, 4-옥사졸릴기, 5-옥사졸릴기, 2-옥사다이아졸릴기, 5-옥사다이아졸릴기, 3-퓨라잔일기, 2-티엔일기, 3-티엔일기, 2-메틸피롤-1-일기, 2-메틸피롤-3-일기, 2-메틸피롤-4-일기, 2-메틸피롤-5-일기, 3-메틸피롤-1-일기, 3-메틸피롤-2-일기, 3-메틸피롤-4-일기, 3-메틸피롤-5-일기, 2-t-뷰틸피롤-4-일기, 3-(2-페닐프로필)피롤-1-일기, 2-메틸-1-인돌릴기, 4-메틸-1-인돌릴기, 2-메틸-3-인돌릴기, 4-메틸-3-인돌릴기, 2-t-뷰틸-1-인돌릴기, 4-t-뷰틸-1-인돌릴기, 2-t-뷰틸-3-인돌릴기, 4-t-뷰틸-3-인돌릴기 등을 들 수 있다.As an aryl group, a phenyl group, 1-naphthyl group, 2-naphthyl group, 1- anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group , 4-phenanthryl group, 1-phenalinyl group, 2-phenalylyl group, 9-phenanthryl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, 2-biphenylyl group, 3-biphenyl Aryl group, 4-biphenylyl group, p-terphenyl-4-yl group, p-terphenyl-3-yl group, p-terphenyl-2-yl group, m-terphenyl-4-yl group, m-terphenyl-3 -Yl group, m-terphenyl-2-yl group, o-tolyl group, m-tolyl group, p-tolyl group, pt-butylphenyl group, p- (2-phenylpropyl) phenyl group, 3-methyl-2-naphthyl group , 4-methyl-1-naphthyl group, 4-methyl-1-anthryl group, 4'-methylbiphenylyl group, 4 ”-t-butyl-p-terphenyl-4-yl group, fluorenyl group, etc. are mentioned. 2-pyrrolyl group, 3-pyrrolyl group, 2-pyrazinyl group, 2-pyridinyl group, 3-pyridinyl group, 4-pyridinyl group, 1-indolyl group, 2-indolyl group, 3-indole Reel group, 4-indolyl group, 5-indolyl group, 6-indolyl group, 7-phosphorus Reel group, 1-isoindoleyl group, 3-isoindoleyl group, 4-isoindoleyl group, 5-isoindoleyl group, 6-isoindoleyl group, 7-isoindoleyl group, 2-furyl group, 3 -Furyl group, 2-benzofuranyl group, 3-benzofuranyl group, 4-benzofuranyl group, 5-benzofuranyl group, 6-benzofuranyl group, 7-benzofuranyl group, 1-isobenzofuranyl group, 3-iso Benzofuranyl group, 4-isobenzofuranyl group, 5-isobenzofuranyl group, 6-isobenzofuranyl group, 7-isobenzofuranyl group, 2-quinolyl group, 3-quinolyl group, 4-quinolyl group, 5-quinolyl group, 6-quinolyl group, 7-quinolyl group, 8-quinolyl group, 1-isoquinolyl group, 3-isoquinolyl group, 4-isoquinolyl group, 5-isoquinolyl Group, 6-isoquinolyl group, 7-isoquinolyl group, 8-isoquinolyl group, 2-quinoxalinyl group, 5-quinoxalinyl group, 6-quinoxalinyl group, 1-carbazolyl group, 2-carba Sleepyl group, 3-carbazolyl group, 4-carbazolyl group, 1-acridinyl group, 2-acridinyl group, 3-acridinyl group, 4 -Acridinyl, 9-acridinyl, 1,10-phenanthroline-2-yl, 1,10-phenanthroline-3-yl, 1,10-phenanthroline-4-yl, 1 , 10-phenanthroline-5- diary, 1-phenazinyl group, 2-phenazinyl group, 1-phenothiazine group, 2-phenothiazine group, 3-phenothiazine group, 4-phenothiazine group , 1-phenoxazinediyl, 2-phenoxazinediyl, 3-phenoxazinediyl, 4-phenoxazinediyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-oxadiazolyl, 5-oxadiazolyl group, 3-furazanyl group, 2-thienyl group, 3-thienyl group, 2-methylpyrrole-1-yl group, 2-methylpyrrole-3-yl group, 2-methylpyrrole-4-yl group, 2-methylpyrrole-5-yl group, 3-methylpyrrole-1-yl group, 3-methylpyrrole-2-yl group, 3-methylpyrrole-4-yl group, 3-methylpyrrole-5-yl group, 2-t-butyl Pyrrole-4-yl group, 3- (2-phenylpropyl) pyrrole-1-yl group, 2-methyl-1-indolyl group, 4-methyl-1-indolyl group, 2-methyl-3-indolyl group, 4-methyl 3-indolyl group, 2-t-butyl-1-indolyl group, 4-t-butyl-1-indolyl group, 2-t-butyl-3-indolyl group And 4-t-butyl-3-indolyl group.
상기 화학식들에 있어서, 헤테로 고리기는 이종원자로 O, N 또는 S를 포함하는 헤테로고리기로서, 탄소수는 특별히 한정되지 않으나 탄소수 2-60일 수 있다. 헤테로고리기의 예로는 티오펜기, 퓨란기, 피롤기, 이미다졸기, 티아졸기, 옥사졸기, 옥사디아졸기, 트리아졸기, 피리딜기, 비피리딜기, 트리아진기, 아크리딜기, 피리다진기, 퀴놀리닐기, 이소퀴놀린기, 인돌기, 카바졸기, 벤즈옥사졸기, 벤즈이미다졸기, 벤즈티아졸기, 벤즈카바졸기, 벤즈티오펜기, 디벤조티오펜기, 벤즈퓨라닐기, 디벤조퓨라닐기 등이 있으나, 이들에만 한정되는 것은 아니다.In the above formula, the hetero ring group is a heterocyclic group containing O, N or S as a hetero atom, carbon number is not particularly limited, but may be 2-60 carbon atoms. Examples of the heterocyclic group include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, triazine group, acridil group, pyridazine group , Quinolinyl group, isoquinoline group, indole group, carbazole group, benzoxazole group, benzimidazole group, benzthiazole group, benzcarbazole group, benzthiophene group, dibenzothiophene group, benzfuranyl group, dibenzofura Although there exist a nil group etc., it is not limited to these.
이때 치환기들은 이웃한 치환기끼리 서로 결합하여 치환 또는 비치환된 포화 또는 불포화 고리 또는 환, 예를 들어 지방족, 방향족, 또는 헤테로방향족의 단환식 또는 다환식 고리를 형성할 수 있다. In this case, the substituents may be bonded to each other to form a substituted or unsubstituted saturated or unsaturated ring or ring, for example, an aliphatic, aromatic, or heteroaromatic monocyclic or polycyclic ring.
본 발명의 또 하나의 실시상태에 따르면, 본 발명은 화학식1 또는 2의 구조를 2이상 포함할 수 있다. According to another exemplary embodiment of the present invention, the present invention may include two or more structures of Formula 1 or 2.
한편 상기 구조식을 가지는 화합물은 용액 공정(soluble process)에 사용될 수 있다. 다시말해 상기 화합물을 용액 공정(soluble process)에 의해 후술할 유기전기소자의 유기물층을 형성할 수 있다. 즉 상기 화합물을 유기물층으로 사용할 때 유기물층은 다양한 고분자 소재를 사용하여 증착법이 아닌 용액 공정 또는 솔벤트 프로세스(solvent process), 예컨대 스핀 코팅, 딥 코팅, 닥터 블레이딩, 스크린 프린팅, 잉크젯 프린팅 또는 열 전사법 등의 방법에 의하여 더 적은 수의 층으로 제조될 수 있다.Meanwhile, the compound having the structural formula may be used in a solution process. In other words, the compound may form an organic material layer of an organic electric device, which will be described later, by a soluble process. In other words, when the compound is used as an organic material layer, the organic material layer may be formed by using various polymer materials, rather than a solution process or a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer. It can be produced in fewer layers by the method.
화학식 1 또는 2로 표시되는 화합물은 치환기들의 종류에 따라 화학식 3 내지 화학식 6로 나누어 표시할 수 있다. The compound represented by the formula (1) or (2) may be divided and represented by the formula (3) to the formula (6) according to the type of the substituents.
화학식 3
Figure PCTKR2012001905-appb-C000003
 Formula 3
Figure PCTKR2012001905-appb-C000003
화학식 4
Figure PCTKR2012001905-appb-C000004
 Formula 4
Figure PCTKR2012001905-appb-C000004
화학식 5
Figure PCTKR2012001905-appb-C000005
 Formula 5
Figure PCTKR2012001905-appb-C000005
화학식 6
Figure PCTKR2012001905-appb-C000006
 Formula 6
Figure PCTKR2012001905-appb-C000006
화학식 3 내지6에서 R1 내지 R4 및 Ar1, Ar2, L은 전술한 화학식 1 및 2와 동일할 수 있다. In Formulas 3 to 6, R 1 to R 4 and Ar 1 , Ar 2 , and L may be the same as those of Formulas 1 and 2 described above.
한편, 화학식 1 내지 6 각각으로 표시되는 화합물은 하기 화학식 7로 표시되는 화합물들 중 하나 또는 하나 이상일 수 있다. Meanwhile, the compounds represented by Formulas 1 to 6 may each be one or more than one of the compounds represented by Formula 7.
화학식 7
Figure PCTKR2012001905-appb-C000007
 Formula 7
Figure PCTKR2012001905-appb-C000007
Figure PCTKR2012001905-appb-I000002
Figure PCTKR2012001905-appb-I000002
Figure PCTKR2012001905-appb-I000003
Figure PCTKR2012001905-appb-I000003
Figure PCTKR2012001905-appb-I000004
Figure PCTKR2012001905-appb-I000004
Figure PCTKR2012001905-appb-I000005
Figure PCTKR2012001905-appb-I000005
Figure PCTKR2012001905-appb-I000006
Figure PCTKR2012001905-appb-I000006
Figure PCTKR2012001905-appb-I000007
Figure PCTKR2012001905-appb-I000007
Figure PCTKR2012001905-appb-I000008
Figure PCTKR2012001905-appb-I000008
Figure PCTKR2012001905-appb-I000009
Figure PCTKR2012001905-appb-I000009
Figure PCTKR2012001905-appb-I000010
Figure PCTKR2012001905-appb-I000010
Figure PCTKR2012001905-appb-I000011
Figure PCTKR2012001905-appb-I000011
Figure PCTKR2012001905-appb-I000012
Figure PCTKR2012001905-appb-I000012
Figure PCTKR2012001905-appb-I000013
Figure PCTKR2012001905-appb-I000013
Figure PCTKR2012001905-appb-I000014
Figure PCTKR2012001905-appb-I000014
Figure PCTKR2012001905-appb-I000015
Figure PCTKR2012001905-appb-I000015
Figure PCTKR2012001905-appb-I000016
Figure PCTKR2012001905-appb-I000016
Figure PCTKR2012001905-appb-I000017
Figure PCTKR2012001905-appb-I000017
Figure PCTKR2012001905-appb-I000018
Figure PCTKR2012001905-appb-I000018
Figure PCTKR2012001905-appb-I000019
Figure PCTKR2012001905-appb-I000019
Figure PCTKR2012001905-appb-I000020
Figure PCTKR2012001905-appb-I000020
Figure PCTKR2012001905-appb-I000021
Figure PCTKR2012001905-appb-I000021
Figure PCTKR2012001905-appb-I000022
Figure PCTKR2012001905-appb-I000022
Figure PCTKR2012001905-appb-I000023
Figure PCTKR2012001905-appb-I000023
Figure PCTKR2012001905-appb-I000024
Figure PCTKR2012001905-appb-I000024
Figure PCTKR2012001905-appb-I000025
Figure PCTKR2012001905-appb-I000025
Figure PCTKR2012001905-appb-I000026
Figure PCTKR2012001905-appb-I000026
Figure PCTKR2012001905-appb-I000027
Figure PCTKR2012001905-appb-I000027
Figure PCTKR2012001905-appb-I000028
Figure PCTKR2012001905-appb-I000028
Figure PCTKR2012001905-appb-I000029
Figure PCTKR2012001905-appb-I000029
Figure PCTKR2012001905-appb-I000030
Figure PCTKR2012001905-appb-I000030
Figure PCTKR2012001905-appb-I000031
Figure PCTKR2012001905-appb-I000031
Figure PCTKR2012001905-appb-I000032
Figure PCTKR2012001905-appb-I000032
Figure PCTKR2012001905-appb-I000033
Figure PCTKR2012001905-appb-I000033
Figure PCTKR2012001905-appb-I000034
Figure PCTKR2012001905-appb-I000034
Figure PCTKR2012001905-appb-I000035
Figure PCTKR2012001905-appb-I000035
Figure PCTKR2012001905-appb-I000036
Figure PCTKR2012001905-appb-I000036
실시예Example
이하, 제조예 및 실험예를 통하여 본 발명을 더욱 상세하게 설명한다. 그러나, 이하의 제조예 및 실험예는 본 발명을 예시하기 위한 것이며, 본 발명의 범위가 이들에 의하여 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Preparation Examples and Experimental Examples. However, the following Production Examples and Experimental Examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.
제조예Production Example
이하, 화학식 1 내지 7에 속하는 화합물들에 대한 제조예 또는 합성예를 설명한다. 다만, 화학식 1 내지 7에 속하는 화합물들의 수가 많기 때문에 화학식 1 내지 7에 속하는 화합물들 중 일부를 예시적으로 설명한다. 본 발명이 속하는 기술분야의 통상의 지식을 가진 자, 즉 당업자라면 하기에서 설명한 제조예들을 통해, 예시하지 않은 본 발명에 속하는 화합물을 제조할 수 있다.Hereinafter, preparation examples or synthesis examples of the compounds belonging to Chemical Formulas 1 to 7 will be described. However, some of the compounds belonging to the general formula 1 to 7 because of the large number of compounds belonging to the general formula (1) 7 will be described by way of example. Those skilled in the art to which the present invention pertains, that is, those skilled in the art can prepare the compounds belonging to the present invention which are not illustrated through the preparation examples described below.
중간체 1의 합성Synthesis of Intermediate 1
[반응식 1]Scheme 1
Figure PCTKR2012001905-appb-I000037
Figure PCTKR2012001905-appb-I000037
질소하에서 2-bromofluorene을 benzene 용매에 녹인 후, N-bromosuccinimide를 넣고 5시간동안 환류시켰다. 반응이 종결되면 반응물의 온도를 상온으로 식힌 후 감압여과를 통해 succinimide를 제거하였다. 유기용매를 농축하여 생성된 생성물을 benzene 용매를 사용하여 재결정을 통해 원하는 중간체 1을 얻었다 (수율: 61%).2-bromofluorene was dissolved in a benzene solvent under nitrogen, and N- bromosuccinimide was added and refluxed for 5 hours. At the end of the reaction, the reaction was cooled to room temperature and succinimide was removed by vacuum filtration. The product obtained by concentrating the organic solvent was recrystallized using a benzene solvent to obtain the desired intermediate 1 (yield: 61%).
중간체 2의 합성Synthesis of Intermediate 2
[반응식 2]Scheme 2
Figure PCTKR2012001905-appb-I000038
Figure PCTKR2012001905-appb-I000038
질소하에서 상기단계에서 합성한 중간체 1과 PPh3를 benzene 용매에 녹인 후, 12시간동안 환류시켰다. 반응이 종결되면 반응물의 온도를 낮춘 후, 생성된 침전물을 감압여과 후 ether로 닦아 원하는 중간체 2를 얻었다 (61%).The intermediate 1 and PPh 3 synthesized in the above step under nitrogen were dissolved in a benzene solvent and refluxed for 12 hours. When the reaction was terminated, the temperature of the reactant was lowered, and the resulting precipitate was filtered under reduced pressure and then washed with ether to obtain the desired intermediate 2 (61%).
중간체 3의 합성Synthesis of Intermediate 3
[반응식 3]Scheme 3
Figure PCTKR2012001905-appb-I000039
Figure PCTKR2012001905-appb-I000039
질소하에서 상기단계에서 합성한 중간체 2와 KOtBu를 THF 용매에 녹인 후, 상온에서 30분동안 교반하였다. 이후 paraformaldehyde를 넣고 30 ℃에서 12시간동안 교반하였다. 반응이 종결되면 hexane을 첨가하고 silica-gel을 이용하여 감압여과 후, CH2Cl2로 닦아주었다. 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 중간체 3을 얻었다 (수율: 93%).The intermediate 2 and KO t Bu synthesized in the above step under nitrogen were dissolved in THF solvent, and then stirred at room temperature for 30 minutes. Then paraformaldehyde was added and stirred at 30 ℃ for 12 hours. After the reaction was completed, hexane was added, and the resultant was filtered under reduced pressure using silica-gel, followed by wiping with CH 2 Cl 2 . The resulting product by concentrating the organic solvent was separated using column chromatography to give the desired intermediate 3 (yield: 93%).
중간체 4의 합성Synthesis of Intermediate 4
[반응식 4]Scheme 4
Figure PCTKR2012001905-appb-I000040
Figure PCTKR2012001905-appb-I000040
질소하에서 diphenylmethane을 THF 용매에 녹인 후, 0 ℃에서 n-BuLi을 천천히 넣었다. 이후 상온에서 30분동안 교반한 후, 2-bromofluorenone을 넣고 상온에서 6시간동안 교반하였다. 반응이 종결되면 ammonium chloride 수용액을 넣고 CH2Cl2로 추출하였다. 무수 MgSO4로 소량의 물을 제거하고 감압 여과 후, 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 중간체 4를 얻었다 (수율: 93%).Diphenylmethane was dissolved in THF solvent under nitrogen, and n-BuLi was slowly added thereto at 0 ° C. After stirring at room temperature for 30 minutes, 2-bromofluorenone was added and stirred at room temperature for 6 hours. After the reaction was terminated, ammonium chloride aqueous solution was added and extracted with CH 2 Cl 2 . After removal of a small amount of water with anhydrous MgSO 4 and filtration under reduced pressure, the organic solvent was concentrated and the resulting product was separated by column chromatography to give the desired intermediate 4 (yield: 93%).
중간체 5의 합성Synthesis of Intermediate 5
[반응식 5]Scheme 5
Figure PCTKR2012001905-appb-I000041
Figure PCTKR2012001905-appb-I000041
질소하에서 상기단계에서 합성한 중간체 4와 p-toluenesulphonic acid를 toluene 용매에 녹인 후, Dean-Stark trap을 통해 4시간동안 환류시켰다. 반응이 종결되면 반응물의 온도를 상온으로 낮춘 후, NaHCO3 수용액을 넣고 30분간 교반한 후, CH2Cl2로 추출하였다. 무수 MgSO4로 소량의 물을 제거하고 감압 여과 후, 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 중간체 5를 얻었다 (수율: 90%).Intermediate 4 and p -toluenesulphonic acid synthesized in the above step under nitrogen were dissolved in toluene solvent and refluxed for 4 hours through Dean-Stark trap. After the reaction was completed, the temperature of the reactant was lowered to room temperature, NaHCO 3 aqueous solution was added thereto, stirred for 30 minutes, and extracted with CH 2 Cl 2 . After removal of a small amount of water with anhydrous MgSO 4 and filtration under reduced pressure, the organic solvent was concentrated and the resulting product was separated by column chromatography to give the desired intermediate 5 (yield: 90%).
중간체 6의 합성Synthesis of Intermediate 6
[반응식 6]Scheme 6
Figure PCTKR2012001905-appb-I000042
Figure PCTKR2012001905-appb-I000042
상기단계에서 합성한 중간체 1과 9-bromofluorene, KOH를 DMSO : MeOH = 8 : 2의 비율로 섞은 용매에 녹인 후, 30분동안 교반하였다. 이후 acetic acid를 넣고 10분간 교반한 후, 반응물을 물에 부었다. 이때 생성된 침전물을 감압여과 후, benzene과 ether 용매를 사용하여 재결정을 통해 원하는 중간체 6을 얻었다 (수율: 78%).Intermediate 1, 9-bromofluorene, and KOH synthesized in the above step were dissolved in a solvent mixed in a ratio of DMSO: MeOH = 8: 2 and stirred for 30 minutes. After adding acetic acid and stirring for 10 minutes, the reaction was poured into water. The precipitate thus formed was filtered under reduced pressure, and the desired intermediate 6 was obtained by recrystallization using benzene and an ether solvent (yield: 78%).
중간체 A의 합성Synthesis of Intermediate A
[반응식 7]Scheme 7
Figure PCTKR2012001905-appb-I000043
Figure PCTKR2012001905-appb-I000043
질소하에서 carbazole을 CH2Cl2 용매에 녹인 후, N-bromosuccinimide를 넣고 상온에서 12시간 동안 교반하였다. 반응이 종결되면 CH2Cl2로 추출하고 물로 닦아주었다. 무수 MgSO4로 소량의 물을 제거하고 감압여과 후, 유기용매를 농축하여 생성된 생성물을 CH2Cl2와 methanol 용매를 사용하여 재결정을 통해 원하는 중간체 A를 얻었다 (수율: 83%).Carbazole was dissolved in CH 2 Cl 2 solvent under nitrogen, N- bromosuccinimide was added and stirred at room temperature for 12 hours. At the end of the reaction, the mixture was extracted with CH 2 Cl 2 and washed with water. After removal of a small amount of water with anhydrous MgSO 4 and filtration under reduced pressure, the product obtained by concentrating the organic solvent was recrystallized using CH 2 Cl 2 and methanol solvent to obtain the desired intermediate A (yield: 83%).
중간체 B의 합성Synthesis of Intermediate B
[반응식 8]Scheme 8
Figure PCTKR2012001905-appb-I000044
Figure PCTKR2012001905-appb-I000044
상기단계에서 합성한 중간체 A와 iodobenzene, copper powder, 18-crown-6, K2CO3를 DMF 용매에 녹이고, 반응물의 온도를 140 ℃에서 24시간동안 교반시켰다. 반응이 종결되면 반응물의 온도를 상온으로 낮춘 후, 1N-HCl 수용액을 넣고 30분간 교반한 후, CH2Cl2로 추출하였다. 무수 MgSO4로 소량의 물을 제거하고 감압여과 후, 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 중간체 B를 얻었다 (수율: 80%).Intermediate A, iodobenzene, copper powder, 18-crown-6, K 2 CO 3 synthesized in the above step was dissolved in a DMF solvent, and the reaction temperature was stirred at 140 ° C. for 24 hours. When the reaction was terminated, the temperature of the reactant was lowered to room temperature, 1N-HCl aqueous solution was added thereto, stirred for 30 minutes, and extracted with CH 2 Cl 2 . After removing a small amount of water with anhydrous MgSO 4 and filtered under reduced pressure, the organic solvent was concentrated and the resulting product was separated by column chromatography to give the desired intermediate B (yield: 80%).
중간체 C의 합성Synthesis of Intermediate C
[반응식 9]Scheme 9
Figure PCTKR2012001905-appb-I000045
Figure PCTKR2012001905-appb-I000045
상기단계에서 합성한 중간체 A와 1-iodonaphthalene, copper powder, 18-crown-6, K2CO3를 DMF 용매에 녹이고, 반응물의 온도를 140 ℃에서 24시간동안 교반시켰다. 반응이 종결되면 반응물의 온도를 상온으로 낮춘 후, 1N-HCl 수용액을 넣고 30분간 교반한 후, CH2Cl2로 추출하였다. 무수 MgSO4로 소량의 물을 제거하고 감압여과 후, 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 중간체 C를 얻었다 (수율: 78%).Intermediate A, 1-iodonaphthalene, copper powder, 18-crown-6, K 2 CO 3 synthesized in the above step was dissolved in a DMF solvent, and the reaction temperature was stirred at 140 ° C. for 24 hours. When the reaction was terminated, the temperature of the reactant was lowered to room temperature, 1N-HCl aqueous solution was added thereto, stirred for 30 minutes, and extracted with CH 2 Cl 2 . After removing a small amount of water with anhydrous MgSO 4 and filtered under reduced pressure, the organic solvent was concentrated and the resulting product was separated by column chromatography to give the desired intermediate C (yield: 78%).
중간체 D의 합성Synthesis of Intermediate D
[반응식 10]Scheme 10
Figure PCTKR2012001905-appb-I000046
Figure PCTKR2012001905-appb-I000046
상기단계에서 합성한 중간체 A와 2-iodonaphthalene, copper powder, 18-crown-6, K2CO3를 DMF 용매에 녹이고, 반응물의 온도를 140 ℃에서 24시간동안 교반시켰다. 반응이 종결되면 반응물의 온도를 상온으로 낮춘 후, 1N-HCl 수용액을 넣고 30분간 교반한 후, CH2Cl2로 추출하였다. 무수 MgSO4로 소량의 물을 제거하고 감압여과 후, 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 중간체 D를 얻었다 (수율: 79%).Intermediate A, 2-iodonaphthalene, copper powder, 18-crown-6, K 2 CO 3 synthesized in the above step was dissolved in a DMF solvent, and the reaction temperature was stirred at 140 ° C. for 24 hours. When the reaction was terminated, the temperature of the reactant was lowered to room temperature, 1N-HCl aqueous solution was added thereto, stirred for 30 minutes, and extracted with CH 2 Cl 2 . After removing a small amount of water with anhydrous MgSO 4 and filtered under reduced pressure, the organic solvent was concentrated and the resulting product was separated by column chromatography to give the desired intermediate D (yield: 79%).
중간체 E의 합성Synthesis of Intermediate E
[반응식 11]Scheme 11
Figure PCTKR2012001905-appb-I000047
Figure PCTKR2012001905-appb-I000047
상기단계에서 합성한 중간체 A와 4-iodobiphenyl, copper powder, 18-crown-6, K2CO3를 DMF 용매에 녹이고, 반응물의 온도를 140 ℃에서 24시간동안 교반시켰다. 반응이 종결되면 반응물의 온도를 상온으로 낮춘 후, 1N-HCl 수용액을 넣고 30분간 교반한 후, CH2Cl2로 추출하였다. 무수 MgSO4로 소량의 물을 제거하고 감압여과 후, 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 중간체 E를 얻었다 (수율: 77%).Intermediate A, 4-iodobiphenyl, copper powder, 18-crown-6, K 2 CO 3 synthesized in the above step was dissolved in a DMF solvent, and the reaction temperature was stirred at 140 ° C. for 24 hours. When the reaction was terminated, the temperature of the reactant was lowered to room temperature, 1N-HCl aqueous solution was added thereto, stirred for 30 minutes, and extracted with CH 2 Cl 2 . After removing a small amount of water with anhydrous MgSO 4 and filtered under reduced pressure, the organic solvent was concentrated and the resulting product was separated by column chromatography to give the desired intermediate E (yield: 77%).
중간체 F의 합성Synthesis of Intermediate F
[반응식 12]Scheme 12
Figure PCTKR2012001905-appb-I000048
Figure PCTKR2012001905-appb-I000048
상기단계에서 합성한 중간체 B를 무수 THF(tetrahydrofuran)에 녹이고, 반응물의 온도를 78 ℃로 낮췄다. n-BuLi (2.5 M in hexane)을 천천히 적가하고 난 후, 반응물을 0 ℃에서 1시간동안 교반시켰다. 이후, 반응물의 온도를 78 ℃로 낮추고, triisopropyl borate 용액을 적가하고 상온에서 12시간동안 교반시켰다. 반응이 종결되면 1N-HCl 수용액을 넣고 30분간 교반한 후, CH2Cl2로 추출하였다. 무수 MgSO4로 소량의 물을 제거하고 감압여과 후, 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 중간체 F를 얻었다 (수율: 73%).Intermediate B synthesized in the above step was dissolved in anhydrous THF (tetrahydrofuran), and the temperature of the reactant was lowered to 78 ° C. After slowly adding dropwise n-BuLi (2.5 M in hexane), the reaction was stirred at 0 ° C. for 1 hour. Then, the temperature of the reaction was lowered to 78 ℃, triisopropyl borate solution was added dropwise and stirred at room temperature for 12 hours. After the reaction was completed, 1N-HCl aqueous solution was added thereto, stirred for 30 minutes, and extracted with CH 2 Cl 2 . After removing a small amount of water with anhydrous MgSO 4 and filtered under reduced pressure, the organic solvent was concentrated and the resulting product was separated by column chromatography to give the desired intermediate F (yield: 73%).
중간체 G의 합성Synthesis of Intermediate G
[반응식 13]Scheme 13
Figure PCTKR2012001905-appb-I000049
Figure PCTKR2012001905-appb-I000049
상기단계에서 합성한 중간체 E를 무수 THF에 녹이고, 반응물의 온도를 -78 ℃로 낮췄다. n-BuLi (2.5 M in hexane)을 천천히 적가하고 난 후, 반응물을 0 ℃에서 1시간동안 교반시켰다. 이후, 반응물의 온도를 -78 ℃로 낮추고, triisopropyl borate 용액을 적가하고 상온에서 12시간동안 교반시켰다. 반응이 종결되면 1N-HCl 수용액을 넣고 30분간 교반한 후, CH2Cl2로 추출하였다. 무수 MgSO4로 소량의 물을 제거하고 감압여과 후, 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 중간체 G를 얻었다(수율: 74%).The intermediate E synthesized in the above step was dissolved in anhydrous THF, and the temperature of the reaction was lowered to -78 ° C. After slowly adding dropwise n-BuLi (2.5 M in hexane), the reaction was stirred at 0 ° C. for 1 hour. Then, the temperature of the reaction was lowered to -78 ℃, triisopropyl borate solution was added dropwise and stirred at room temperature for 12 hours. After the reaction was completed, 1N-HCl aqueous solution was added thereto, stirred for 30 minutes, and extracted with CH 2 Cl 2 . After removing a small amount of water with anhydrous MgSO 4 and filtered under reduced pressure, the organic solvent was concentrated and the resulting product was separated by column chromatography to give the desired intermediate G (yield: 74%).
중간체 H의 합성Synthesis of Intermediate H
[반응식 14]Scheme 14
Figure PCTKR2012001905-appb-I000050
Figure PCTKR2012001905-appb-I000050
상기단계에서 합성한 중간체 F와 4-bromoaniline, Pd(PPh3)4, K2CO3를 THF와 H2O에 녹이고, 24시간동안 환류시켰다. 반응이 종료되면 반응물의 온도를 상온으로 식히고, CH2Cl2로 추출하고 물로 닦아주었다. 무수 MgSO4로 소량의 물을 제거하고 감압여과 후, 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 중간체 H를 얻었다 (수율: 64%).Intermediate F, 4-bromoaniline, Pd (PPh 3 ) 4 and K 2 CO 3 synthesized in the above step were dissolved in THF and H 2 O, and refluxed for 24 hours. After the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH 2 Cl 2 , and washed with water. After removing a small amount of water with anhydrous MgSO 4 and filtered under reduced pressure, the organic solvent was concentrated and the resulting product was separated by column chromatography to give the desired intermediate H (yield: 64%).
중간체 I의 합성Synthesis of Intermediate I
[반응식 15]Scheme 15
Figure PCTKR2012001905-appb-I000051
Figure PCTKR2012001905-appb-I000051
상기단계에서 합성한 중간체 G와 4-bromoaniline, Pd(PPh3)4, K2CO3를 THF와 H2O에 녹이고, 24시간동안 환류시켰다. 반응이 종료되면 반응물의 온도를 상온으로 식히고, CH2Cl2로 추출하고 물로 닦아주었다. 무수 MgSO4로 소량의 물을 제거하고 감압여과 후, 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 중간체 I를 얻었다 (수율: 62%).The intermediate G, 4-bromoaniline, Pd (PPh 3 ) 4 , and K 2 CO 3 synthesized in the above step were dissolved in THF and H 2 O, and refluxed for 24 hours. After the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH 2 Cl 2 , and washed with water. After removal of a small amount of water with anhydrous MgSO 4 and filtration under reduced pressure, the organic solvent was concentrated and the resulting product was separated using column chromatography to give the desired intermediate I (yield: 62%).
중간체 J의 합성Synthesis of Intermediate J
[반응식 16]Scheme 16
Figure PCTKR2012001905-appb-I000052
Figure PCTKR2012001905-appb-I000052
상기단계에서 합성한 중간체 C와 aniline, Pd2(dba)3, P(tBu)3 그리고 NaOtBu를 toluene 용매에 녹인 후, 100 ℃에서 24시간동안 교반시켰다. 반응이 종결되면 반응온도를 상온으로 낮추고, 뜨거운 toluene용매를 이용하여 Celite/silica-gel를 사용하여 감압여과하였다. 감압여과 후, 유기용매를 농축하여 생성된 생성물을 toluene과 acetone 용매를 사용하여 재결정을 통해 원하는 중간체 J를 얻었다 (수율: 76%).Intermediate C and aniline, Pd 2 (dba) 3 , P (tBu) 3 and NaOtBu synthesized in the above step were dissolved in a toluene solvent and stirred at 100 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the resultant organic solvent was concentrated, and the resultant product was recrystallized using a toluene and acetone solvent to obtain the desired intermediate J (yield: 76%).
중간체 K의 합성Synthesis of Intermediate K
[반응식 17]Scheme 17
Figure PCTKR2012001905-appb-I000053
Figure PCTKR2012001905-appb-I000053
상기단계에서 합성한 중간체 D와 9-aminophenanthrene, Pd2(dba)3, P(tBu)3 그리고 NaOtBu를 toluene 용매에 녹인 후, 100 ℃에서 24시간동안 교반시켰다. 반응이 종결되면 반응온도를 상온으로 낮추고, 뜨거운 toluene용매를 이용하여 Celite/silica-gel를 사용하여 감압여과하였다. 감압여과 후, 유기용매를 농축하여 생성된 생성물을 toluene과 acetone 용매를 사용하여 재결정을 통해 원하는 중간체 K를 얻었다 (수율: 69%).Intermediate D, 9-aminophenanthrene, Pd 2 (dba) 3 , P (tBu) 3 and NaOtBu synthesized in the above step were dissolved in a toluene solvent and stirred at 100 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the resultant organic solvent was concentrated and the resultant product was recrystallized using a toluene and acetone solvent to obtain the desired intermediate K (yield: 69%).
중간체 L의 합성Synthesis of Intermediate L
[반응식 18]Scheme 18
Figure PCTKR2012001905-appb-I000054
Figure PCTKR2012001905-appb-I000054
상기단계에서 합성한 중간체 H와 4-iodobiphenyl, Pd2(dba)3, P(tBu)3 그리고 NaOtBu를 toluene용매에 녹인 후, 80 ℃에서 24시간동안 교반시켰다. 반응이 종결되면 반응온도를 상온으로 낮추고, 뜨거운 toluene용매를 이용하여 Celite/silica-gel를 사용하여 감압여과하였다. 감압여과 후, 유기용매를 농축하여 생성된 생성물을 toluene과 acetone 용매를 사용하여 재결정을 통해 원하는 중간체 L을 얻었다 (수율: 54%).The intermediate H synthesized in the above step and 4-iodobiphenyl, Pd 2 (dba) 3 , P (tBu) 3 and NaOtBu were dissolved in a toluene solvent and stirred at 80 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the organic solvent was concentrated, and the resulting product was recrystallized using a toluene and acetone solvent to obtain the desired intermediate L (yield: 54%).
중간체 M의 합성Synthesis of Intermediate M
[반응식 19]Scheme 19
Figure PCTKR2012001905-appb-I000055
Figure PCTKR2012001905-appb-I000055
상기단계에서 합성한 중간체 I와 iodobenzene, Pd2(dba)3, P(tBu)3 그리고 NaOtBu를 toluene용매에 녹인 후, 80 ℃에서 24시간동안 교반시켰다. 반응이 종결되면 반응온도를 상온으로 낮추고, 뜨거운 toluene용매를 이용하여 Celite/silica-gel를 사용하여 감압여과하였다. 감압여과 후, 유기용매를 농축하여 생성된 생성물을 toluene과 acetone 용매를 사용하여 재결정을 통해 원하는 중간체 M을 얻었다 (수율: 60%).The intermediate I and iodobenzene, Pd 2 (dba) 3 , P (tBu) 3 and NaOtBu synthesized in the above step were dissolved in a toluene solvent and stirred at 80 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the resultant organic solvent was concentrated, and the resultant product was recrystallized using a toluene and acetone solvent to obtain the desired intermediate M (yield: 60%).
화합물 1의 합성Synthesis of Compound 1
[반응식 20]Scheme 20
Figure PCTKR2012001905-appb-I000056
Figure PCTKR2012001905-appb-I000056
상기단계에서 합성한 중간체 J와 중간체 3, Pd2(dba)3, P(tBu)3 그리고 NaOtBu를 toluene 용매에 녹인 후, 110 ℃에서 24시간동안 교반시켰다. 반응이 종결되면 반응온도를 상온으로 낮추고, 뜨거운 toluene용매를 이용하여 Celite/silica-gel를 사용하여 감압여과하였다. 감압여과 후, 유기용매를 농축하여 생성된 생성물을 toluene과 acetone 용매를 사용하여 재결정을 통해 원하는 화합물 1을 얻었다 (수율: 60%).Intermediate J and the intermediate 3, Pd 2 (dba) 3 , P (tBu) 3 and NaOtBu synthesized in the above step was dissolved in a toluene solvent, and stirred at 110 ℃ for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired product 1 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 60%).
화합물 2의 합성Synthesis of Compound 2
[반응식 21]Scheme 21
Figure PCTKR2012001905-appb-I000057
Figure PCTKR2012001905-appb-I000057
상기단계에서 합성한 중간체 J와 중간체 5, Pd2(dba)3, P(tBu)3 그리고 NaOtBu를 toluene 용매에 녹인 후, 110 ℃에서 24시간동안 교반시켰다. 반응이 종결되면 반응온도를 상온으로 낮추고, 뜨거운 toluene용매를 이용하여 Celite/silica-gel를 사용하여 감압여과하였다. 감압여과 후, 유기용매를 농축하여 생성된 생성물을 toluene과 acetone 용매를 사용하여 재결정을 통해 원하는 화합물 2를 얻었다 (수율: 58%).The intermediate J and the intermediate 5, Pd 2 (dba) 3 , P (tBu) 3 and NaOtBu synthesized in the above step were dissolved in a toluene solvent and then stirred at 110 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired compound 2 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 58%).
화합물 3의 합성Synthesis of Compound 3
[반응식 22]Scheme 22
Figure PCTKR2012001905-appb-I000058
Figure PCTKR2012001905-appb-I000058
상기단계에서 합성한 중간체 J와 중간체 6, Pd2(dba)3, P(tBu)3 그리고 NaOtBu를 toluene 용매에 녹인 후, 110 ℃에서 24시간동안 교반시켰다. 반응이 종결되면 반응온도를 상온으로 낮추고, 뜨거운 toluene용매를 이용하여 Celite/silica-gel를 사용하여 감압여과하였다. 감압여과 후, 유기용매를 농축하여 생성된 생성물을 toluene과 acetone 용매를 사용하여 재결정을 통해 원하는 화합물 3을 얻었다 (수율: 55%).The intermediate J and the intermediate 6, Pd 2 (dba) 3 , P (tBu) 3 and NaOtBu synthesized in the above step were dissolved in a toluene solvent and then stirred at 110 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired compound 3 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 55%).
화합물 61의 합성Synthesis of Compound 61
[반응식 23]Scheme 23
Figure PCTKR2012001905-appb-I000059
Figure PCTKR2012001905-appb-I000059
상기단계에서 합성한 중간체 K와 중간체 3, Pd2(dba)3, P(tBu)3 그리고 NaOtBu를 toluene 용매에 녹인 후, 110 ℃에서 24시간동안 교반시켰다. 반응이 종결되면 반응온도를 상온으로 낮추고, 뜨거운 toluene용매를 이용하여 Celite/silica-gel를 사용하여 감압여과하였다. 감압여과 후, 유기용매를 농축하여 생성된 생성물을 toluene과 acetone 용매를 사용하여 재결정을 통해 원하는 화합물 61을 얻었다 (수율: 55%).The intermediate K and the intermediate 3, Pd 2 (dba) 3 , P (tBu) 3 and NaOtBu synthesized in the above step were dissolved in a toluene solvent and then stirred at 110 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired product 61 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 55%).
화합물 62의 합성Synthesis of Compound 62
[반응식 24]Scheme 24
Figure PCTKR2012001905-appb-I000060
Figure PCTKR2012001905-appb-I000060
상기단계에서 합성한 중간체 K와 중간체 5, Pd2(dba)3, P(tBu)3 그리고 NaOtBu를 toluene 용매에 녹인 후, 110 ℃에서 24시간동안 교반시켰다. 반응이 종결되면 반응온도를 상온으로 낮추고, 뜨거운 toluene용매를 이용하여 Celite/silica-gel를 사용하여 감압여과하였다. 감압여과 후, 유기용매를 농축하여 생성된 생성물을 toluene과 acetone 용매를 사용하여 재결정을 통해 원하는 화합물 62를 얻었다 (수율: 49%).The intermediate K and the intermediate 5, Pd 2 (dba) 3 , P (tBu) 3 and NaOtBu synthesized in the above step were dissolved in a toluene solvent and stirred at 110 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired product 62 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 49%).
화합물 63의 합성Synthesis of Compound 63
[반응식 25]Scheme 25
Figure PCTKR2012001905-appb-I000061
Figure PCTKR2012001905-appb-I000061
상기단계에서 합성한 중간체 K와 중간체 6, Pd2(dba)3, P(tBu)3 그리고 NaOtBu를 toluene 용매에 녹인 후, 110 ℃에서 24시간동안 교반시켰다. 반응이 종결되면 반응온도를 상온으로 낮추고, 뜨거운 toluene용매를 이용하여 Celite/silica-gel를 사용하여 감압여과하였다. 감압여과 후, 유기용매를 농축하여 생성된 생성물을 toluene과 acetone 용매를 사용하여 재결정을 통해 원하는 화합물 63을 얻었다 (수율: 42%).The intermediate K and the intermediate 6, Pd 2 (dba) 3 , P (tBu) 3 and NaOtBu synthesized in the above step were dissolved in a toluene solvent and then stirred at 110 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired product 63 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 42%).
화합물 88의 합성Synthesis of Compound 88
[반응식 26]Scheme 26
Figure PCTKR2012001905-appb-I000062
Figure PCTKR2012001905-appb-I000062
상기단계에서 합성한 중간체 L과 중간체 3, Pd2(dba)3, P(tBu)3 그리고 NaOtBu를 toluene 용매에 녹인 후, 110 ℃에서 24시간동안 교반시켰다. 반응이 종결되면 반응온도를 상온으로 낮추고, 뜨거운 toluene용매를 이용하여 Celite/silica-gel를 사용하여 감압여과하였다. 감압여과 후, 유기용매를 농축하여 생성된 생성물을 toluene과 acetone 용매를 사용하여 재결정을 통해 원하는 화합물 88을 얻었다 (수율: 81%).The intermediate L and the intermediate 3, Pd 2 (dba) 3 , P (tBu) 3 and NaOtBu synthesized in the above step were dissolved in a toluene solvent and then stirred at 110 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired compound 88 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 81%).
화합물 89의 합성Synthesis of Compound 89
[반응식 27]Scheme 27
Figure PCTKR2012001905-appb-I000063
Figure PCTKR2012001905-appb-I000063
상기단계에서 합성한 중간체 L과 중간체 5, Pd2(dba)3, P(tBu)3 그리고 NaOtBu를 toluene 용매에 녹인 후, 110 ℃에서 24시간동안 교반시켰다. 반응이 종결되면 반응온도를 상온으로 낮추고, 뜨거운 toluene용매를 이용하여 Celite/silica-gel를 사용하여 감압여과하였다. 감압여과 후, 유기용매를 농축하여 생성된 생성물을 toluene과 acetone 용매를 사용하여 재결정을 통해 원하는 화합물 89를 얻었다 (수율: 79%).The intermediate L and the intermediate 5, Pd 2 (dba) 3 , P (tBu) 3 and NaOtBu synthesized in the above step were dissolved in a toluene solvent and stirred at 110 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired compound 89 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 79%).
화합물 90의 합성Synthesis of Compound 90
[반응식 28]Scheme 28
Figure PCTKR2012001905-appb-I000064
Figure PCTKR2012001905-appb-I000064
상기단계에서 합성한 중간체 L과 중간체 6, Pd2(dba)3, P(tBu)3 그리고 NaOtBu를 toluene 용매에 녹인 후, 110 ℃에서 24시간동안 교반시켰다. 반응이 종결되면 반응온도를 상온으로 낮추고, 뜨거운 toluene용매를 이용하여 Celite/silica-gel를 사용하여 감압여과하였다. 감압여과 후, 유기용매를 농축하여 생성된 생성물을 toluene과 acetone 용매를 사용하여 재결정을 통해 원하는 화합물 90을 얻었다 (수율: 77%).The intermediate L and the intermediate 6, Pd 2 (dba) 3 , P (tBu) 3 and NaOtBu synthesized in the above step were dissolved in a toluene solvent and then stirred at 110 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired compound 90 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 77%).
화합물 121의 합성Synthesis of Compound 121
[반응식 29]Scheme 29
Figure PCTKR2012001905-appb-I000065
Figure PCTKR2012001905-appb-I000065
상기단계에서 합성한 중간체 M과 중간체 3, Pd2(dba)3, P(tBu)3 그리고 NaOtBu를 toluene 용매에 녹인 후, 110 ℃에서 24시간동안 교반시켰다. 반응이 종결되면 반응온도를 상온으로 낮추고, 뜨거운 toluene용매를 이용하여 Celite/silica-gel를 사용하여 감압여과하였다. 감압여과 후, 유기용매를 농축하여 생성된 생성물을 toluene과 acetone 용매를 사용하여 재결정을 통해 원하는 화합물 121을 얻었다 (수율: 83%).Intermediate M and the intermediate 3, Pd 2 (dba) 3 , P (tBu) 3 and NaOtBu synthesized in the above step was dissolved in a toluene solvent and stirred at 110 ℃ for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired compound 121 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 83%).
화합물 122의 합성Synthesis of Compound 122
[반응식 30]Scheme 30
Figure PCTKR2012001905-appb-I000066
Figure PCTKR2012001905-appb-I000066
상기단계에서 합성한 중간체 M과 중간체 5, Pd2(dba)3, P(tBu)3 그리고 NaOtBu를 toluene 용매에 녹인 후, 110 ℃에서 24시간동안 교반시켰다. 반응이 종결되면 반응온도를 상온으로 낮추고, 뜨거운 toluene용매를 이용하여 Celite/silica-gel를 사용하여 감압여과하였다. 감압여과 후, 유기용매를 농축하여 생성된 생성물을 toluene과 acetone 용매를 사용하여 재결정을 통해 원하는 화합물 122를 얻었다 (수율: 80%).Intermediate M and the intermediate 5, Pd 2 (dba) 3 , P (tBu) 3 and NaOtBu synthesized in the above step was dissolved in a toluene solvent and stirred at 110 ℃ for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired product 122 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 80%).
화합물 123의 합성Synthesis of Compound 123
[반응식 31]Scheme 31
Figure PCTKR2012001905-appb-I000067
Figure PCTKR2012001905-appb-I000067
상기단계에서 합성한 중간체 M과 중간체 6, Pd2(dba)3, P(tBu)3 그리고 NaOtBu를 toluene 용매에 녹인 후, 110 ℃에서 24시간동안 교반시켰다. 반응이 종결되면 반응온도를 상온으로 낮추고, 뜨거운 toluene용매를 이용하여 Celite/silica-gel를 사용하여 감압여과하였다. 감압여과 후, 유기용매를 농축하여 생성된 생성물을 toluene과 acetone 용매를 사용하여 재결정을 통해 원하는 화합물 123을 얻었다 (수율: 73%).Intermediate M and the intermediate 6, Pd 2 (dba) 3 , P (tBu) 3 and NaOtBu synthesized in the above step was dissolved in a toluene solvent and stirred at 110 ℃ for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired product 123 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 73%).
중간체 N의 합성Synthesis of Intermediate N
[반응식 32]Scheme 32
Figure PCTKR2012001905-appb-I000068
Figure PCTKR2012001905-appb-I000068
상기단계에서 합성한 중간체 F와 1,3,5-tribromobenzene, Pd(PPh3)4, K2CO3를 THF와 H2O 용매에 녹이고, 24시간동안 환류시켰다. 반응이 종료되면 반응물의 온도를 상온으로 식히고, CH2Cl2로 추출하고 물로 닦아주었다. 무수 MgSO4로 소량의 물을 제거하고 감압여과 후, 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피를 이용하여 분리하여 원하는 중간체 N을 얻었다 (수율: 59%).Intermediate F, 1,3,5-tribromobenzene, Pd (PPh 3 ) 4 and K 2 CO 3 synthesized in the above step were dissolved in THF and H 2 O solvents and refluxed for 24 hours. After the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH 2 Cl 2 , and washed with water. After removing a small amount of water with anhydrous MgSO 4 and filtered under reduced pressure, the organic solvent was concentrated and the resulting product was separated by column chromatography to give the desired intermediate N (yield: 59%).
중간체 O의 합성Synthesis of Intermediate O
[반응식 33]Scheme 33
Figure PCTKR2012001905-appb-I000069
Figure PCTKR2012001905-appb-I000069
상기단계에서 합성한 중간체 N과 aniline, Pd2(dba)3, P(tBu)3 그리고 NaOtBu를 toluene 용매에 녹인 후, 100 ℃에서 24시간동안 교반시켰다. 반응이 종결되면 반응온도를 상온으로 낮추고, 뜨거운 toluene용매를 이용하여 Celite/silica-gel를 사용하여 감압여과하였다. 감압여과 후, 유기용매를 농축하여 생성된 생성물을 toluene과 acetone 용매를 사용하여 재결정을 통해 원하는 중간체 O를 얻었다 (수율: 43%).Intermediate N, aniline, Pd 2 (dba) 3 , P (tBu) 3 and NaOtBu synthesized in the above step were dissolved in a toluene solvent and stirred at 100 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the resultant organic solvent was concentrated and the resultant product was recrystallized using a toluene and acetone solvent to obtain the desired intermediate O (yield: 43%).
화합물 163의 합성Synthesis of Compound 163
[반응식 34]Scheme 34
Figure PCTKR2012001905-appb-I000070
Figure PCTKR2012001905-appb-I000070
상기단계에서 합성한 중간체 O와 중간체 3, Pd2(dba)3, P(tBu)3 그리고 NaOtBu를 toluene 용매에 녹인 후, 110 ℃에서 24시간동안 교반시켰다. 반응이 종결되면 반응온도를 상온으로 낮추고, 뜨거운 toluene용매를 이용하여 Celite/silica-gel를 사용하여 감압여과하였다. 감압여과 후, 유기용매를 농축하여 생성된 생성물을 toluene과 acetone 용매를 사용하여 재결정을 통해 원하는 화합물 163을 얻었다 (수율: 51%).The intermediate O synthesized in the above step and the intermediate 3, Pd 2 (dba) 3 , P (tBu) 3 and NaOtBu was dissolved in a toluene solvent, and stirred at 110 ℃ for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired product 163 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 51%).
화합물 164의 합성Synthesis of Compound 164
[반응식 35]Scheme 35
Figure PCTKR2012001905-appb-I000071
Figure PCTKR2012001905-appb-I000071
상기단계에서 합성한 중간체 O와 중간체 5, Pd2(dba)3, P(tBu)3 그리고 NaOtBu를 toluene 용매에 녹인 후, 110 ℃에서 24시간동안 교반시켰다. 반응이 종결되면 반응온도를 상온으로 낮추고, 뜨거운 toluene용매를 이용하여 Celite/silica-gel를 사용하여 감압여과하였다. 감압여과 후, 유기용매를 농축하여 생성된 생성물을 toluene과 acetone 용매를 사용하여 재결정을 통해 원하는 화합물 164를 얻었다 (수율: 46%).Intermediate O and the intermediate 5, Pd 2 (dba) 3 , P (tBu) 3 and NaOtBu synthesized in the above step were dissolved in a toluene solvent and then stirred at 110 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired product 164 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 46%).
화합물 165의 합성Synthesis of Compound 165
[반응식 36]Scheme 36
Figure PCTKR2012001905-appb-I000072
Figure PCTKR2012001905-appb-I000072
상기단계에서 합성한 중간체 O와 중간체 6, Pd2(dba)3, P(tBu)3 그리고 NaOtBu를 toluene 용매에 녹인 후, 110 ℃에서 24시간동안 교반시켰다. 반응이 종결되면 반응온도를 상온으로 낮추고, 뜨거운 toluene용매를 이용하여 Celite/silica-gel를 사용하여 감압여과하였다. 감압여과 후, 유기용매를 농축하여 생성된 생성물을 toluene과 acetone 용매를 사용하여 재결정을 통해 원하는 화합물 165을 얻었다 (수율: 41%).Intermediate O and the intermediate 6, Pd 2 (dba) 3 , P (tBu) 3 and NaOtBu synthesized in the above step were dissolved in a toluene solvent and stirred at 110 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired product 165 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 41%).
중간체 P의 합성Synthesis of Intermediate P
[반응식 37]Scheme 37
Figure PCTKR2012001905-appb-I000073
Figure PCTKR2012001905-appb-I000073
질소하에서 상기단계에서 합성한 중간체 B를 CH2Cl2 용매에 녹인 후, N-bromosuccinimide를 넣고 상온에서 12시간동안 교반하였다. 반응이 종결되면 CH2Cl2로 추출하고 물로 닦아주었다. 무수 MgSO4로 소량의 물을 제거하고 감압여과 후, 유기용매를 농축하여 생성된 생성물을 CH2Cl2와 methanol 용매를 사용하여 재결정을 통해 원하는 중간체 P를 얻었다 (수율: 90%).The intermediate B synthesized in the above step under nitrogen was dissolved in a solvent of CH 2 Cl 2 , and then N- bromosuccinimide was added and stirred at room temperature for 12 hours. At the end of the reaction, the mixture was extracted with CH 2 Cl 2 and washed with water. After removal of a small amount of water with anhydrous MgSO 4 and filtration under reduced pressure, the product obtained by concentrating the organic solvent was recrystallized using CH 2 Cl 2 and methanol solvent to obtain the desired intermediate P (yield: 90%).
중간체 Q의 합성Synthesis of Intermediate Q
[반응식 38]Scheme 38
Figure PCTKR2012001905-appb-I000074
Figure PCTKR2012001905-appb-I000074
상기단계에서 합성한 중간체 P와 aniline, Pd2(dba)3, P(tBu)3 그리고 NaOtBu를 toluene 용매에 녹인 후, 100 ℃에서 24시간동안 교반시켰다. 반응이 종결되면 반응온도를 상온으로 낮추고, 뜨거운 toluene용매를 이용하여 Celite/silica-gel를 사용하여 감압여과하였다. 감압여과 후, 유기용매를 농축하여 생성된 생성물을 toluene과 acetone 용매를 사용하여 재결정을 통해 원하는 중간체 Q를 얻었다 (수율: 83%).The intermediate P and aniline, Pd 2 (dba) 3 , P (tBu) 3 and NaOtBu synthesized in the above step were dissolved in a toluene solvent and stirred at 100 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the resultant organic solvent was concentrated, and the resultant product was recrystallized using a toluene and acetone solvent to obtain the desired intermediate Q (yield: 83%).
화합물 175의 합성Synthesis of Compound 175
[반응식 39]Scheme 39
Figure PCTKR2012001905-appb-I000075
Figure PCTKR2012001905-appb-I000075
상기단계에서 합성한 중간체 Q와 중간체 3, Pd2(dba)3, P(tBu)3 그리고 NaOtBu를 toluene 용매에 녹인 후, 110 ℃에서 24시간동안 교반시켰다. 반응이 종결되면 반응온도를 상온으로 낮추고, 뜨거운 toluene용매를 이용하여 Celite/silica-gel를 사용하여 감압여과하였다. 감압여과 후, 유기용매를 농축하여 생성된 생성물을 toluene과 acetone 용매를 사용하여 재결정을 통해 원하는 화합물 175을 얻었다 (수율: 66%).Intermediate Q synthesized in the above step and intermediate 3, Pd 2 (dba) 3 , P (tBu) 3 and NaOtBu was dissolved in toluene solvent, and stirred at 110 ℃ for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired product 175 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 66%).
화합물 176의 합성Synthesis of Compound 176
[반응식 40]Scheme 40
Figure PCTKR2012001905-appb-I000076
Figure PCTKR2012001905-appb-I000076
상기단계에서 합성한 중간체 Q와 중간체 5, Pd2(dba)3, P(tBu)3 그리고 NaOtBu를 toluene 용매에 녹인 후, 110 ℃에서 24시간동안 교반시켰다. 반응이 종결되면 반응온도를 상온으로 낮추고, 뜨거운 toluene용매를 이용하여 Celite/silica-gel를 사용하여 감압여과하였다. 감압여과 후, 유기용매를 농축하여 생성된 생성물을 toluene과 acetone 용매를 사용하여 재결정을 통해 원하는 화합물 176을 얻었다 (수율: 62%).The intermediate Q and the intermediate 5, Pd 2 (dba) 3 , P (tBu) 3 and NaOtBu synthesized in the above step were dissolved in a toluene solvent and then stirred at 110 ° C. for 24 hours. After the reaction was completed, the reaction temperature was lowered to room temperature, and filtered under reduced pressure using Celite / silica-gel using a hot toluene solvent. After filtration under reduced pressure, the desired product 176 was obtained by recrystallization of the product obtained by concentrating the organic solvent using toluene and acetone solvent (yield: 62%).
화합물 177의 합성Synthesis of Compound 177
[반응식 41]Scheme 41
Figure PCTKR2012001905-appb-I000077
Figure PCTKR2012001905-appb-I000077
기타 화합물들의 합성Synthesis of Other Compounds
기타 화합물들의 합성은 출발물질들이나 중간체들의 일부가 해당하는 화합물들의 출발물질이나 중간체들로 치횐된 것을 제외하고 구체적으로 제조예들을 설명한 화합물들의 합성방법과 실질적으로 동일하다. Synthesis of other compounds is substantially the same as the method for synthesizing compounds that specifically describes the preparation examples, except that some of the starting materials or intermediates are replaced with starting materials or intermediates of the corresponding compounds.
예를 들어 화학물들 4, 7, 10, 13, 16, 19, 22, 25, 28, 31, 34, 37의 합성방법은 중간체 J에서 아민기의 N원자에 페닐 대신에 나프틸기나 바이페닐기, 안트릴기, 카바졸기, 플루오렌기 등으로 치환된 중간체와 중간체 3을 반응하는 점을 제외하고 화합물 1과 합성방법이 실질적으로 동일하다. 화학물들 40, 43, 46, 49, 53, 55, 58의 합성방법은 중간체 J에서 아민기의 N원자에 페닐 대신에 나프틸기나 바이페닐기, 안트릴기, 카바졸기, 플루오렌기 등으로 치환되고 카바졸의 N원자의 나프틸기의 결합위치가 다른 중간체와 중간체 3을 반응하는 점을 제외하고 화합물 1과 합성방법이 실질적으로 동일하다. For example, the synthesis of the chemicals 4, 7, 10, 13, 16, 19, 22, 25, 28, 31, 34, 37, in the intermediate J, instead of phenyl at the N atom of the amine group, naphthyl or biphenyl group, Synthesis method is substantially the same as that of Compound 1 except that Intermediate 3, which is substituted with an anthryl group, a carbazole group, a fluorene group, and the like are reacted. Synthesis of chemicals 40, 43, 46, 49, 53, 55, 58 replaces the naphthyl group, biphenyl group, anthryl group, carbazole group, fluorene group, etc. instead of phenyl in N atom of amine group in intermediate J. And the method of synthesis is substantially the same as that of compound 1, except that the intermediate of the naphthyl group of the N atom of carbazole reacts with intermediate 3.
마찬가지로 다른 화합물들의 합성방법도 전술한 예들과 출발물질이나 중간체들들이 해당 화합물들로 대체된 점을 제외하고 동일하며 다른 화합물들의 합성방법들도 본 명세서의 일부를 이룬다. Likewise, the method for synthesizing other compounds is the same except that the above-described examples and starting materials or intermediates are replaced with the corresponding compounds, and methods for synthesizing other compounds form part of the present specification.
또한, 상기와 같은 구조의 코어 구조에 다양한 치환기를 도입함으로써 도입된 치환기의 고유 특성을 갖는 화합물을 합성할 수 있다. 예컨대, 유기발광소자를 비롯한 유기전자소자의 제조시 사용되는 정공주입층 물질, 정공수송층 물질, 발광층 물질, 및 전자 수송층 물질에 사용되는 치환기를 상기 구조에 도입함으로써 각 유기물층에서 요구하는 조건들을 충족시키는 물질을 제조할 수 있다.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, by introducing a substituent used in the hole injection layer material, the hole transport layer material, the light emitting layer material, and the electron transport layer material used in the manufacture of the organic electronic device, including the organic light emitting device to satisfy the conditions required for each organic material layer Materials can be prepared.
본 발명에 따른 화합물은 치환기의 종류 및 성질에 따라 유기전계발광전자소자에서 다양한 용도로 사용될 수 있다.The compound according to the present invention can be used for various purposes in the organic light emitting electronic device according to the type and nature of the substituent.
본 발명의 화합물은 코어와 치환체에 의해 조절이 자유롭기 때문에 인광 또는 형광 발광층의 호스트 이외의 다양한 층으로 작용할 수 있다.The compounds of the present invention can act as various layers other than the host of the phosphorescent or fluorescent light emitting layer because they are freely controlled by the core and the substituents.
본 발명의 유기전자소자는 전술한 화합물들을 이용하여 한층 이상의 유기물층을 형성하는 것을 제외하고는, 통상의 유기전자소자의 제조방법 및 재료에 의하여 제조될 수 있다.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 at least one organic material layer is formed using the above-described compounds.
본 발명의 화합물들을 유기전계발광소자의 다른 유기물층들, 예를 들어 발광 보조층, 전자주입층, 전자수송층, 및 정공주입층에 사용되더라도 동일한 효과를 얻을 수 있는 것은 자명하다.When the compounds of the present invention are used in other organic material layers of the organic light emitting device, for example, a light emitting auxiliary layer, an electron injection layer, an electron transport layer, and a hole injection layer, it is obvious that the same effect can be obtained.
한편 본 발명의 화합물은 용액 공정(soluble process)에 사용될 수 있다. 다시 말해 상기 화합물을 용액 공정(soluble process)에 의해 후술할 유기전자소자의 유기물층을 형성할 수 있다. 즉 상기 화합물을 유기물층으로 사용할 때 유기물층은 다양한 고분자 소재를 사용하여 증착법이 아닌 용액 공정 또는 솔벤트 프로세스(solvent process), 예컨대 스핀 코팅, 딥 코팅, 닥터 블레이딩, 스크린 프린팅, 잉크젯 프린팅 또는 열 전사법 등의 방법에 의하여 더 적은 수의 층으로 제조될 수 있다.Meanwhile, the compound of the present invention can be used in a soluble process. In other words, the compound may form an organic material layer of an organic electronic device, which will be described later, by a solution process. In other words, when the compound is used as an organic material layer, the organic material layer may be formed by using various polymer materials, rather than a solution process or a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer. It can be produced in fewer layers by the method.
본 발명의 화합물들이 사용될 수 있는 유기전기소자는 예를 들어, 유기전계발광소자(OLED), 유기태양전지, 유기감광체(OPC) 드럼, 유기트랜지스트(유기 TFT) 등이 있다.Organic electroluminescent devices in which the compounds of the present invention can be used include, for example, organic electroluminescent devices (OLEDs), organic solar cells, organic photoconductor (OPC) drums, organic transistors (organic TFTs), and the like.
본 발명의 화합물들이 적용될 수 있는 유기전기소자 중 일예로 유기전계발광소자(OLED)에 대하여 설명하나, 본 발명은 이에 제한되지 않고 다양한 유기전기소자에 위에서 설명한 화합물들이 적용될 수 있다.As an example of the organic electroluminescent device to which the compounds of the present invention can be applied, an organic light emitting diode (OLED) will be described. However, the present invention is not limited thereto, and the above-described compounds may be applied to various organic electroluminescent devices.
본 발명의 다른 실시예는 제1 전극, 제2 전극 및 이들 전극 사이에 배치된 유기물층을 포함하는 유기전기소자에 있어서, 상기 유기물층 중 1층 이상이 본 발명의 화합물들을 포함하는 유기전계발광소자를 제공한다.Another embodiment of the present invention is an organic electroluminescent device comprising a first electrode, a second electrode and an organic material layer disposed between the electrodes, wherein at least one of the organic material layer comprises an organic electroluminescent device comprising the compounds of the present invention to provide.
도 1 내지 도 6은 본 발명의 화합물을 적용할 수 있는 유기전계발광소자의 예를 도시한 것이다.1 to 6 show examples of the organic light emitting display device to which the compound of the present invention can be applied.
본 발명의 다른 실시예에 따른 유기전계발광소자는, 정공주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층을 포함하는 유기물층 중 1층 이상을 본 발명의 화합물을 포함하도록 형성하는 것을 제외하고는, 당 기술 분야에 통상의 제조 방법 및 재료를 이용하여 당 기술 분야에 알려져 있는 구조로 제조될 수 있다.The organic light emitting device according to another embodiment of the present invention, except that at least one layer of an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer to include the compound of the present invention. Can be prepared with a structure known in the art using conventional manufacturing methods and materials in the art.
본 발명에 다른 실시예에 따른 유기전기발광소자의 구조는 도 1 내지 6에 예시되어 있으나, 이들 구조에만 한정된 것은 아니다. The structure of the organic electroluminescent device according to another embodiment of the present invention is illustrated in Figures 1 to 6, but is not limited to these structures.
도 1 내지 도 6을 참조해보면, 유기전기발광소자는 기판(101, 201, 301, 401, 501, 601), 양극(102, 202, 302, 402, 502, 602), 정공주입층(103, 203, 303), 정공수송층(104, 204, 304, 404), 발광층(105, 205, 305, 405, 505, 605), 전자수송층(106, 206, 406, 506), 전자주입층(107)을 포함하며, 도 2 내지 도 6에 도시된 것과 같이 발광층을 제외한 유기물층 중 적어도 일층이 생략될 수 있다.1 to 6, the organic electroluminescent device includes a substrate 101, 201, 301, 401, 501, 601, an anode 102, 202, 302, 402, 502, 602, a hole injection layer 103, 203, 303, hole transport layer 104, 204, 304, 404, light emitting layer 105, 205, 305, 405, 505, 605, electron transport layer 106, 206, 406, 506, electron injection layer 107 2 to 6, at least one layer of the organic material layer except for the light emitting layer may be omitted.
미도시하였지만, 이러한 유기전계발광소자는 정공의 이동을 저지하는 정공저지층(HBL), 전자의 이동을 저지하는 전자저지층(EBL), 발광을 돕거나 보조하는 발광보조층 및 보호층이 더 위치할 수도 있다. 보호층의 경우 최상위층에서 유기물층을 보호하거나 음극을 보호하도록 형성될 수 있다.Although not shown, the organic light emitting diode further includes a hole blocking layer (HBL) that blocks hole movement, an electron blocking layer (EBL) that blocks electrons from moving, a light emitting auxiliary layer that helps or assists light emission, and a protective layer. It may be located. The protective layer may be formed to protect the organic material layer or the cathode at the uppermost layer.
이때, 본 발명의 화합물은 정공주입층, 정공수송층, 발광층 및 전자수송층을 포함하는 유기물층 중 하나 이상에 포함될 수 있다.In this case, the compound of the present invention may be included in one or more of an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer.
구체적으로, 본 발명의 화합물은 정공주입층, 정공수송층, 발광층, 전자수송층, 전자주입층, 정공저지층, 전자저지층, 발광보조층 및 보호층 중 하나 이상을 대신하여 사용되거나 이들과 함께 층을 형성하여 사용될 수도 있다. 물론 유기물층 중 한층에만 사용되는 것이 아니라 두층 이상에 사용될 수 있다.Specifically, the compound of the present invention is used in place of or in combination with one or more of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a hole blocking layer, an electron blocking layer, a light emitting auxiliary layer and a protective layer It may be used to form. Of course, the organic layer may be used not only in one layer but also in two or more layers.
특히, 본 발명의 화합물에 따라서 정공주입 재료, 정공수송 재료, 전자주입 재료, 전자수송 재료, 발광 재료 및 패시베이션(케핑) 재료로 사용될 수 있고, 특히 단독으로 발광물질 및 호스트/도판트에서 호스트 또는 도판트로 사용될 수 있으며, 정공 주입, 정공수송층으로 사용될 수 있다.In particular, it can be used as a hole injection material, a hole transport material, an electron injection material, an electron transport material, a luminescent material and a passivation (kepping) material according to the compound of the present invention, in particular a host or in a luminescent material and host / dopant alone Can be used as a dopant, can be used as a hole injection, a hole transport layer.
예컨대, 본 발명의 다른 실시예에 따른 유기전계발광소자는 스퍼터링(sputtering)이나 전자빔 증발(e-beam evaporation)과 같은 PVD(physical vapor deposition) 방법을 이용하여, 기판 상에 금속 또는 전도성을 가지는 금속 산화물 또는 이들의 합금을 증착시켜 양극을 형성하고, 그 위에 정공주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층을 포함하는 유기물층을 형성한 후, 그 위에 음극으로 사용할 수 있는 물질을 증착시킴으로써 제조될 수 있다.For example, the organic light emitting device according to another embodiment of the present invention is a metal having a metal or conductivity on a substrate by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation An oxide or an alloy thereof is deposited to form an anode, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer is formed thereon, and then a material that can be used as a cathode is deposited thereon. Can be prepared.
이와 같은 방법 외에도, 기판 상에 음극 물질부터 유기물층, 양극 물질을 차례로 증착시켜 유기전기소자를 만들 수도 있다. 상기 유기물층은 정공주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층 등을 포함하는 다층 구조일 수도 있으나, 이에 한정되지 않고 단층 구조일 수 있다. In addition to the above method, an organic electronic device may be fabricated 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, an electron transport layer and an electron injection layer, but is not limited thereto and may have a single layer structure.
또한, 상기 유기물층은 다양한 고분자 소재를 사용하여 증착법이 아닌 용액 공정 또는 솔벤트 프로세스(solvent process), 예컨대 스핀 코팅, 딥 코팅, 닥터 블레이딩, 스크린 프린팅, 잉크젯 프린팅 또는 열 전사법 등의 방법에 의하여 더 적은 수의 층으로 제조할 수 있다.In addition, the organic layer may be formed using a variety of polymer materials, but not by a deposition process or a solvent process, such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer. It can be made with a small number of layers.
본 발명의 다른 실시예에 따른 유기전계발광소자는 위에서 설명한 화합물을 스핀 코팅(spin coating)이나 잉크젯(ink jet) 공정과 같은 용액 공정(soluble process)에 사용될 수도 있다.The organic light emitting device according to another embodiment of the present invention may be used in a solution process such as spin coating or ink jet process.
기판은 유기전계발광소자의 지지체이며, 실리콘 웨이퍼, 석영 또는 유리판, 금속판, 플라스틱 필름이나 시트 등이 사용될 수 있다.The substrate is a support of the organic light emitting device, and a silicon wafer, quartz or glass plate, metal plate, plastic film or sheet, or the like can be used.
기판 위에는 양극이 위치된다. 이러한 양극은 그 위에 위치되는 정공주입층으로 정공을 주입한다. 양극 물질로는 통상 유기물층으로 정공주입이 원활할 수 있도록 일함수가 큰 물질일 수 있다. 본 발명에서 사용될 수 있는 양극 물질의 구체적인 예로는 바나듐, 크롬, 구리, 아연, 금과 같은 금속 또는 이들의 합금; 아연산화물, 인듐산화물, 인듐주석 산화물(ITO), 인듐아연산화물(IZO)과 같은 금속 산화물; ZnO:Al 또는 SnO2:Sb와 같은 금속과 산화물의 조합; 폴리(3-메틸티오펜), 폴리[3,4-(에틸렌-1,2-디옥시)티오펜](PEDT), 폴리피롤 및 폴리아닐린과 같은 전도성 고분자 등이 있으나, 이들에만 한정되는 것은 아니다.An anode is positioned over the substrate. This anode injects holes into the hole injection layer located thereon. The positive electrode material may be a material having a large work function 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 oxides with metals 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.
양극 위에는 정공주입층이 위치된다. 이러한 정공주입층의 물질로 요구되는 조건은 양극으로부터의 정공주입 효율이 높으며, 주입된 정공을 효율적으로 수송할 수 있어야 한다. 이를 위해서는 이온화 포텐셜이 작고 가시광선에 대한 투명성이 높으며, 정공에 대한 안정성이 우수해야 한다.The hole injection layer is located on the anode. The conditions required for the material of the hole injection layer are high hole injection efficiency from the anode, it should be able to transport the injected holes efficiently. This requires a small ionization potential, high transparency to visible light, and excellent hole stability.
정공주입 물질로는 낮은 전압에서 양극으로부터 정공을 잘 주입받을 수 있는 물질로서, 정공주입 물질의 HOMO(highest occupied molecular orbital)가 양극 물질의 일함수와 주변 유기물층의 HOMO 사이일 수 있다. 정공주입 물질의 구체적인 예로는 금속 포피린(porphyrine), 올리고티오펜, 아릴아민 계열의 유기물, 헥사니트릴 헥사아자트리페닐렌, 퀴나크리돈(quinacridone) 계열의 유기물, 페릴렌(perylene) 계열의 유기물, 안트라퀴논 및 폴리아닐린과 폴리티오펜 계열의 전도성 고분자 등이 있으나, 이들에만 한정되는 것은 아니다.The hole injection material is a material that can be injected well from the anode at a low voltage, the highest occupied molecular orbital (HOMO) of the hole injection material may be 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.
상기 정공주입층 위에는 정공수송층이 위치된다. 이러한 정공수송층은 정공주입층으로부터 정공을 전달받아 그 위에 위치되는 유기발광층으로 수송하는 역할을 하며, 높은 정공 이동도와 정공에 대한 안정성 및 전자를 막아주는 역할를 한다. 이러한 일반적 요구 이외에 차체 표시용으로 응용할 경우 소자에 대한 내열성이 요구되며, 유리 전이 온도(Tg)가 70 ℃ 이상의 값을 갖는 재료일 수 있다.The hole transport layer is positioned on the hole injection layer. The hole transport layer receives holes from the hole injection layer and transports the holes to the organic light emitting layer located thereon, and serves to prevent high hole mobility, hole stability, and electrons. In addition to these general requirements, applications for vehicle body display require heat resistance to the device, and may be a material having a glass transition temperature (Tg) of 70 ° C. or higher.
이와 같은 조건을 만족하는 물질들로는 NPD(혹은 NPB라 함), 스피로-아릴아민계화합물, 페릴렌-아릴아민계화합물, 아자시클로헵타트리엔화합물, 비스(디페닐비닐페닐)안트라센, 실리콘게르마늄옥사이드화합물, 실리콘계아릴아민화합물 등이 될 수 있다.Materials satisfying these conditions include NPD (or NPB), spiro-arylamine compounds, perylene-arylamine compounds, azacycloheptatriene compounds, bis (diphenylvinylphenyl) anthracene and silicon germanium oxide. Compound, a silicon-based arylamine compound, and the like.
정공수송층 위에는 유기발광층이 위치된다. 이러한 유기발광층는 양극과 음극으로부터 각각 주입된 정공과 전자가 재결합하여 발광을 하는 층이며, 양자효율이 높은 물질로 이루어져 있다. 발광 물질로는 정공수송층과 전자수송층으로부터 정공과 전자를 각각 수송받아 결합시킴으로써 가시광선 영역의 빛을 낼 수 있는 물질로서, 형광이나 인광에 대한 양자효율이 좋은 물질일 수 있다.The organic light emitting layer is positioned on the hole transport layer. The organic light emitting layer is a layer for emitting light by recombination of holes and electrons injected from the anode and the cathode, respectively, and is made of a material having high quantum efficiency. 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 may be a material having good quantum efficiency for fluorescence or phosphorescence.
이와 같은 조건을 만족하는 물질 또는 화합물로는 녹색의 경우 Alq3가, 청색의 경우 Balq(8-hydroxyquinoline beryllium salt), DPVBi(4,4'-bis(2,2-diphenylethenyl)-1,1'-biphenyl) 계열, 스피로(Spiro) 물질, 스피로-DPVBi(Spiro-4,4'-bis(2,2-diphenylethenyl)-1,1'-biphenyl), LiPBO(2-(2-benzoxazoyl)-phenollithium salt), 비스(디페닐비닐페닐비닐)벤젠, 알루미늄-퀴놀린 금속착체, 이미다졸, 티아졸 및 옥사졸의 금속착체 등이 있으며, 청색 발광 효율을 높이기 위해 페릴렌, 및 BczVBi(3,3'[(1,1'-biphenyl)-4,4'-diyldi-2,1-ethenediyl]bis(9-ethyl)-9H-carbazole; DSA(distrylamine)류)를 소량 도핑하여 사용할 수 있다. 적색의 경우는 녹색 발광 물질에 DCJTB([2-(1,1-dimethylethyl)-6-[2-(2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H,5H-benzo(ij)quinolizin-9-yl)ethenyl]-4H-pyran-4-ylidene]-propanedinitrile)와 같은 물질을 소량 도핑하여 사용할 수 있다. Substances or compounds that satisfy these conditions include Alq3 for green, Balq (8-hydroxyquinoline beryllium salt) for blue, DPVBi (4,4'-bis (2,2-diphenylethenyl) -1,1'- biphenyl) series, Spiro material, Spiro-DPVBi (Spiro-4,4'-bis (2,2-diphenylethenyl) -1,1'-biphenyl), LiPBO (2- (2-benzoxazoyl) -phenollithium salt ), Bis (diphenylvinylphenylvinyl) benzene, aluminum-quinoline metal complex, metal complexes of imidazole, thiazole and oxazole, and the like, perylene, and BczVBi (3,3 '[ (1,1'-biphenyl) -4,4'-diyldi-2,1-ethenediyl] bis (9-ethyl) -9H-carbazole; DSA (distrylamine) can be used by doping in small amounts. In the case of red, DCJTB ([2- (1,1-dimethylethyl) -6- [2- (2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H, 5H Small amounts of doping such as -benzo (ij) quinolizin-9-yl) ethenyl] -4H-pyran-4-ylidene] -propanedinitrile) can be used.
잉크젯프린팅, 롤코팅, 스핀코팅 등의 공정을 사용하여 발광층을 형성할 경우에, 폴리페닐렌비닐렌(PPV) 계통의 고분자나 폴리 플로렌(poly 플루오렌(fluorene)) 등의 고분자를 유기발광층에 사용할 수 있다.When the light emitting layer is formed using a process such as inkjet printing, roll coating, or spin coating, an organic light emitting layer is formed of a polymer of polyphenylene vinylene (PPV) or a polymer such as poly fluorene. Can be used for
유기발광층 위에는 전자수송층이 위치된다. 이러한 전자수송층은 그 위에 위치되는 음극으로부터 전자주입 효율이 높고 주입된 전자를 효율적으로 수송할 수 있는 물질이 필요하다. 이를 위해서는 전자 친화력과 전자 이동속도가 크고 전자에 대한 안정성이 우수한 물질로 이루어져야 한다. The electron transport layer is positioned on the organic light emitting layer. The electron transport layer needs a material having high electron injection efficiency from the cathode positioned thereon and capable of efficiently transporting the injected electrons. To this end, it must be made of a material having high electron affinity and electron transfer speed and excellent stability to electrons.
이와 같은 조건을 충족시키는 전자수송 물질로는 구체적인 예로 8-히드록시퀴놀린의 Al 착물; Alq3를 포함한 착물; 유기 라디칼 화합물; 히드록시플라본-금속 착물 등이 있으나, 이들에만 한정되는 것은 아니다.Examples of the electron transport material that satisfies such conditions include Al complexes of 8-hydroxyquinoline; Complexes including Alq3; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto.
전자수송층 위에는 전자주입층이 적층된다. 전자주입층은 Balq, Alq3,Be(bq)2, Zn(BTZ)2, Zn(phq)2, PBD, spiro-PBD, TPBI, Tf-6P 등과 같은 금속착제화합물, imidazole ring 을 갖는 aromatic화합물이나 boron화합물 등을 포함하는 저분자 물질을 이용하여 제작할 수 있다. 이때, 전자주입층은 100Å ~ 300Å의 두께 범위에서 형성될 수 있다.The electron injection layer is stacked on the electron transport layer. The electron injection layer is a metal complex compound such as Balq, Alq3, Be (bq) 2, Zn (BTZ) 2, Zn (phq) 2, PBD, spiro-PBD, TPBI, Tf-6P, aromatic compound with imidazole ring, It can be produced using a low molecular material containing a boron compound and the like. At this time, the electron injection layer may be formed in a thickness range of 100 ~ 300Å.
전자주입층 위에는 음극이 위치된다. 이러한 음극은 전자를 주입하는 역할을 한다. 음극으로 사용하는 재료는 양극에 사용된 재료를 이용하는 것이 가능하며, 효율적인 전자주입을 위해서는 일 함수가 낮은 금속일 수 있다. 특히 주석, 마그네슘, 인듐, 칼슘, 나트륨, 리튬, 알루미늄, 은 등의 적당한 금속, 또는 그들의 적절한 합금이 사용될 수 있다. 또한 100 ㎛ 이하 두께의 리튬플루오라이드와 알루미늄, 산화리튬과 알루미늄, 스트론튬산화물과 알루미늄 등의 2 층 구조의 전극도 사용될 수 있다.The cathode is positioned on the electron injection layer. This cathode serves to inject electrons. The material used as the cathode may use the material used for the anode, and may be a metal having a low work function for efficient electron injection. In particular, a suitable metal such as tin, magnesium, indium, calcium, sodium, lithium, aluminum, silver, or a suitable alloy thereof can be used. In addition, electrodes having a two-layer structure such as lithium fluoride and aluminum, lithium oxide and aluminum, strontium oxide and aluminum having a thickness of 100 μm or less may also be used.
전술하였듯이, 본 발명의 화합물에 따라서 적색, 녹색, 청색, 흰색 등의 모든 칼라의 형광과 인광소자에 적합한 정공주입 재료, 정공수송 재료, 발광 재료, 전자수송 재료 및 전자주입 재료로 사용할 수 있으며, 다양한 색의 호스트 또는 도판트 물질로 사용될 수 있다.As described above, according to the compound of the present invention, it can be used as a hole injection material, a hole transport material, a light emitting material, an electron transport material, and an electron injection material suitable for fluorescence and phosphorescent devices of all colors such as red, green, blue, and white, It can be used as a host or dopant material of various colors.
본 발명에 따른 유기전계발광소자는 사용되는 재료에 따라 전면 발광형, 후면 발광형 또는 양면 발광형일 수 있다.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.
한편 본 발명은, 위에서 설명한 유기전기소자를 포함하는 디스플레이장치와, 이 디스플레이장치를 구동하는 제어부를 포함하는 단말을 포함한다. 이 단말은 현재 또는 장래의 유무선 통신단말을 의미한다. 이상에서 전술한 본 발명에 따른 단말은 휴대폰 등의 이동 통신 단말기일 수 있으며, PDA, 전자사전, PMP, 리모콘, 네비게이션, 게임기, 각종 TV, 각종 컴퓨터 등 모든 단말을 포함한다.Meanwhile, the present invention includes a display device including the organic electric element described above, and a terminal including a control unit for driving the display device. This terminal means a current or future wired or wireless communication terminal. The terminal according to the present invention described above may be a mobile communication terminal such as a mobile phone, and includes all terminals such as a PDA, an electronic dictionary, a PMP, a remote control, a navigation device, a game machine, various TVs, various computers, and the like.
이하 위에서 설명한 합성법에 따라 화합물들을 합성하고 그 화합물들을 유기전기소자, 예를 들어 유기전계발광소자의 유기물층에 적용한 예를 일반적으로 사용하는 화합물들과 비교하였다.Hereinafter, the compounds were synthesized according to the synthesis method described above, and the examples in which the compounds were applied to an organic material layer of an organic electroluminescent device, for example, an organic electroluminescent device, were compared with those of commonly used compounds.
비교예Comparative example
합성을 통해 얻은 여러 화합물을 각각 발광층의 발광 호스트 물질이나 정공 수송층으로 사용하여 통상적인 방법에 따라 유기전계 발광소자를 제작하였다.Various compounds obtained through synthesis were used as light emitting host materials or hole transporting layers of the light emitting layer, respectively, to fabricate an organic light emitting device according to a conventional method.
먼저, 유기 기판에 형성된 ITO층(양극)위에 우선 정공주입층으로서 구리프탈로사이아닌(이하 CuPc로 약기함)막을 진공증착하여 10 nm 두께로 형성하였다. 이어서 상기 발명화합물 및 비교예를 정공 수송층을으로 20 nm 두께로 진공 증착하였다. 진공 증착하여 비교 실험을 진행하였다. 이후, BD-052X(Idemitsu사)를 발광 도펀트로 사용하고 호스트 물질은 9,10-다이-(나프탈렌-2-안트라센) (이하 ADN으로 약기함)을 사용하였으며, 도핑 농도는 4%로 고정하여 비교 실험을 진행하였다. 이어서 전자주입층으로 트리스(8-퀴놀리놀)알루미늄을 40 nm의 두께로 성막하였다. 이후, 할로겐화 알킬리 금속인 LiF를 0.2 nm의 두께로 증착하고, 이어서 Al을 150 nm의 두께로 증착하여 Al/LiF를 음극으로 사용함으로서 유기전계 발광소자를 제조하였다.First, a copper phthalocyanine (hereinafter abbreviated as CuPc) film was vacuum-deposited as a hole injection layer on the ITO layer (anode) formed on the organic substrate to form a thickness of 10 nm. Subsequently, the inventive compound and the comparative example were vacuum deposited with a hole transport layer to a thickness of 20 nm. Vacuum deposition was carried out for comparative experiments. Subsequently, BD-052X (Idemitsu Co., Ltd.) was used as a light emitting dopant, and the host material was 9,10-di- (naphthalene-2-anthracene) (hereinafter abbreviated as ADN), and the doping concentration was fixed at 4%. A comparative experiment was conducted. Subsequently, tris (8-quinolinol) aluminum was deposited to a thickness of 40 nm with an electron injection layer. Subsequently, LiF, which is an alkyl halide metal, was deposited to a thickness of 0.2 nm, and then Al was deposited to a thickness of 150 nm to prepare an organic light emitting device by using Al / LiF as a cathode.
이와 같이 제조된 실시예 및 비교예 유기전기발광소자들에 순바이어스 직류전압을 가하여 포토리서치(photoresearch)사의 PR-650으로 전기발광(EL) 특성을 측정하였으며, 그 측정결과를 1000 cd/m2 기준 휘도에서 맥사이언스사에서 제조된 수명측정 장비를 통해 T95 수명을 측정하였다.The electroluminescent (EL) characteristics of the Example and Comparative Example organic electroluminescent devices manufactured as described above were applied to the PR-650 of photoresearch by applying a forward bias DC voltage, and the measurement result was 1000 cd / m 2. The T95 lifetime was measured using a life measurement instrument manufactured by McScience Inc. at the reference luminance.
비교실험예Comparative Experiment
합성된 화합물의 비교를 위해 본 발명의 화합물 대신에 하기식으로 표시되는 화합물을 정공수송층 물질로 사용하여 동일한 구조의 유기전계발광소자를 제작하였다.In order to compare the synthesized compound, an organic electroluminescent device having the same structure was manufactured using the compound represented by the following formula instead of the compound of the present invention as the hole transport layer material.
화학식 8
Figure PCTKR2012001905-appb-C000008
 Formula 8
Figure PCTKR2012001905-appb-C000008
표 1
정공수송층의 재료 전압( V ) 발광효율( cd/A ) 발광색 수명(h)
비교예 1 NPD 5.72 6.15 청색 120.22
실시예 1 화합물 1 5.49 6.34 청색 255.91
실시예 2 화합물 2 4.99 6.21 청색 255.83
실시예 3 화합물 3 4.95 6.17 청색 255.23
실시예 4 화합물 61 4.81 6.37 청색 269.41
실시예 5 화합물 62 4.83 6.21 청색 228.98
실시예 6 화합물 63 4.99 6.56 청색 254.55
실시예 7 화합물 88 4.88 6.12 청색 246.05
실시예 8 화합물 89 4.65 6.96 청색 245.95
실시예 9 화합물 90 4.71 6.70 청색 253.23
실시예 10 화합물 121 4.90 6.14 청색 248.19
실시예 11 화합물 122 4.53 6.88 청색 259.12
실시예 12 화합물 123 4.87 6.54 청색 251.35
실시예 13 화합물 163 5.03 6.54 청색 236.41
실시예 14 화합물 164 5.52 6.24 청색 238.35
실시예 15 화합물 165 5.50 6.09 청색 259.38
실시예 16 화합물 175 5.54 6.00 청색 234.25
실시예 17 화합물 176 5.44 6.57 청색 258.07
실시예 18 화합물 177 5.18 6.34 청색 272.02
Table 1
Material of hole transport layer Voltage (V) Luminous Efficiency (cd / A) Luminous color Life (h)
Comparative Example 1 NPD 5.72 6.15 blue 120.22
Example 1 Compound 1 5.49 6.34 blue 255.91
Example 2 Compound 2 4.99 6.21 blue 255.83
Example 3 Compound 3 4.95 6.17 blue 255.23
Example 4 Compound 61 4.81 6.37 blue 269.41
Example 5 Compound 62 4.83 6.21 blue 228.98
Example 6 Compound 63 4.99 6.56 blue 254.55
Example 7 Compound 88 4.88 6.12 blue 246.05
Example 8 Compound 89 4.65 6.96 blue 245.95
Example 9 Compound 90 4.71 6.70 blue 253.23
Example 10 Compound 121 4.90 6.14 blue 248.19
Example 11 Compound 122 4.53 6.88 blue 259.12
Example 12 Compound 123 4.87 6.54 blue 251.35
Example 13 Compound 163 5.03 6.54 blue 236.41
Example 14 Compound 164 5.52 6.24 blue 238.35
Example 15 Compound 165 5.50 6.09 blue 259.38
Example 16 Compound 175 5.54 6.00 blue 234.25
Example 17 Compound 176 5.44 6.57 blue 258.07
Example 18 Compound 177 5.18 6.34 blue 272.02
상기 표의 결과로부터 알 수 있듯이, 본 발명의 유기전계발광소자용 재료를 이용한 유기전계발광소자는 고효율이면서 색순도가 향상될 뿐만 아니라 구동전압 또한 현저히 향상시킬 수 있다.As can be seen from the results of the above table, the organic light emitting device using the organic light emitting device material of the present invention can not only improve color purity but also improve driving voltage significantly.
따라서 이러한 특성을 바탕으로 유기전계발광소자 효율 및 수명특성을 현저히 개선시킬 수 있다.Therefore, it is possible to remarkably improve the efficiency and lifespan of the organic light emitting device based on these characteristics.
표 1에 표시하지 않은 화합물들을 정공수송층으로 사용할 경우 구동전압이나 발광효율, 발광색, 수명도 표 1의 실시예들과 동일하게 비교예보다 고효율이면서 색순도가 향상될 뿐만 아니라 구동전압 또한 현저히 향상시킬 수 있는 것을 확인하였다. 이러한 결과들은 표1과 실질적으로 동일하여 생략하나 필요에 따라 본 명세서의 일부를 구성할 수 있다.When the compounds not shown in Table 1 are used as the hole transport layer, the driving voltage, luminous efficiency, emission color, and lifespan are not only higher than those of the comparative example, but also higher in color purity and improved in driving voltage. It confirmed that there was. These results are substantially the same as Table 1 and omitted, but may form part of the present specification as necessary.
상기 실시예와 비교예의 표를 통하여 본 발명의 화합물의 발광효율 및 구동특성이 현저히 우수함을 확인하였으나 상기 실시예와 비교예의 표의 화합물들에서 치환기들은 다른 치환체로 치환될 수 있다. 따라서, 상기 실시예와 비교예의 표의 화합물들에서 치환기들이 다른 치환체로 치환된 실시예와 비교예는 본 명세서의 일부를 구성할 수 있다. Although the luminous efficiency and driving characteristics of the compounds of the present invention were remarkably excellent through the tables of Examples and Comparative Examples, the substituents in the compounds of the Examples and Comparative Examples may be substituted with other substituents. Therefore, the Examples and Comparative Examples in which the substituents are substituted with other substituents in the compounds of Tables of Examples and Comparative Examples may form part of the present specification.
이상의 설명은 본 발명을 예시적으로 설명한 것에 불과한 것으로, 본 발명이 속하는 기술분야에서 통상의 지식을 가지는 자라면 본 발명의 본질적인 특성에서 벗어나지 않는 범위에서 다양한 변형이 가능할 것이다. 따라서, 본 명세서에 개시된 실시예들은 본 발명을 한정하기 위한 것이 아니라 설명하기 위한 것이고, 이러한 실시예에 의하여 본 발명의 사상과 범위가 한정되는 것은 아니다. 본 발명의 보호범위는 아래의 청구범위에 의하여 해석되어야 하며, 그와 동등한 범위 내에 있는 모든 기술은 본 발명의 권리범위에 포함하는 것으로 해석되어야 할 것이다.The above description is merely illustrative of the present invention, and those skilled in the art to which the present invention pertains may various modifications without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed herein are not intended to limit the present invention but to describe the present invention, and the spirit and scope of the present invention are not limited by these embodiments. The protection scope of the present invention should be interpreted by the following claims, and all the technologies within the equivalent scope should be interpreted as being included in the scope of the present invention.
CROSS-REFERENCE TO RELATED APPLICATIONCROSS-REFERENCE TO RELATED APPLICATION
본 특허출원은 2011년 03월 21일 한국에 출원한 특허출원번호 제 10-2011-0024817 호에 대해 미국 특허법 119(a)조 (35 U.S.C § 119(a))에 따라 우선권을 주장하며, 그 모든 내용은 참고문헌으로 본 특허출원에 병합된다. 아울러, 본 특허출원은 미국 이외에 국가에 대해서도 위와 동일한 이유로 우선권을 주장하면 그 모든 내용은 참고문헌으로 본 특허출원에 병합된다.This patent application claims priority to US Patent Application No. 10-2011-0024817, filed in Korea on March 21, 2011, pursuant to Article 119 (a) (35 USC § 119 (a)). All content is incorporated by reference in this patent application. In addition, if this patent application claims priority to a country other than the United States for the same reason, all its contents are incorporated into this patent application by reference.

Claims (10)

  1. 하기 화학식 1 또는 화학식 2로 표시되는 화합물.A compound represented by the following formula (1) or (2).
    [화학식 1]                     [Formula 1]
    Figure PCTKR2012001905-appb-I000078
    Figure PCTKR2012001905-appb-I000078
    [화학식 2]                            [Formula 2]
    Figure PCTKR2012001905-appb-I000079
    Figure PCTKR2012001905-appb-I000079
    상기 화학식에서,In the above formula,
    (1) R1, R2, R3 및 R4는 각각 서로 독립적으로,(1) R 1 , R 2 , R 3 and R 4 are each independently of one another,
    수소; 중수소; 치환 또는 비치환된 C1~C50의 알킬기; 치환 또는 비치환된 C6~C60의 아릴기; 또는 황(S), 질소(N), 산소(O), 인(P), 규소(Si) 중 적어도 하나의 헤테로원자를 포함하는 치환 또는 비치환된 C2~C50의 헤테로아릴기;이며, Hydrogen; heavy hydrogen; Substituted or unsubstituted C One Through C 50 Alkyl group; Substituted or unsubstituted C 6 ~ C 60 An aryl group; Or a substituted or unsubstituted C 2 to C 50 heteroaryl group including at least one hetero atom of sulfur (S), nitrogen (N), oxygen (O), phosphorus (P), or silicon (Si); ,
    (2) L은 단일결합; (2) L is a single bond;
    할로겐기, C1~C20의 알킬기, C2~C20의 알케닐기, C1~C20의 알콕시기, C6~C20의 아릴기, C7~C20의 아릴알킬기, C8~C20의 아릴알케닐기, C2~C20의 헤테로 고리기, 니트릴기 및 아세틸렌기로 이루어진 군에서 선택된 1개 이상의 치환기로 치환 또는 비치환된 C6~C60의 아릴렌기; 또는Halogen group, C 1 ~ C 20 alkyl group, C 2 ~ C 20 alkenyl group, C 1 ~ C 20 alkoxy group, C 6 ~ C 20 aryl group, C 7 ~ C 20 arylalkyl group, C 8 ~ C 6 ~ C 60 arylene group unsubstituted or substituted with one or more substituents selected from the group consisting of C 20 arylalkenyl group, C 2 ~ C 20 heterocyclic group, nitrile group and acetylene group; or
    할로겐기, C1~C20의 알킬기, C2~C20의 알케닐기, C1~C20의 알콕시기, C6~C20의 아릴아민기, C6~C20의 아릴기, C7~C20의 아릴알킬기, C8~C20의 아릴알케닐기, C2~C20의 헤테로 고리기, 니트릴기 및 아세틸렌기로 이루어진 군에서 선택된 하나 이상의 치환기로 치환 또는 비치환 되고 O, N 또는 S 중 적어도 하나의 헤테로원자를 포함하는 C2~C50의 헤테로아릴렌기;이며, A halogen group, a C 1 to C 20 alkyl group, a C 2 to C 20 alkenyl group, a C 1 to C 20 alkoxy group, a C 6 to C 20 arylamine group, a C 6 to C 20 aryl group, C 7 Or unsubstituted or substituted with one or more substituents selected from the group consisting of -C 20 arylalkyl group, C 8 -C 20 arylalkenyl group, C 2 -C 20 heterocyclic group, nitrile group and acetylene group C 2 ~ C 50 Heteroarylene group containing at least one hetero atom;
    (3) Ar1 및 Ar2는 각각 서로 독립적으로,(3) Ar 1 and Ar 2 are each independently of the other,
    C1~C20의 알킬기, C2~C20의 알케닐기, C1~C20의 알콕시기, C6~C20의 아릴기, C7~C20의 아릴알킬기, C8~C20의 아릴알케닐기, C2~C20의 헤테로 고리기, 니트릴기 및 아세틸렌기로 이루어진 군에서 선택된 치환기로 치환 또는 비치환된 C1~C50의 알킬기; C 1 ~ C 20 Alkyl group, C 2 ~ C 20 Alkenyl group, C 1 ~ C 20 Alkoxy group, C 6 ~ C 20 Aryl group, C 7 ~ C 20 arylalkyl group, C 8 ~ C 20 A C 1 -C 50 alkyl group unsubstituted or substituted with a substituent selected from the group consisting of an aryl alkenyl group, a C 2 -C 20 heterocyclic group, a nitrile group and an acetylene group;
    할로겐, 아미노기, 니트릴기, 니트로기, C1~C20의 알킬기, C1~C20의 알콕시기, C1~C20의 알킬아민기, C1~C20의 알킬티오펜기, C6~C20의 아릴티오펜기, C2~C20의 알케닐기, C2~C20의 알키닐기, C3~C20의 시클로알킬기, 중수소로 치환된 C6~C20의 아릴기, C6~C20의 아릴기, C8~C20의 아릴알케닐기, 실란기, 붕소기, 게르마늄기, C2~C20의 헤테로고리기로 이루어진 군으로부터 선택되는 하나 이상의 기로 치환 또는 비치환된 C6~C20의 아릴기; 또는Halogen, amino group, nitrile group, nitro group, C 1 ~ C 20 alkyl group, C 1 ~ C 20 alkoxy group, C 1 ~ C 20 alkylamine group, C 1 ~ C 20 alkylthiophene group, C 6 C 20 -C 20 arylthiophene group, C 2 -C 20 alkenyl group, C 2 -C 20 alkynyl group, C 3 -C 20 cycloalkyl group, C 6 -C 20 aryl group substituted with deuterium, C C unsubstituted or substituted with one or more groups selected from the group consisting of an aryl group of 6 to C 20 , an aryl alkenyl group of C 8 to C 20 , a silane group, a boron group, a germanium group and a heterocyclic group of C 2 to C 20 Aryl groups of 6 to C 20 ; or
    할로겐기, C1~C20의 알킬기, C2~C20의 알케닐기, C1~C20의 알콕시기, C6~C20의 아릴아민기, C6~C20의 아릴기, C7~C20의 아릴알킬기, C8~C20의 아릴알케닐기, C2~C20의 헤테로 고리기, 니트릴기 및 아세틸렌기로 이루어진 군에서 선택된 하나 이상의 치환기로 치환 또는 비치환 되고 O, N, S 중 적어도 하나의 헤테로 원자를 포함하는 C2~C50의 헤테로아릴기;이며,A halogen group, a C 1 to C 20 alkyl group, a C 2 to C 20 alkenyl group, a C 1 to C 20 alkoxy group, a C 6 to C 20 arylamine group, a C 6 to C 20 aryl group, C 7 Or an unsubstituted or substituted with one or more substituents selected from the group consisting of -C 20 arylalkyl group, C 8 -C 20 arylalkenyl group, C 2 -C 20 heterocyclic group, nitrile group and acetylene group C 2 ~ C 50 Heteroaryl group containing at least one hetero atom;
    (4) l과 o는 0~2의 정수이고, n 과 m은 1~4의 정수이며,(4) l and o are integers from 0 to 2, n and m are integers from 1 to 4,
    (5) R1 내지 R4 는 인접한 기와 서로 결합 또는 반응하여 포화 또는 불포화 고리를 형성할 수 있다.(5) ROne To R4                  May combine or react with adjacent groups to form a saturated or unsaturated ring.
  2. 제 1항에 있어서,The method of claim 1,
    하기 화학식 중 하나인 것을 특징으로 하는 화합물. Compounds, characterized in that one of the formula.
    [화학식 3][Formula 3]
    Figure PCTKR2012001905-appb-I000080
    Figure PCTKR2012001905-appb-I000080
    [화학식 4][Formula 4]
    Figure PCTKR2012001905-appb-I000081
    Figure PCTKR2012001905-appb-I000081
    [화학식 5][Formula 5]
    Figure PCTKR2012001905-appb-I000082
    Figure PCTKR2012001905-appb-I000082
    [화학식 6][Formula 6]
    Figure PCTKR2012001905-appb-I000083
    Figure PCTKR2012001905-appb-I000083
  3. 제 1항에 있어서, The method of claim 1,
    상기 아릴기는, 페닐기, 1-나프틸기, 2-나프틸기, 1-안트릴기, 2-안트릴기, 9-안트릴기, 1-페난트릴기, 2-페난트릴기, 3-페난트릴기, 4-페난트릴기, 1-페날리닐기, 2-페날리닐기, 9-페난트릴기, 1-피렌일기, 2-피렌일기, 4-피렌일기, 2-바이페닐릴기, 3-바이페닐릴기, 4-바이페닐릴기, p-터페닐-4-일기, p-터페닐-3-일기, p-터페닐-2-일기, m-터페닐-4-일기, m-터페닐-3-일기, m-터페닐-2-일기, o-톨릴기, m-톨릴기, p-톨릴기, p-t-뷰틸페닐기, p-(2-페닐프로필)페닐기, 3-메틸-2-나프틸기, 4-메틸-1-나프틸기, 4-메틸-1-안트릴기, 4’-메틸바이페닐릴기, 4”-t-뷰틸-p-터페닐-4-일기, 플루오렌일기로 이루어진 군에서 선택된 하나 또는 하나 이사이며, 상기 헤테로아닐기는 2-피롤릴기, 3-피롤릴기, 2-피라진일기, 2-피리딘일기, 3-피리딘일기, 4-피리딘일기, 1-인돌릴기, 2-인돌릴기, 3-인돌릴기, 4-인돌릴기, 5-인돌릴기, 6-인돌릴기, 7-인돌릴기, 1-아이소인돌릴기, 3-아이소인돌릴기, 4-아이소인돌릴기, 5-아이소인돌릴기, 6-아이소인돌릴기, 7-아이소인돌릴기, 2-퓨릴기, 3-퓨릴기, 2-벤조퓨란일기, 3-벤조퓨란일기, 4-벤조퓨란일기, 5-벤조퓨란일기, 6-벤조퓨란일기, 7-벤조퓨란일기, 1-아이소벤조퓨란일기, 3-아이소벤조퓨란일기, 4-아이소벤조퓨란일기, 5-아이소벤조퓨란일기, 6-아이소벤조퓨란일기, 7-아이소벤조퓨란일기, 2-퀴놀릴기, 3-퀴놀릴기, 4-퀴놀릴기, 5-퀴놀릴기, 6-퀴놀릴기, 7-퀴놀릴기, 8-퀴놀릴기, 1-아이소퀴놀릴기, 3-아이소퀴놀릴기, 4-아이소퀴놀릴기, 5-아이소퀴놀릴기, 6-아이소퀴놀릴기, 7-아이소퀴놀릴기, 8-아이소퀴놀릴기, 2-퀴녹살린일기, 5-퀴녹살린일기, 6-퀴녹살린일기, 1-카바졸릴기, 2-카바졸릴기, 3-카바졸릴기, 4-카바졸릴기, 1-아크리딘일기, 2-아크리딘일기, 3-아크리딘일기, 4-아크리딘일기, 9-아크리딘일기, 1,10-페난트롤린-2-일기, 1,10-페난트롤린-3-일기, 1,10-페난트롤린-4-일기, 1,10-페난트롤린-5-일기,1-페나진일기, 2-페나진일기, 1-페노티아진일기, 2-페노티아진일기, 3-페노티아진일기, 4-페노티아진일기, 1-페녹사진일기, 2-페녹사진일기, 3-페녹사진일기, 4-페녹사진일기, 2-옥사졸릴기, 4-옥사졸릴기, 5-옥사졸릴기, 2-옥사다이아졸릴기, 5-옥사다이아졸릴기, 3-퓨라잔일기, 2-티엔일기, 3-티엔일기, 2-메틸피롤-1-일기, 2-메틸피롤-3-일기, 2-메틸피롤-4-일기, 2-메틸피롤-5-일기, 3-메틸피롤-1-일기, 3-메틸피롤-2-일기, 3-메틸피롤-4-일기, 3-메틸피롤-5-일기, 2-t-뷰틸피롤-4-일기, 3-(2-페닐프로필)피롤-1-일기, 2-메틸-1-인돌릴기, 4-메틸-1-인돌릴기, 2-메틸-3-인돌릴기, 4-메틸-3-인돌릴기, 2-t-뷰틸-1-인돌릴기, 4-t-뷰틸-1-인돌릴기, 2-t-뷰틸-3-인돌릴기, 4-t-뷰틸-3-인돌릴기로 이루어지 군에서 선택된 적어도 하나인 것을 특징으로 하는 화합물. The aryl group is a phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl Group, 4-phenanthryl group, 1-phenalinyl group, 2-phenalylyl group, 9-phenanthryl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, 2-biphenylyl group, 3-bi Phenylyl group, 4-biphenylyl group, p-terphenyl-4-yl group, p-terphenyl-3-yl group, p-terphenyl-2-yl group, m-terphenyl-4-yl group, m-terphenyl- 3-yl group, m-terphenyl-2-yl group, o-tolyl group, m-tolyl group, p-tolyl group, pt-butylphenyl group, p- (2-phenylpropyl) phenyl group, 3-methyl-2-naph A methyl group, 4-methyl-1-naphthyl group, 4-methyl-1-anthryl group, 4'-methylbiphenylyl group, 4 ”-t-butyl-p-terphenyl-4-yl group, fluorenyl group One or one member selected from the group, wherein the heteroanyl group is 2-pyrrolyl group, 3-pyrrolyl group, 2-pyrazinyl group, 2-pyridinyl group, 3-pyridinyl group, 4-pyridinyl group, 1-indolyl group, 2- Indolyl group, 3-indolyl group, 4-indolyl group, 5-indolyl group, 6-indolyl group, 7-indolyl group, 1-isoindoleyl group, 3-isoindoleyl group, 4-isoindoleyl group, 5-isoindoleyl group, 6- Isoindolyl group, 7-isoindolyl group, 2-furyl group, 3-furyl group, 2-benzofuranyl group, 3-benzofuranyl group, 4-benzofuranyl group, 5-benzofuranyl group, 6-benzofuran Diary, 7-benzofuranyl group, 1-isobenzofuranyl group, 3-isobenzofuranyl group, 4-isobenzofuranyl group, 5-isobenzofuranyl group, 6-isobenzofuranyl group, 7-isobenzofuranyl group, 2-quinolyl group, 3-quinolyl group, 4-quinolyl group, 5-quinolyl group, 6-quinolyl group, 7-quinolyl group, 8-quinolyl group, 1-isoquinolyl group, 3 Isoquinolyl group, 4-isoquinolyl group, 5-isoquinolyl group, 6-isoquinolyl group, 7-isoquinolyl group, 8-isoquinolyl group, 2-quinoxalinyl group, 5-quinoxyl group Salinyl group, 6-quinoxalinyl group, 1-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, 4-carbazolyl group, 1-acryl Diary, 2-acridinyl, 3-acridinyl, 4-acridinyl, 9-acridinyl, 1,10-phenanthroline-2-yl, 1,10-phenanthroline- 3-yl, 1,10-phenanthroline-4-yl, 1,10-phenanthroline-5-yl, 1-phenazineyl, 2-phenazineyl, 1-phenothiazineyl, 2-phene Notthiazine group, 3-phenothiazine group, 4-phenothiazine group, 1-phenoxazine group, 2-phenoxazine group, 3-phenoxazine group, 4-phenoxazine group, 2-oxazolyl group, 4- Oxazolyl group, 5-oxazolyl group, 2-oxadiazolyl group, 5-oxadiazolyl group, 3-furazanyl group, 2-thienyl group, 3-thienyl group, 2-methylpyrrole-1-yl group, 2 -Methylpyrrole-3-yl group, 2-methylpyrrole-4-yl group, 2-methylpyrrole-5-yl group, 3-methylpyrrole-1-yl group, 3-methylpyrrole-2-yl group, 3-methylpyrrole-4 -Yl group, 3-methylpyrrole-5-yl group, 2-t-butylpyrrole-4-yl group, 3- (2-phenylpropyl) pyrrole-1-yl group, 2-methyl-1-indolyl group, 4-methyl- 1-indolyl group, 2-methyl-3-indolyl group, 4-methyl-3-indolyl group, 2-t-butyl-1-indolyl group And 4-t-butyl-1-indolyl group, 2-t-butyl-3-indolyl group, 4-t-butyl-3-indolyl group.
  4. 제 1항에 있어서, The method of claim 1,
    하기 화합물 중 하나인 것을 특징으로 하는 화합물.Compound which is one of the following compounds.
    Figure PCTKR2012001905-appb-I000084
    Figure PCTKR2012001905-appb-I000084
    Figure PCTKR2012001905-appb-I000085
    Figure PCTKR2012001905-appb-I000085
    Figure PCTKR2012001905-appb-I000086
    Figure PCTKR2012001905-appb-I000086
    Figure PCTKR2012001905-appb-I000087
    Figure PCTKR2012001905-appb-I000087
    Figure PCTKR2012001905-appb-I000088
    Figure PCTKR2012001905-appb-I000088
    Figure PCTKR2012001905-appb-I000089
    Figure PCTKR2012001905-appb-I000089
    Figure PCTKR2012001905-appb-I000090
    Figure PCTKR2012001905-appb-I000090
    Figure PCTKR2012001905-appb-I000091
    Figure PCTKR2012001905-appb-I000091
    Figure PCTKR2012001905-appb-I000092
    Figure PCTKR2012001905-appb-I000092
    Figure PCTKR2012001905-appb-I000093
    Figure PCTKR2012001905-appb-I000093
    Figure PCTKR2012001905-appb-I000094
    Figure PCTKR2012001905-appb-I000094
    Figure PCTKR2012001905-appb-I000095
    Figure PCTKR2012001905-appb-I000095
    Figure PCTKR2012001905-appb-I000096
    Figure PCTKR2012001905-appb-I000096
    Figure PCTKR2012001905-appb-I000097
    Figure PCTKR2012001905-appb-I000097
    Figure PCTKR2012001905-appb-I000098
    Figure PCTKR2012001905-appb-I000098
    Figure PCTKR2012001905-appb-I000099
    Figure PCTKR2012001905-appb-I000099
    Figure PCTKR2012001905-appb-I000100
    Figure PCTKR2012001905-appb-I000100
    Figure PCTKR2012001905-appb-I000101
    Figure PCTKR2012001905-appb-I000101
    Figure PCTKR2012001905-appb-I000102
    Figure PCTKR2012001905-appb-I000102
    Figure PCTKR2012001905-appb-I000103
    Figure PCTKR2012001905-appb-I000103
    Figure PCTKR2012001905-appb-I000104
    Figure PCTKR2012001905-appb-I000104
    Figure PCTKR2012001905-appb-I000105
    Figure PCTKR2012001905-appb-I000105
    Figure PCTKR2012001905-appb-I000106
    Figure PCTKR2012001905-appb-I000106
    Figure PCTKR2012001905-appb-I000107
    Figure PCTKR2012001905-appb-I000107
    Figure PCTKR2012001905-appb-I000108
    Figure PCTKR2012001905-appb-I000108
    Figure PCTKR2012001905-appb-I000109
    Figure PCTKR2012001905-appb-I000109
    Figure PCTKR2012001905-appb-I000110
    Figure PCTKR2012001905-appb-I000110
    Figure PCTKR2012001905-appb-I000111
    Figure PCTKR2012001905-appb-I000111
    Figure PCTKR2012001905-appb-I000112
    Figure PCTKR2012001905-appb-I000112
    Figure PCTKR2012001905-appb-I000113
    Figure PCTKR2012001905-appb-I000113
    Figure PCTKR2012001905-appb-I000114
    Figure PCTKR2012001905-appb-I000114
    Figure PCTKR2012001905-appb-I000115
    Figure PCTKR2012001905-appb-I000115
    Figure PCTKR2012001905-appb-I000116
    Figure PCTKR2012001905-appb-I000116
    Figure PCTKR2012001905-appb-I000117
    Figure PCTKR2012001905-appb-I000117
    Figure PCTKR2012001905-appb-I000118
    Figure PCTKR2012001905-appb-I000118
    Figure PCTKR2012001905-appb-I000119
    Figure PCTKR2012001905-appb-I000119
  5. 제 1항의 화합물을 포함하는 1층 이상의 유기물층을 포함하는 유기전기소자.An organic electric device comprising at least one organic material layer comprising the compound of claim 1.
  6. 제 5항에 있어서,The method of claim 5,
    상기 화합물을 용액공정에 의해 상기 유기물층으로 형성하는 것을 특징으로 하는 유기전기소자.An organic electric device, characterized in that to form the compound to the organic material layer by a solution process.
  7. 제 5항에 있어서, The method of claim 5,
    상기 유기전기소자는 제 1전극, 제 2전극 및, 상기 제 1전극과 상기 제 2전극 사이에 형성된 상기 유기물층을 포함하는 유기전계발광소자인 것을 특징으로 하는 유기전기소자.The organic electroluminescent device is an organic electroluminescent device comprising a first electrode, a second electrode, and the organic material layer formed between the first electrode and the second electrode.
  8. 제 7항에 있어서, The method of claim 7, wherein
    상기 유기물층은 정공주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층 중 적어도 하나인 것을 특징으로 하는 유기전기소자.The organic material layer is an organic electric device, characterized in that at least one of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.
  9. 제 5항의 유기전기소자를 포함하는 디스플레이 장치 및; A display device comprising the organic electroluminescent element of claim 5;
    상기 디스플레이 장치를 구동하는 제어부를 포함하는 전자장치.And a controller for driving the display device.
  10. 제 9항에 있어서, The method of claim 9,
    상기 유기전기소자는 유기전계발광소자(OLED), 유기태양전지, 유기감광체(OPC) 드럼, 유기트랜지스트(유기 TFT)중 적어도 하나인 것을 특징으로 하는 전자장치. The organic electronic device is at least one of an organic light emitting diode (OLED), an organic solar cell, an organic photoconductor (OPC) drum, and an organic transistor (organic TFT).
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103468245A (en) * 2013-08-16 2013-12-25 石家庄诚志永华显示材料有限公司 OLED material with carrier transmittability as well as preparation method and application thereof
CN103601668A (en) * 2013-11-26 2014-02-26 大连联化化学有限公司 Preparation method of N-phenyl-3-bromocarbazole
WO2016201513A1 (en) * 2015-06-18 2016-12-22 Commonwealth Scientific And Industrial Research Organisation Electroactive materials, printing compositions and methods of manufacturing solar cells
CN107868031A (en) * 2016-09-28 2018-04-03 江苏三月光电科技有限公司 One kind is using the fluorenes of 9,9 ' spiral shell two as the organic compound of core and its application on organic electroluminescence device
CN107868038A (en) * 2016-09-28 2018-04-03 江苏三月光电科技有限公司 One kind contains organic compound and its application of the fluorenes of 9,9 ' spiral shell two
CN109134348A (en) * 2018-09-30 2019-01-04 长春海谱润斯科技有限公司 A kind of carbazole compound and its organic luminescent device
CN110835304A (en) * 2018-08-17 2020-02-25 江苏三月光电科技有限公司 Compound with spirofluorene structure as core, preparation method and application thereof
CN111362866A (en) * 2018-12-26 2020-07-03 江苏三月光电科技有限公司 Azabenzene modified organic compound and application thereof

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2762478A1 (en) * 2011-09-15 2014-08-06 Idemitsu Kosan Co., Ltd Aromatic amine derivative and organic electroluminescence element using same
KR101973030B1 (en) * 2012-06-20 2019-04-30 덕산네오룩스 주식회사 Compound for organic electronic element, organic electronic element using the same, and a electronic device thereof
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050221124A1 (en) * 2004-04-02 2005-10-06 Seok-Hwan Hwang Fluorene-based compound and organic electroluminescent display device using the same
KR20090112148A (en) * 2008-04-23 2009-10-28 덕산하이메탈(주) Organic electroluminescent devices comprising fluorene derivatives in organic layer thereof
KR20090129799A (en) * 2008-06-13 2009-12-17 덕산하이메탈(주) Novel carbazole derivatives and organic electroluminescent device comprising same
KR20100008947A (en) * 2008-07-17 2010-01-27 덕산하이메탈(주) Fluorenecarbazole derivative and organic electroluminescent device comprising same

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101072812B1 (en) * 2009-03-30 2011-10-14 덕산하이메탈(주) Chemiclal having an asymmetric structure which froms the ring by combining carbazole and fluorine and organic electroric element using the same, terminal thererof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050221124A1 (en) * 2004-04-02 2005-10-06 Seok-Hwan Hwang Fluorene-based compound and organic electroluminescent display device using the same
KR20090112148A (en) * 2008-04-23 2009-10-28 덕산하이메탈(주) Organic electroluminescent devices comprising fluorene derivatives in organic layer thereof
KR20090129799A (en) * 2008-06-13 2009-12-17 덕산하이메탈(주) Novel carbazole derivatives and organic electroluminescent device comprising same
KR20100008947A (en) * 2008-07-17 2010-01-27 덕산하이메탈(주) Fluorenecarbazole derivative and organic electroluminescent device comprising same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
OZLEM USLUER ET AL.: 'Fluorene-Carbazole Dendrimers : Synthesis, Thermal, Photophysical and Electroluminescent Device Properties' ADVANCED FUNCTIONAL MATERIAL vol. 20, no. 23, 2010, ISSN 1616-3028 pages 4152 - 4161 *

Cited By (8)

* Cited by examiner, † Cited by third party
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CN103601668A (en) * 2013-11-26 2014-02-26 大连联化化学有限公司 Preparation method of N-phenyl-3-bromocarbazole
WO2016201513A1 (en) * 2015-06-18 2016-12-22 Commonwealth Scientific And Industrial Research Organisation Electroactive materials, printing compositions and methods of manufacturing solar cells
CN107868031A (en) * 2016-09-28 2018-04-03 江苏三月光电科技有限公司 One kind is using the fluorenes of 9,9 ' spiral shell two as the organic compound of core and its application on organic electroluminescence device
CN107868038A (en) * 2016-09-28 2018-04-03 江苏三月光电科技有限公司 One kind contains organic compound and its application of the fluorenes of 9,9 ' spiral shell two
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CN109134348A (en) * 2018-09-30 2019-01-04 长春海谱润斯科技有限公司 A kind of carbazole compound and its organic luminescent device
CN111362866A (en) * 2018-12-26 2020-07-03 江苏三月光电科技有限公司 Azabenzene modified organic compound and application thereof

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